Unsteady state diffusion-adsorption-reaction. Selectivity of consecutive reactions on porous catalyst particles
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Juan Rafael García
Abstract
The simultaneous processes of diffusion, adsorption and chemical reaction, considering the transient nature of the concentration profiles in the porous catalyst particles as applied to the analysis of consecutive reactions A → B → C, where reactant and products are subjected to diffusion limitations, are analyzed. The concentrations of the desired intermediate product B, both the average in the catalytic particles and the observed in the fluid phase, initially increase as a function of time until reaching a maximum value and then decline due to the consumption in the secondary reaction. Due to the diffusion restrictions and the adsorption effect, the observed selectivities, calculated from the concentrations in the fluid phase, are always lower than the true selectivities, which also include the amounts accumulated in the particles. Besides depending on the rates of the primary and secondary reactions, the observed yield of product B also depends on the system adsorption capacity, i.e., the relationship between the capacities of the particles and the external fluid phase to accumulate the reactant species. For a given relationship between the intrinsic rates of the primary and secondary reactions, the higher the system adsorption capacity, the lower the observed yield of B as a function of conversion. The relationship between the observed yield of B and the observed conversion of A, calculated considering the transient state of the concentration profiles in the particles, is coincident with that predicted by classical models, which assume the steady state in the particles, when the system adsorption capacity is extremely small.
Funding source: Universidad Nacional del Litoral (UNL, Santa Fe, Argentina)
Award Identifier / Grant number: Proj. CAID 50420150100068LI
Funding source: Universidad Nacional de Mar del Plata
Award Identifier / Grant number: Project ING 448/16
Funding source: Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT)
Award Identifier / Grant number: PICT 1208/2016
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Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
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Research funding: This work has been carried out with financial support of the Universidad Nacional del Litoral (UNL, Santa Fe, Argentina), Proj. CAID 50420150100068LI; Universidad Nacional de Mar del Plata (Project ING 448/16); and Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT), PICT 1208/2016.
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Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
References
Al-Khattaf, S., J. A. Atias, K. Jarosch, A. L. Bonivardi, and H. de Lasa. 2002. “Diffusion and Catalytic Cracking of 1,3,5 Tri-iso-propyl-benzene in FCC Catalysts.” Chemical Engineering Science 57: 4909–20.10.1016/S0009-2509(02)00277-4Search in Google Scholar
Al-Sabawi, M., and H. de Lasa. 2010. “Modeling Thermal and Catalytic Conversion of Decalin Under Industrial FCC Operating Conditions.” Chemical Engineering Science 65 (2): 626–44. https://doi.org/10.1016/j.ces.2009.08.035.Search in Google Scholar
Balakotaiah, V. 2008. “On the Relationship Between Aris and Sherwood Numbers and Friction and Effectiveness Factors.” Chemical Engineering Science 63 (24): 5802–12. https://doi.org/10.1016/j.ces.2008.08.025.Search in Google Scholar
