STUDY OF CARBON DIOXIDE ADSORPTION ON CHROMOXIDE CATALYST ON NON-STATIONARY CONCENTRATIONS

  • Nikolay I. Kol'tsov Chuvash State University named after I.N. Ulyanov
  • Vladislav Kh. Fedotov Chuvash State University named after I.N. Ulyanov
Keywords: adsorption, desorption, carbon dioxide, nonstationary concentrations, chromium oxide catalyst

Abstract

Investigation of the regularities of chemical processes, not only near but also far from the stationary state, gives additional information on their mechanisms. In this paper, we present a new method for estimating rate constants of adsorption-desorption processes from the experimentally measured values of the nonstationary concentrations of an adsorbed substance, based on calculating the instantaneous rates of the adsorption (or desorption) process. This method allows to connect unknown kinetic parameters of adsorption (desorption) of a substance on the catalyst surface for various most probable assumed mechanisms with the calculated values of the instantaneous rates of adsorption-desorption processes. As a consequence, the method makes it possible to solve two types of inverse problems of chemical kinetics: calculate point and interval values of rates constants of adsorption and desorption; determine the most likely mechanism from several proposed mechanisms of implementation of these processes. Using this method, point and interval values of the rates constants of adsorption and desorption of carbon dioxide were determined on the base of nonstationary experimental data on adsorption on the assumption of carbon dioxide adsorption on a chromoxide catalyst to three proposed mechanisms: linear, bimolecular and dissociative. Based on the results of calculations, the corresponding non-stationary dependences of carbon dioxide adsorption were restored, which were compared with the experimental data. The obtained results confirm that the previously established dissociative mechanism of adsorption of carbon dioxide on the chromoside catalyst is the most probable. The developed simple method does not require the use of complex optimization calculations and can be used to solve the inverse problem of chemical kinetics associated with the determination of mechanisms and the estimation of the rates constants of adsorption and desorption of substances on various catalysts.

Forcitation:

Kol’tsov N.I., Fedotov V.Kh. Study of carbon dioxide adsorption on chromoxide catalyst on non-stationary concentrations. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 7. P. 37-42

References

Ismagilova A.S., Spivak S.I. Inverse problems of chemical kinetics, Saarbrucken: Lap Lambert Academic Publishingю 2013. 118 p.

Alekseev B.V., Koltsov N.I. Estimation of nonlinear relaxations of catalytic reactions. React. Kinet. Catal. Lett. 1984. V. 24. N 3-4. P. 309-314.

Kol'tsov N.I., Fedotov V.Kh., Alekseev B.V. Relaxation, multiplicity and auto-oscillations in the kinetics of catalytic reactions. Kinetika i Kataliz. 1995. V. 36. N 1. P. 51-59 (in Russian).

Bykov V.I., Tsybenova S.B. Nonlinear models of chemical kinetics. M.: Krasand. 2011. 400 p. (in Russian).

Fedotov V.Kh., Kol'tsov N.I. Estimates of nonlinear relaxation times of catalytic reactions. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2014. V. 57. N 2. P. 63-67 (in Russian).

Fedotov V.Kh., Kol'tsov N.I. Estimates of the relaxation times of multi-route catalytic reactions. Khim. Fizika. 2014. V. 33. N 6. P. 18-26 (in Russian).

Kol'tsov N.I. Mathematical modeling of catalytic reactions. Cheboksary: Publishing House of the Chuvash University Press. 2007. 294 p. (in Russian).

Fedotov V.Kh., Kol'tsov N.I. Method of solving the inverse problem of chemical kinetics for catalytic reactions in which each step involves main reactants. Russ. J. Phys. Chem. B. 2016. V. 10. N 5. P. 753–759.

Fedotov V.Kh., Kol'tsov N.I., Gaidai N.A., Agafonov Yu.A., Botavina M.A., Lapidus A.L. Study of carbon dioxide adsorp-tion on chromium oxide and gallium oxide catalysts on the basis of linear relaxation times. J. Appl. Chem. 2016. V. 89. N 5. P. 719-726.

