From Chemistry Towards Technology Step-By-Step From Chemistry Towards Technology Step-By-Step От химии к технологии шаг за шагом 2782-1900 83097 10.52957/27821900_2021_01_144 Научные статьи Scientific articles Научные статьи Formation of the active state of the promoted iron oxide catalyst for dehydrogenation Formation of the active state of the promoted iron oxide catalyst for dehydrogenation Дворецкий Николай Витальевич Dvoretskii Nikolay Vitalievich dvoretskiin@mail.ru

доктор химических наук;

doctor of chemical sciences;

 Аниканова Любовь Германовна Anikanova Lyubov Germanovna anikanoval@mail.ru

кандидат химических наук;

candidate of chemical sciences;

 Малышева Зоя Геннадьевна Malysheva Zoya Gennad'evna malyshevazg@mail.ru

кандидат химических наук;

candidate of chemical sciences;

 Судзиловская Татьяна Николаевна Sudzilovskaya Tatiana Nikolaevna sudzilovskayatn@mail.ru

кандидат химических наук;

candidate of chemical sciences;

 Ярославский государственный технический университет Yaroslavl State Technical University 23 03 2021 23 03 2021 2 1 144 156 15 12 2020 11 03 2021 https://chemintech.ru/en/nauka/article/83097/view

It was found that for K-β"Fe2O3 the maximum probability of realization of the active centers representing a cluster consisting of potassium ions, iron 3+ and 2+, and oxygen. The ability to self-reproduction and self-regulation in the reaction medium is an integral attribute of K-β"Fe2O3 as the main catalytically active component. This type of catalyst can be called a "catalyst with a permanently migrating promoter". Polyferrite serves as a conductor of the alkaline promoter. The monoferrite concentrated in the depth of the catalyst granules, for example, on the inner surface of closed pores can be a source of potassium. Polyferrites are solid electrolytes with a cationic type of conductivity and provide not only the delivery of the promoter to a required location through channels embedded in the crystal structure, but also its regular placement in the composition of active clusters. K-β"Fe2O3 is able to place the alloying additives in its structure. Only in this case, extremely small amounts of injected agent can greatly change the properties of the system. The rearrangement is not chaotic, if the K-β"Fe2O3 surface is chemically dispersed in the reaction medium to form a catalytically active short-lived substance - a nanoheterogeneous mixture of monoferrite and magnetite.

It was found that for K-β"Fe2O3 the maximum probability of realization of the active centers representing a cluster consisting of potassium ions, iron 3+ and 2+, and oxygen. The ability to self-reproduction and self-regulation in the reaction medium is an integral attribute of K-β"Fe2O3 as the main catalytically active component. This type of catalyst can be called a "catalyst with a permanently migrating promoter". Polyferrite serves as a conductor of the alkaline promoter. The monoferrite concentrated in the depth of the catalyst granules, for example, on the inner surface of closed pores can be a source of potassium. Polyferrites are solid electrolytes with a cationic type of conductivity and provide not only the delivery of the promoter to a required location through channels embedded in the crystal structure, but also its regular placement in the composition of active clusters. K-β"Fe2O3 is able to place the alloying additives in its structure. Only in this case, extremely small amounts of injected agent can greatly change the properties of the system. The rearrangement is not chaotic, if the K-β"Fe2O3 surface is chemically dispersed in the reaction medium to form a catalytically active short-lived substance - a nanoheterogeneous mixture of monoferrite and magnetite.

 potassium polyferrite hematite promoted iron oxide catalyst ferrite system phase diagram