Baronas, R., J. Kulys, and L. Petkevičius. 2020. “Modeling Carbohydrates Oxidation by Oxygen Catalyzed by Bienzyme Glucose Dehydrogenase/Laccase System Immobilized into Microreactor with Carbon Nanotubes.” Journal of Mathematical Chemistry 59: 168–85. https://doi.org/10.1007/s10910-020-01187-2.Search in Google Scholar
Benguerba, Y., and B. Djellouli. 2011. “Enhancement of the Catalytic Performances Under Non-Steady State Conditions.” Chemical Engineering Journal 166 (3): 1090–4. https://doi.org/10.1016/j.cej.2010.11.073.Search in Google Scholar
Bidabehere, C. M., and U. Sedran. 2001. “Simultaneous Diffusion, Adsorption, and Reaction in Fluid Catalytic Cracking Catalysts.” Industrial & Engineering Chemistry Research 40 (2): 530–5. https://doi.org/10.1021/ie990803z.Search in Google Scholar
Bidabehere, C. M., and U. Sedran. 2006. “Use of Stirred Batch Reactors for the Assessment of Adsorption Constants in Porous Solid Catalysts with Simultaneous Diffusion and Reaction. Theoretical Analysis.” Chemical Engineering Science 61 (6): 2048–55. https://doi.org/10.1016/j.ces.2005.10.043.Search in Google Scholar
Bidabehere, C. M., J. R. García, and U. Sedran. 2015. “Transient Effectiveness Factors in the Dynamic Analysis of Heterogeneous Reactors with Porous Catalyst Particles.” Chemical Engineering Science 137: 293–300. https://doi.org/10.1016/j.ces.2015.06.041.Search in Google Scholar
Bidabehere, C. M., J. R. García, and U. Sedran. 2017. “Transient Effectiveness Factor in Porous Catalyst Particles. Application to Kinetic Studies with Batch Reactors.” Chemical Engineering Research and Design 118: 41–50. https://doi.org/10.1016/j.cherd.2016.11.029.Search in Google Scholar
Biswas, J., D. Do, P. Greenfield, and J. Smith. 1986. “Evaluation of Bidisperse Diffusivities and Tortuosity Factors in Porous Catalysts using Batch and Continuous Adsorbers: A Theoretical Study.” Applied Catalysis 22: 97–113. https://doi.org/10.1016/j.cherd.2016.11.029.Search in Google Scholar
Bidabehere, C. M., J. R. García, and U. Sedran. 2018. “Transient Effectiveness Factor. Simultaneous Determination of Kinetic, Diffusion and Adsorption Equilibrium Parameters in Porous Catalyst Particles Under Diffusion Control Conditions.” Chemical Engineering Journal 345: 196–208. https://doi.org/10.1016/j.cej.2018.03.141.Search in Google Scholar
Cohen, D., J. Merchuk, Y. Zeiri, and O. Sadot. 2017. “Catalytic Effectiveness of Porous Particles: A Continuum Analytic Model Including Internal and External Surfaces.” Chemical Engineering Science 166: 101–6. https://doi.org/10.1016/j.ces.2017.03.032.Search in Google Scholar
de Jong, K. P., J. Zečević, H. Friedrich, P. E. de Jongh, M. Bulut, S. Van Donk, R. Kenmogne, A. Finiels, V. Hulea, and F. Fajula. 2010. “Zeolite Y Crystals with Trimodal Porosity as Ideal Hydrocracking Catalysts.” Angewandte Chemie International Edition 49 (52): 10074–8. https://doi.org/10.1002/anie.201004360.Search in Google Scholar PubMed
de Lasa, H., and D. Kraemer. 1992. “Novel Techniques for FCC Catalyst Selection and Kinetic Modelling.” In Chemical Reactor Technology for Environmentally Safe Reactors and Products, 71–131. Dordrecht: Springer.10.1007/978-94-011-2747-9_5Search in Google Scholar
Fogler, H. S. 1999. Elements of Chemical Reaction Engineering, 3rd ed. Englewood Cliffs, New Jersey: Prentice-Hall.Search in Google Scholar
