Quantification of active sites in yttrium containing dealuminated Beta zeolites during conversion of ethanol and acetaldehyde to butadiene

Borate, Shivangi N.; Samad, Nohor “River”; Purdy, Stephen C.; Zhang, Junyan; Bornes, Carlos; Cordon, Michael J.; Li, Meijun; Mafra, Luís; Sutton, Andrew D.; Li, Zhenglong; Harris, James W.

doi:10.1016/j.jcat.2024.115468

Title: Quantification of active sites in yttrium containing dealuminated Beta zeolites during conversion of ethanol and acetaldehyde to butadiene

Journal Article · 30 March 2024 · Journal of Catalysis

DOI: https://doi.org/10.1016/j.jcat.2024.115468 · OSTI ID:2438947

^[1]; Samad, Nohor “River” ^[1];

^[2];

^[3]; Cordon, Michael J. ^[2];

^[2]; Mafra, Luís ^[3]; Sutton, Andrew D. ^[2]; Li, Zhenglong ^[2];

^[1]

Univ. of Alabama, Tuscaloosa, AL (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
University of Aveiro (Portugal)

Here, in this work, yttrium containing dealuminated Beta zeolites (Y/deAlBeta) were synthesized and characterized by various spectroscopic techniques to improve understanding of ethanol upgrading over these materials. Characterization results indicate yttrium atoms partially condense with framework silanol nests formed during dealumination of parent Al-Beta supports. Active sites for conversion of ethanol and acetaldehyde to butadiene were quantified on a series of Y/deAlBeta catalysts (0.1–10 wt% yttrium) via ex situ chemisorption and transmission Fourier transformed infrared (FTIR) spectroscopy measurements by first measuring the integrated molar extinction coefficient (IMEC) for pyridine bound to Lewis acidic yttrium sites. In situ titrations with pyridine demonstrate that the number of sites quantified by ex situ chemisorption IR is quantitatively similar to the number of sites that catalyze butadiene formation, which varies (from 0.05 to 0.35) across the series of catalysts. In situ pyridine titrations impact butadiene site time yields (STY), but not crotonaldehyde STY, indicating that a distribution of yttrium sites is present, and that discrete yttrium site types participate in distinct steps in the pathway from ethanol to butadiene. Apparent kinetic parameters including activation energies and reaction orders were measured, these suggest differences in reactant (or reactant-derived intermediate) surface coverages result in higher STYs (per mol Y or per Lewis acidic Y site) for samples with low Y loadings relative to those with higher Y loadings. Isotopic labeling experiments evince the existence of other kinetically relevant steps in addition to the crotonaldehyde transformation to crotyl alcohol. Together, these findings provide further guidance into the heterogeneities in site structures in yttrium-containing zeolites and their relevance for the various steps in the pathway from ethanol to C₄ products useful for production of sustainable aviation fuel and renewable butadiene.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO)

Grant/Contract Number:: AC05-00OR22725; EE0010304

OSTI ID:: 2438947

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 433; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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