Weiss W., Zscherpel D., Schlogl R. On the Nature of the Active Site for the Ethylbenzene Dehydrogenation Over Iron Oxide Catalysts. Catalysis Letters. 1998. Vol. 52. N 3-4. P. 215-220. URL: https://doi.org/10.1023/A:1019052310644 Weiss W., Zscherpel D., Schlogl R. On the Nature of the Active Site for the Ethylbenzene Dehydrogenation Over Iron Oxide Catalysts. Catalysis Letters. 1998. Vol. 52. N 3-4. P. 215-220. URL: https://doi.org/10.1023/A:1019052310644 Weiss W., Schlögl R. An Integrated Surface Science Approach Towards Metal Oxide Catalysis. Topics in Catalysis. 2000. Vol. 13. N 1-2. P. 75-90. Weiss W., Schlögl R. An Integrated Surface Science Approach Towards Metal Oxide Catalysis. Topics in Catalysis. 2000. Vol. 13. N 1-2. P. 75-90. Shaikhutdinov Sh.K., Weiss W., Schlogl R. Interaction of potassium with Fe3O4 (111) at elevated temperatures. Applied Surface Science. 2000. Vol. 161. N 3-4. P 497-507. DOI: 10.1016/S0169-4332(00)00373-1 Shaikhutdinov Sh.K., Weiss W., Schlogl R. Interaction of potassium with Fe3O4 (111) at elevated temperatures. Applied Surface Science. 2000. Vol. 161. N 3-4. P 497-507. DOI: 10.1016/S0169-4332(00)00373-1 Shekhah O., Ranke W., Schlögl R. Styrene synthesis: In-situ characterization and reactivity studies of unpromoted and potassium promoted iron oxide model catalysts. Journal Catalysis. 2004. Vol. 225. N 1. P. 56-68. DOI: 10.1016/j.jcat.2004.03.024 Shekhah O., Ranke W., Schlögl R. Styrene synthesis: In-situ characterization and reactivity studies of unpromoted and potassium promoted iron oxide model catalysts. Journal Catalysis. 2004. Vol. 225. N 1. P. 56-68. DOI: 10.1016/j.jcat.2004.03.024 Garry R., Meima P., Menon G. Catalyst Deactivation Phenomena in Styrene Production // Applied Catalysis A: General. 2001. Vol. 212. P. 239-245. URL: https://ru.scribd.com/document/342010350/Catalyst-Deactivation-Phenomena-in-Styrene Garry R., Meima P., Menon G. Catalyst Deactivation Phenomena in Styrene Production // Applied Catalysis A: General. 2001. Vol. 212. P. 239-245. URL: https://ru.scribd.com/document/342010350/Catalyst-Deactivation-Phenomena-in-Styrene Muhler M., Schütze J., Wesemann M., Rayment T., Dent A., Schlögl R., Ertl G. The Nature of the Iron Oxide-Based Catalyst for Dehydrogenation of Ethylbenzene to Styrene: I. Solid-State Chemistry and Bulk Characterization. Journal of Catalysis. 1990. Vol. 126. N 2. P. 339-360. URL: https://doi.org/10.1016/0021-9517(90)90003-3 Muhler M., Schütze J., Wesemann M., Rayment T., Dent A., Schlögl R., Ertl G. The Nature of the Iron Oxide-Based Catalyst for Dehydrogenation of Ethylbenzene to Styrene: I. Solid-State Chemistry and Bulk Characterization. Journal of Catalysis. 1990. Vol. 126. N 2. P. 339-360. URL: https://doi.org/10.1016/0021-9517(90)90003-3 Muhler M., Schlögl R., Ertl G. The Nature of the Iron Oxide-Based Catalyst for Dehydrogenation of Ethylbenzene to Styrene 2. Surface Chemistry of the Active Phase. Journal of Catalysis. 