Fornero, E. L., J. L. Giombi, D. L. Chiavassa, A. L. Bonivardi, and M. A. Baltanás. 2015. “A Versatile Carberry-Type Microcatalytic Reactor for Transient and/or Continuous Flow Operation at Atmospheric or Medium Pressure.” Chemical Engineering Journal 264: 664–71. https://doi.org/10.1016/j.cej.2014.11.106.Search in Google Scholar
Fornero, E. L., D. L. Chiavassa, A. L. Bonivardi, and M. A. Baltanás. 2017. “Transient Analysis of the Reverse Water Gas Shift Reaction on Cu/ZrO2 and Ga2O3/Cu/ZrO2 Catalysts.” Journal of CO2 Utilization 22: 289–98. https://doi.org/10.1016/j.jcou.2017.06.002.Search in Google Scholar
Froment, G., K. Bischoff, and J. De Wilde. 2011. Chemical Reactor Analysis and Design, 3rd ed. New York: John Wiley and Sons Inc.Search in Google Scholar
García, J. R., M. Falco, and U. Sedran. 2016. “Impact of the Desilication Treatment of Y Zeolite on the Catalytic Cracking of Bulky Hydrocarbon Molecules.” Topics in Catalysis 59 (2–4): 268–77. https://doi.org/10.1007/s11244-015-0432-7.Search in Google Scholar
García, J. R., M. Falco, and U. Sedran. 2017a. “Intracrystalline Mesoporosity Over Y Zeolites: PASCA Evaluation of the Secondary Cracking Inhibition in the Catalytic Cracking of Hydrocarbons.” Industrial & Engineering Chemistry Research 56 (6): 1416–23. https://doi.org/10.1021/acs.iecr.6b04350.Search in Google Scholar
García, J. R., M. Falco, and U. Sedran. 2017b. “Intracrystalline Mesoporosity Over Y Zeolites. Processing of VGO and Resid-VGO Mixtures in FCC.” Catalysis Today 296: 247–53. https://doi.org/10.1016/j.cattod.2017.04.010.Search in Google Scholar
Glueckauf, E. 1955. “Theory of Chromatography. Part 10.-Formulae for Diffusion into Spheres and Their Application to Chromatography.” Transactions of the Faraday Society 51: 1540–51. https://doi.org/10.1039/tf9555101540.Search in Google Scholar
Golbig, K. G., and J. Werther. 1997. “Selective Synthesis of Maleic Anhydride by Spatial Separation of N-Butane Oxidation and Catalyst Reoxidation.” Chemical Engineering Science 52 (4): 583–95. https://doi.org/10.1016/s0009-2509(96)00419-8.Search in Google Scholar
Herrmann, J. M. 1997. “Isokinetic Consecutive Reactions in Heterogeneous Catalysis.” Applied Catalysis A: General 156 (2): 285–97. https://doi.org/10.1016/s0926-860x(97)00005-7.Search in Google Scholar
Hudgins, R. R., P. L. Silveston, and A. Renken. 2013. “Modulation of Multiple Reactions.” In Periodic Operation of Chemical Reactors, 341–67. Kidlington: Elsevier Butterworth-Heinemann.10.1016/B978-0-12-391854-3.00012-7Search in Google Scholar
Jiménez-García, G., H. de Lasa, and R. Maya-Yescas. 2014. “Simultaneous Estimation of Kinetics and Catalysts Activity During Cracking of 1, 3, 5-Tri-Isopropyl Benzene on FCC Catalyst.” Catalysis Today 220: 178–85. https://doi.org/10.1016/j.cattod.2013.10.026.Search in Google Scholar
Juncu, G. 2006. “Unsteady Conjugate Mass Transfer to a Sphere Accompanied by a Consecutive Second-Order Chemical Reaction Inside the Sphere.” Chemical Engineering and Processing: Process Intensification 45 (1): 22–30. https://doi.org/10.1016/j.cep.2005.05.004.Search in Google Scholar
Kang, J., P. Puthiaraj, W. S. Ahn, and E. D. Park. 2020. “Direct Synthesis of Oxygenates via Partial Oxidation of Methane in the Presence of O2 and H2 over a Combination of Fe-ZSM-5 and Pd Supported on an Acid-Functionalized Porous Polymer.” Applied Catalysis A: General 602: 117711. https://doi.org/10.1016/j.apcata.2020.117711.Search in Google Scholar