Kol'tsov N.I. Investigation of the adsorption of carbon dioxide on chromium and gallium oxide catalysts by nonlinear relaxation times. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 2. P. 46-52. (in Russian). DOI: 10.6060/tcct.20186102.5584.

Tekehira K., Ohishi Y., Shishido T., Kawabata T., Takaki K., Zhang Q., Wang Y. Behavior of active sites on Cr-MCM-41 catalysts during the dehydrogenation of propane with СО2. J. Catal. 2004. V. 224. P. 404-416.

Ostrovskii V.E., Agafonov Yu.A., Gostev B.V., Kadyshevich E.A. Lapidus A.L. Chemisorption of gases and reaction of propane dehydration at chromic oxide. Solid Fuel Chem. 2010. V. 44. N 4. P. 275–286.

Botavina M.A., Evangelisti C., Agafonov Yu.A., Gaidai N.A., Panziera N., Lapidus A.L., Martra G. CrOx/SiO2 catalysts prepared by metal vapour synthesis: physical-chemical characterisation and functional testing in oxidative dehydrogenation of pro-pane. Chem. Eng. J. 2011. V. 166. P. 1132–1138.

Lapidus A.L., Agafonov Yu.A., Gaidai N.A., Nekrasov N.V., Menshova M.V., Kunusova R.M. Dehydrogenation of pro-pane in the presence of carbon dioxide over chromium and gallium oxides. Catalysts Innovative Applications in Petrochemistry and Refining. DGMK Conference October 4–6, 2011. Dresden, Germany. 2011. P. 201-210.

Lapidus A.L., Gaidai N.A., Nekrasov N.V., Agafonov Yu.A., Botavina M.A. Kinetics of propane dehydrogenation in СО2 presence over chromium and gallium oxide catalysts based on MCM-41. Reducing the carbon footprint of fuels and petrochemi-cals. DGMK сonference October 8 – 10, 2012. Berlin, Germany. 2012. P. 181-188.

Lapidus. A.L., Agafonov Yu.A., Gaiydaiy N.A., Trushin D.V., Nekrasov N.V. Effect of introduction of alkaline promoters in oxide-chromium catalysts of propane dehydrogenation in the presence of СО2. Khimia Tverdogo Topliva. 2012. N 1. P. 22-31 (in Russian).

Michorczyk P., Pietrzyk P., Ogonowski J. Preparation and characterization of SBA-1-supported chromium oxide catalysts for assisted dehydrogenation of propane. Micropor. Mesopor. Materials. 2012. V. 161. P. 56-66.

Agafonov Yu.A., Gaiydaiy N.A., Lapidus A.L. Influence of the conditions for the preparation of CrOx/SiO2 catalysts on their efficiency in the dehydrogenation of propane in the presence of CO2. Izv. Akademii Nauk. Ser. Khim. 2014. N 2. P. 381–388 (in Russian).

Botavina M.A., Agafonov Yu.A., Gaidai N.A., Groppo E., Cortés Corberán V., Lapidus A., Martra G. Towards efficient catalysts for the oxidative dehydrogenation of propane in the presence of СО2: Cr/SiO2 systems prepared by direct hydrothermal synthesis. Catal. Sci. Technol. 2016. V. 6. P.840-850.

Atanga M.A., Jawad A., Fitch M., Rownaghi A.A. Oxidative dehydrogenation of propane to propylene with carbon dioxide. Appl. Catal. B. 2018. V. 220. P. 429-445.

How to Cite
Kol’tsov, N. I., & Fedotov, V. K. (1). STUDY OF CARBON DIOXIDE ADSORPTION ON CHROMOXIDE CATALYST ON NON-STATIONARY CONCENTRATIONS. ChemChemTech, 61(7), 37-43. https://doi.org/10.6060/ivkkt.20186107.5714
Section
CHEMISTRY (inorganic, organic, analytical, physical, colloid and high-molecular compounds)