1992. Vol. 138. N 2. P. 413-444. URL: https://doi.org/10.1016/0021-9517(92)90295-S Muhler M., Schlögl R., Ertl G. The Nature of the Iron Oxide-Based Catalyst for Dehydrogenation of Ethylbenzene to Styrene 2. Surface Chemistry of the Active Phase. Journal of Catalysis. 1992. Vol. 138. N 2. P. 413-444. URL: https://doi.org/10.1016/0021-9517(92)90295-S Lundin J., Holmlid L., Menon P.G., Nyborg L. Surface Composition of Iron Oxide Catalysts Used for Styrene Production: An Auger Electron Spectroscopy/Scanning Electron Microscopy Study. Ind. Eng. Chem. Res. 1993. Vol. 32. N 11. P. 2500-2505. DOI: 10.1021/ie00023a010 Lundin J., Holmlid L., Menon P.G., Nyborg L. Surface Composition of Iron Oxide Catalysts Used for Styrene Production: An Auger Electron Spectroscopy/Scanning Electron Microscopy Study. Ind. Eng. Chem. Res. 1993. Vol. 32. N 11. P. 2500-2505. DOI: 10.1021/ie00023a010 Muhler M., Schlögl R., Reller A., Ertl G. The Nature of the Active Phase of the Fe/K-Catalyst for Dehydrogenation of Ethylbenzene. Catalysis Letters. 1989. Vol. 2. N 4. P. 201-210. DOI: 10.1007/BF00766208 Muhler M., Schlögl R., Reller A., Ertl G. The Nature of the Active Phase of the Fe/K-Catalyst for Dehydrogenation of Ethylbenzene. Catalysis Letters. 1989. Vol. 2. N 4. P. 201-210. DOI: 10.1007/BF00766208 Muhler M., Schlögl R., Ertl G. Analysis of In Situ Prepared Surfaces of an Iron Oxide Based Dehydrogenation Catalyst. Surface and Interface Analysis. 1988. Vol. 12. N 4. P. 233-238. DOI: 10.1002/sia.740120402 Muhler M., Schlögl R., Ertl G. Analysis of In Situ Prepared Surfaces of an Iron Oxide Based Dehydrogenation Catalyst. Surface and Interface Analysis. 1988. Vol. 12. N 4. P. 233-238. DOI: 10.1002/sia.740120402 Shekhah O., Schüle A., Kolios G., Huang W.X., Ranke W. Iron Oxide Based Model Catalysts – Adsorption and Catalysis. 13th Meeting of the Fachbeirat. Berlin, 2005. P. AC 1.2 URL: http://w0.rz-berlin.mpg.de/fbr2005/posterabstracts2005.pdf Shekhah O., Schüle A., Kolios G., Huang W.X., Ranke W. Iron Oxide Based Model Catalysts – Adsorption and Catalysis. 13th Meeting of the Fachbeirat. Berlin, 2005. P. AC 1.2 URL: http://w0.rz-berlin.mpg.de/fbr2005/posterabstracts2005.pdf Joseph Y, Ketteler G., Kuhrs C., Ranke W., Weiss W., Schlögl R. On the Preparation and Composition of Potassium Promoted Iron Oxide Model Catalyst Films. Phys. Chem. Chem. Phys. 2001. Vol. 18. N 3. P. 4141-4153. DOI: 10.1039/B104263G Joseph Y, Ketteler G., Kuhrs C., Ranke W., Weiss W., Schlögl R. On the Preparation and Composition of Potassium Promoted Iron Oxide Model Catalyst Films. Phys. Chem. Chem. Phys. 2001. Vol. 18. N 3. P. 4141-4153. DOI: 10.1039/B104263G Ketteler G., Ranke W., Schlögl R. Potassium-Promoted Iron Oxide Model Catalyst Films for the Dehydrogenation of Ethylbenzene: An Example for Complex Model Systems. Journal of Catalysis. 2002. Vol. 212. N 1. P. 104-111. URL: https://doi.org/10.1006/jcat.2002.3785 Ketteler G., Ranke W., Schlögl R. Potassium-Promoted Iron Oxide Model Catalyst Films for the Dehydrogenation of Ethylbenzene: An Example for Complex Model Systems. Journal of Catalysis. 