Kim, D. H. 1989. “Linear Driving Force Formulas for Diffusion and Reaction in Porous Catalysts.” AI Ch. EJ; (United States) 35 (2): 343–6. https://doi.org/10.1002/aic.690350225.Search in Google Scholar
Levenspiel, O. 1999. Chemical Reaction Engineering, 3rd ed. New York: John Wiley & Sons, Inc.Search in Google Scholar
Ma, Y., and T. Lee. 1976. “Transient Diffusion in Solids with a Bipore Distribution.” AIChE Journal 22: 147–52.10.1002/aic.690220118Search in Google Scholar
Ma, Y., and A. Roux. 1973. “Multicomponents Rates of Sorption of SO2 and CO2 in Sodium Mordenite.” AIChE Journal 19: 1055–9.10.1002/aic.690190531Search in Google Scholar
Marroquín de la Rosa, J. M., R. M. Escobar, T. V. Garcia, and J. A. Ochoa-Tapia. 2002. “An Analytic Solution to the Transient Diffusion-Reaction Problem in Particles Dispersed in a Slurry Reactor.” Chemical Engineering Science 57 (8): 1409–17. https://doi.org/10.1016/s0009-2509(02)00054-4.Search in Google Scholar
Miro, E. E., D. R. Ardiles, E. A. Lombardo, and J. O. Petunchi. 1986. “Continuous-Stirred Tank Reactor (CSTR) Transient Studies in Heterogeneous Catalysis: CO Oxidation Over CuY Zeolite.” Journal of Catalysis 97 (1): 43–51. https://doi.org/10.1016/0021-9517(86)90035-7.Search in Google Scholar
Oberoi, A., J. Kelly, and O. Fuller. 1980. “Methods of Interpreting Transient Response Curves from Dynamic Sorption Experiments.” Industrial and Engineering Chemistry Fundamentals 19: 17–21.10.1021/i160073a003Search in Google Scholar
Pangarkar, V. G., and M. M. Sharma. 1974. “Consecutive Reactions: Role of Mass Transfer Factors.” Chemical Engineering Science 29 (2): 561–9. https://doi.org/10.1016/0009-2509(74)80067-9.Search in Google Scholar
Schobert, M. A., and Y. H. Ma. 1981a. “Isomerization of Cyclopropane on Synthetic Faujasite by Pulse Technique: I. Mathematical Model.” Journal of Catalysis 70 (1): 102–10. https://doi.org/10.1016/0021-9517(81)90320-1.Search in Google Scholar
Schobert, M. A., and Y. H. Ma. 1981b. “Isomerization of Cyclopropane on Synthetic Faujasite by Pulse Technique: II. Experimental Study.” Journal of Catalysis 70 (1): 111–22. https://doi.org/10.1016/0021-9517(81)90321-3.Search in Google Scholar
Sie, S. T. 1993. “Intraparticle Diffusion and Reaction Kinetics as Factors in Catalyst Particle Design.” The Chemical Engineering Journal and the Biochemical Engineering Journal 53 (1): 1–11. https://doi.org/10.1016/0923-0467(93)80002-e.Search in Google Scholar
Stankiewicz, A., and M. Kuczynski. 1995. “An Industrial View on the Dynamic Operation of Chemical Converters.” Chemical Engineering and Processing: Process Intensification 34 (4): 367–77. https://doi.org/10.1016/0255-2701(95)00537-4.Search in Google Scholar
Sutradhar, B. C., P. Ray, P. Ray, and B. K. Dutta. 1991. “Selectivity Behaviour of Non-Uniform Catalysts for the Consecutive Reactions A → B → C.” The Chemical Engineering Journal 46 (2): 91–6. https://doi.org/10.1016/0300-9467(91)80027-t.Search in Google Scholar
Szczygieł, J. 2011. “Effect of the Diffusion Phenomena in the Catalyst Grain on the Selectivity of a System of Parallel-Consecutive Reactions Involved in the Process of N-Heptane Dehydrocyclization.” Computers & Chemical Engineering 35 (6): 985–98. https://doi.org/10.1016/j.compchemeng.2010.12.001.Search in Google Scholar
