Vol.:(0123456789) Reaction Kinetics, Mechanisms and Catalysis https://doi.org/10.1007/s11144-019-01618-5 1 3 1,3‑Butadiene production from ethanol–water mixtures over Zn–La–Zr–Si oxide catalyst Olga V. Larina 1  · Ivan M. Remezovskyi 1  · Pavlo I. Kyriienko 1  · Sergiy O. Soloviev 1  · Svitlana M. Orlyk 1 Received: 2 May 2019 / Accepted: 7 June 2019 © Akadémiai Kiadó, Budapest, Hungary 2019 Abstract Zn–La–Zr–Si oxide composition has been investigated in the ethanol-to-butadiene process using ethanol–water mixtures with diferent water content. An increase of H 2 O content in the initial reaction mixture decreases ethanol conversion, 1,3-buta- diene selectivity, yield and productivity. The results of in situ FTIR spectroscopy (with ethanol and acetone as probe molecules) have shown the main reason for a decrease in activity of the catalyst to be H 2 O adsorption on active sites of aldol con- densation of acetaldehyde and, to a lesser extent, ethanol dehydrogenation. Zn–La– Zr–Si oxide composition is a highly active and selective catalyst for the ethanol-to- butadiene process when ethanol–water mixture of 80 vol% ethanol and 20 vol% H 2 O is used, 60% 1,3-butadiene yield is achieved. Keywords Ethanol · 1,3-Butadiene · H 2 O efect · Lewis acidic site · Aldol condensation of acetaldehyde · In situ FTIR Introduction 1,3-Butadiene (BD) is one of the most important conjugated dienes and is used as an intermediate for the synthesis of rubber, elastomers and polymer resins. Tradition- ally, BD can be produced as a side product in the steam cracking process and a pro- cess of oxidation of butenes [1]. The alternative non-fossil method of BD production is bioethanol conversion [2–5]. An overall scheme of ethanol (EtOH) conversion into BD involves multiple con- secutive reaction steps such as: acetaldehyde (AA) formation from EtOH, cross-con- densation of AA, Meerwein–Ponndorf–Verley (MPV) reduction of crotonaldehyde (CA) with EtOH to crotyl alcohol and AA, and dehydration of crotyl alcohol to BD * Olga V. Larina olga.larina@ukr.net 1 L.V. Pisarzhevskii Institute of Physical Chemistry, The National Academy of Sciences of Ukraine, 31 Prosp. Nauky, Kyiv 03028, Ukraine