2002. Vol. 212. N 1. P. 104-111. URL: https://doi.org/10.1006/jcat.2002.3785 Kotarba A., Kruk I., Sojka Z. Energetics of Potassium Loss from Styrene Catalyst Model Components: Reassignment of K Storage and Release Phases. Journal of Catalysis. 2002. Vol. 211. N 1. P. 265-272. URL: https://doi.org/10.1006/jcat.2002.3725 Kotarba A., Kruk I., Sojka Z. Energetics of Potassium Loss from Styrene Catalyst Model Components: Reassignment of K Storage and Release Phases. Journal of Catalysis. 2002. Vol. 211. N 1. P. 265-272. URL: https://doi.org/10.1006/jcat.2002.3725 Kotarba A., Rożek W., Serafin I., Sojka Z. Reverse Effect of Doping on Stability of Principal Components of Styrene Catalyst: KFeO2 and K2Fe22O34. Journal of Catalysis. 2007. Vol. 247. N 2. P. 238-244. URL: https://doi.org/10.1016/j.jcat.2007.02.009 Kotarba A., Rożek W., Serafin I., Sojka Z. Reverse Effect of Doping on Stability of Principal Components of Styrene Catalyst: KFeO2 and K2Fe22O34. Journal of Catalysis. 2007. Vol. 247. N 2. P. 238-244. URL: https://doi.org/10.1016/j.jcat.2007.02.009 Lai Wu-jiang, Bai Zhen-gu. A Model of Active Center, Modes of Reaction Transition States and Reaction Mechanism for Dehydrogenation of Ethylbenzene to Styrene Over Potassium Promoted Iron Oxide. Chinese Journal of Catalysis. 1986. Vol. 7. N 2. P. 147-153. URL: http://en.cnki.com.cn/Article_en/CJFDTOTAL-CHUA198602007.htm Lai Wu-jiang, Bai Zhen-gu. A Model of Active Center, Modes of Reaction Transition States and Reaction Mechanism for Dehydrogenation of Ethylbenzene to Styrene Over Potassium Promoted Iron Oxide. Chinese Journal of Catalysis. 1986. Vol. 7. N 2. P. 147-153. URL: http://en.cnki.com.cn/Article_en/CJFDTOTAL-CHUA198602007.htm Anikanova L.G., Dvoreckij N.V. Distribution of alkaline promoters in the structure of the iron oxide dehydrogenation catalyst. Kataliz v promyshlennosti. 2012. T. 12. N 4. P. 18-23. URL: http://dx.doi.org/10.18412/1816-0387-2012-4-18-23 (in Russian). Anikanova L.G., Dvoreckij N.V. Distribution of alkaline promoters in the structure of the iron oxide dehydrogenation catalyst. Kataliz v promyshlennosti. 2012. T. 12. N 4. P. 18-23. URL: http://dx.doi.org/10.18412/1816-0387-2012-4-18-23 (in Russian). Dvoreckij N.V., Stepanov E.G., YUn V.V., Kotel'nikov G.R. The phase composition of the promoted iron oxide catalysts under the conditions of the dehydrogenation reaction. Izv. vuzov. Himiya i him. tekhnologiya. 1990. T. 33. N 8. P. 3-9. (in Russian). Dvoreckij N.V., Stepanov E.G., YUn V.V., Kotel'nikov G.R. The phase composition of the promoted iron oxide catalysts under the conditions of the dehydrogenation reaction. Izv. vuzov. Himiya i him. tekhnologiya. 1990. T. 33. N 8. P. 3-9. (in Russian). Dvoreckij N.V., Stepanov E.G., YUn V.V. ¬Phase diagram of systems Fe2O3-Fe3O4-KFeO2. Izv. Akademii Nauk SSSR. Neorg. Mater. 1991. T. 27. N 6. P. 1265-1268 (in Russian). Dvoreckij N.V., Stepanov E.G., YUn V.V. ¬Phase diagram of systems Fe2O3-Fe3O4-KFeO2. Izv. Akademii Nauk SSSR. Neorg. Mater. 