Print Email Facebook Twitter Hydride transfer versus deprotonation kinetics in the isobutane−propene alkylation reaction Title Hydride transfer versus deprotonation kinetics in the isobutane−propene alkylation reaction: A computational study Author Liu, Chong (Eindhoven University of Technology) Van Santen, Rutger A. (Eindhoven University of Technology) Poursaeidesfahani, A. (TU Delft Engineering Thermodynamics) Vlugt, T.J.H. (TU Delft Engineering Thermodynamics) Pidko, Evgeny A. (Eindhoven University of Technology; ITMO University) Hensen, Emiel J M (Eindhoven University of Technology) Date 2017 Abstract The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C–C bond formation between a tert-butyl fragment and an additional olefin, or via deprotonation of the tert-butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle. Subject hydride transferalkylationdeactivationfaujasiteperiodic DFTmicrokinetics To reference this document use: http://resolver.tudelft.nl/uuid:9c663ca9-a4ce-48c7-a9f6-62052a78f80d DOI https://doi.org/10.1021/acscatal.7b02877 ISSN 2155-5435 Source ACS Catalysis, 7 (12), 8613–8627 Part of collection Institutional Repository Document type journal article Rights © 2017 Chong Liu, Rutger A. Van Santen, A. Poursaeidesfahani, T.J.H. Vlugt, Evgeny A. Pidko, Emiel J M Hensen Files PDF acscatal.7b02877.pdf 4.56 MB Close viewer /islandora/object/uuid:9c663ca9-a4ce-48c7-a9f6-62052a78f80d/datastream/OBJ/view