Titze, T., C. Chmelik, J. Kullmann, L. Prager, E. Miersemann, R. Gläser, and J. Kärger. 2015. “Microimaging of Transient Concentration Profiles of Reactant and Product Molecules During Catalytic Conversion in Nanoporous Materials.” Angewandte Chemie International Edition 54 (17): 5060–4. https://doi.org/10.1002/anie.201409482.Search in Google Scholar PubMed
van de Vusse, J. G. 1966. “Consecutive Reactions in Heterogeneous Systems II-Influence of Order of Reaction Rates on Selectivity.” Chemical Engineering Science 21 (8): 645–53. https://doi.org/10.1016/0009-2509(66)80014-3.Search in Google Scholar
Vayenas, C. G., and S. Pavlou. 1987. “Optimal Catalyst Distribution for Selectivity Maximization in Pellets: Parallel and Consecutive Reactions.” Chemical Engineering Science 42 (7): 1655–66. https://doi.org/10.1016/0009-2509(87)80170-7.Search in Google Scholar
Weisz, P. B., and J. S. Hicks. 1962. “The Behaviour of Porous Catalyst Particles in View of Internal Mass and Heat Diffusion Effects.” Chemical Engineering Science 17 (4): 265–75. https://doi.org/10.1016/0009-2509(62)85005-2.Search in Google Scholar
Weisz, P. B., and C. D. Prater. 1954. “Interpretation of Measurements in Experimental Catalysis.” Advances in Catalysis 6: 143–96. https://doi.org/10.1016/S0360-0564(08)60390-9.Search in Google Scholar
Weisz, P. B., and E. W. Swegler. 1955. “Effect of Intra-Particle Diffusion on the Kinetics of Catalytic Dehydrogenation of Cyclohexane.” The Journal of Physical Chemistry 59 (9): 823–6. https://doi.org/10.1021/j150531a006.Search in Google Scholar
Wheeler, A. 1951. “Reaction Rates and Selectivity in Catalyst Pores.” Advances in Catalysis 3: 249–327. https://doi.org/10.1016/S0360-0564(08)60109-1.Search in Google Scholar
Wirges, H. P., and W. Rähse. 1975. “The Isothermal Selectivity of Porous Catalysts: Competitive-Consecutive Reactions.” Chemical Engineering Science 30 (7): 647–51. https://doi.org/10.1016/0009-2509(75)85087-1.Search in Google Scholar
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Articles in the same Issue
- Frontmatter
- Editorial
- In honour of Dr. Orlando M. Alfano: researcher, engineer, and academic
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Articles in the same Issue
- Frontmatter
- Editorial
- In honour of Dr. Orlando M. Alfano: researcher, engineer, and academic
- Special Issue Articles
- Absorbed radiation and kinetic model in photocatalysis by TiO2
- Hydrogen production via surrogate biomass gasification using 5% Ni and low loading of lanthanum co-impregnated on fluidizable γ-alumina catalysts
- Simplified estimation of anisotropic non-homogeneous extinction coefficients in porous solids considering spherical and cylindrical pore networks
- Co-processing of hydrodeoxygenation and hydrodesulfurization of phenol and dibenzothiophene with NiMo/Al2O3–ZrO2 and NiMo/TiO2–ZrO2 catalysts
- Radiative transfer in a Solar CPC Photoreactor using the First-Order Scattering Method
- Selective hydrogenation of light cycle oil for BTX and gasoline production purposes
- Unsteady state diffusion-adsorption-reaction. Selectivity of consecutive reactions on porous catalyst particles
- Photocatalytic degradation of acetaminophen from water solutions via thin films part I: preparation, characteriation, and analysis of titanium dioxide thin films
- Photocatalytic degradation of acetaminophen in water via ultraviolet light and titanium dioxide thin films part II: chemical and kinetic aspects
- Ti-Co mixed oxide as photocatalysts in the generation of hydrogen from water