1991. T. 27. N 6. P. 1265-1268 (in Russian). Ito S., Kurosawa H., Akashi K., Michiue Y., Watanabe M. Crystal structure and electric conductivity of K+-β-ferrite with ideal composition KFe11O17. Solid State Ionics. 1996. Vol. 86-88. Part 2. P. 745-750. URL: https://doi.org/10.1016/0167-2738(96)00164-6 Ito S., Kurosawa H., Akashi K., Michiue Y., Watanabe M. Crystal structure and electric conductivity of K+-β-ferrite with ideal composition KFe11O17. Solid State Ionics. 1996. Vol. 86-88. Part 2. P. 745-750. URL: https://doi.org/10.1016/0167-2738(96)00164-6 Lamberov A.A., Gil'manov H.H., Dement'eva E.V., Kuz'mina O.V. Investigation of the mechanism of influence of cerium additives on the properties of the iron-potassium system-the active component of the catalysts for the dehydrogenation of hydrocarbons. Message 2. Kataliz v promyshlennosti. 2012. T. 12. N 6. P. 60-68. URL: https://www.catalysis-kalvis.ru/jour/article/view/72/69 (in Russian). Lamberov A.A., Gil'manov H.H., Dement'eva E.V., Kuz'mina O.V. Investigation of the mechanism of influence of cerium additives on the properties of the iron-potassium system-the active component of the catalysts for the dehydrogenation of hydrocarbons. Message 2. Kataliz v promyshlennosti. 2012. T. 12. N 6. P. 60-68. URL: https://www.catalysis-kalvis.ru/jour/article/view/72/69 (in Russian). Dvoreckij N.V., Anikanova L.G., Malysheva Z.G. Types of active centers on the surface of the promoted iron oxide catalyst. Izv. vuzov. Himiya i him. tekhnologiya. 2018. T. 61. N 6. P. 61-68 (in Russian). Dvoreckij N.V., Anikanova L.G., Malysheva Z.G. Types of active centers on the surface of the promoted iron oxide catalyst. Izv. vuzov. Himiya i him. tekhnologiya. 2018. T. 61. N 6. P. 61-68 (in Russian). Anikanova L.G., Dvoreckij N.V. Stabilization of alkaline promoters in the structure of iron oxide dehydrogenation catalysts. Kataliz v promyshlennosti. 2016. T. 16. N 1. P. 29-36. URL: http://dx.doi.org/10.18412/1816-0387-2016-1-29-36 (in Russian). Anikanova L.G., Dvoreckij N.V. Stabilization of alkaline promoters in the structure of iron oxide dehydrogenation catalysts. Kataliz v promyshlennosti. 2016. T. 16. N 1. P. 29-36. URL: http://dx.doi.org/10.18412/1816-0387-2016-1-29-36 (in Russian). Anikanova L.G., Dvoreckij N.V., Malysheva Z.G. Cationic conductivity in mixed polyferrites. Izv. vuzov. Himiya i him. tekhnologiya. 2016. T. 59. N 1. P. 23-26 (in Russian). Anikanova L.G., Dvoreckij N.V., Malysheva Z.G. Cationic conductivity in mixed polyferrites. Izv. vuzov. Himiya i him. tekhnologiya. 2016. T. 59. N 1. P. 23-26 (in Russian). Hersog B.D., Rase H.F. In Situ Catalyst Reactivation Used Ethylbenzene Dehydrogenation Catalyst with Agglomerated Potassium Promoter. Ind. and Eng. Chem. Prod. Res. and Div. 1984. Vol. 23. N 2. P.187-196. DOI: 10.1002/chin.198446140 Hersog B.D., Rase H.F. In Situ Catalyst Reactivation Used Ethylbenzene Dehydrogenation Catalyst with Agglomerated Potassium Promoter. Ind. and Eng. Chem. Prod. Res. and Div. 1984. Vol. 23. N 2. P.187-196. DOI: 10.1002/chin.198446140