Nanocomposites and nanomaterials
Catalytic properties of Zn-Mg(Zr)Si oxide nanosystems modified with alkali metals and rare-earth elements in the 1,3-butadiene production from ethanol
Larina O.V., Zikrata O.V., Alekseenko L.M., Kyriienko P.I., Soloviev S.O.
L.V. Pisarzhevskii Institute of Physical Chemistry of the NAS of Ukraine, Prospect Nauky, 31, Kyiv-03028, Ukraine.
E-mail: olga.larina@ukr.net

The processes for production of valuable chemicals and fuels based on bio-raw materials, in particular bioethanol, is an alternative to a number of petrochemical processes. Ethanol is considered as a universal precursor for the synthesis of such industrially important substances as ethene, propene, 1,3-butadiene, etc. hydrocarbons. Zeolite and silica-supported acid-base materials (e.g. Mg and Zr containing systems) doped with dehydrogenating components (ZnO, Ag, Cu, etc.) are promising catalysts for the ethanol-to-butadiene process.
In present work, the effect of alkali metal ions (Na+, K+) and rare-earth elements (Y, La, Ce) on acid–base and catalytic properties of Zn-Mg(Zr)Si oxide nanosystems in the process of obtaining 1,3-butadiene from ethanol was studied. It was found [1] that the modification of Zn-MgSi oxide systems with Na(K) leads to an increase in the 1,3-butadiene selectivity by reducing the formation of by-products. In the composition of Zn-ZrSi oxide systems, alkali metal additives lead to a decrease in the ethene and diethyl ether selectivity due to a decrease in the content of strong acid sites which catalyze ethanol dehydration reaction. Among the catalysts modified with rare-earth elements, higher indices of the ethanol-to-butadiene process are achieved in the presence of Mg-containing oxide catalysts, which are characterized by higher concentration of base and acid surface sites of medium strength. Among Zr-containing systems modified with rare-earth elements, Zn-Y-ZrSi sample is characterized by a higher number of Lewis acid sites of weak and medium strength, which accelerates the reaction of aldol condensation of acetaldehyde, a key step of the ethanol-to-butadiene process.

1.	Larina O. V., Kyriienko P. I., Morozov O. V., Obushenko T. I., Tolstopalova N. M., Soloviev S. O. Influence of Modification of Zn-Mg(Zr)Si Oxide Systems by Sodium and Potassium on their Catalytic Properties in the Process of Obtaining 1,3-Butadiene from Ethanol // Theor. Exp. Chem. – 2022. – 57, N 6. – P. 443-450.