Assessing C3–C4 alcohol synthesis pathways over a MgAl oxide supported K/MoS2 catalyst via 13C2-ethanol and 13C2-ethylene co-feeds
| Autor: | Jin Wai Goh, Pradeep K. Agrawal, Micaela Taborga Claure, Christopher W. Jones, Leslie T. Gelbaum, Li-Chen Lee |
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| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Ethylene Ethanol 010405 organic chemistry Process Chemistry and Technology Alcohol 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound chemistry Alkoxy group Propionate Organic chemistry Methanol Physical and Theoretical Chemistry Carbonylation |
| Zdroj: | Journal of Molecular Catalysis A: Chemical. 423:224-232 |
| ISSN: | 1381-1169 |
| DOI: | 10.1016/j.molcata.2016.06.025 |
| Popis: | Mechanisms of C 3 –C 4 alcohol synthesis from syngas are elucidated over a Mg/Al mixed metal oxide (MMO) supported K/MoS 2 catalyst via 13 C 2 -ethanol and 13 C 2 -ethylene co-feeds. K/bulk-MoS 2 is used as a control catalyst to provide insight into the role of K/MoS 2 and K/MoS 2 -MMO sites on higher alcohol formation pathways. Analysis of the products via 13 C NMR show preferential enrichment of terminal carbons in C 3 –C 4 alcohols with both co-feeds, suggesting that CO insertion is the primary higher alcohol synthesis pathway, and that olefin carbonylation proceeds through the same pathway as alcohol formation. The observation of 13 C 4 -1-butanol species during the CO hydrogenation reactions with 13 C 2 -ethanol co-feeds provides conclusive evidence of ethanol self-coupling to 1-butanol as a secondary pathway. Additionally, acetate species are shown to be formed via an acyl precursor reacting with an alkoxy anion. Hydrogenation of an acetyl species (CH 3 CO*) to an ethoxy intermediate (C 2 H 5 O*) is shown to be largely irreversible under the reaction conditions employed, as no preferential enrichment is observed for the acetyl group in acetate species. Propionate species are shown to be formed via esterification of propionate with the corresponding alcohol, while isobutyl alcohol formation observed over both the K/bulk-MoS 2 and the MMO supported catalysts occurs via methanol coupling with 1-propanol or 1-propanol derived species. |
| Databáze: | OpenAIRE |
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