Gas Phase Catalytic Hydrogenation of C4 Alkynols over Pd/Al2O3

Alberto Gonzalez Fernandez, Chiara Pischetola, Fernando Cardenas-Lizana

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Abstract

Alkenols are commercially important chemicals employed in the pharmaceutical and agro-food industries. The conventional production route via liquid phase (batch) alkynol hydrogenation suffers from the requirement for separation/purification unit operations to extract the target product. We have examined, for the first time, the continuous gas phase hydrogenation (P = 1 atm; T = 373 K) of primary (3-butyn-1-ol), secondary (3-butyn-2-ol) and tertiary (2-methyl-3-butyn-2-ol) C4 alkynols using a 1.2% wt. Pd/Al2O3 catalyst. Post-TPR, the catalyst exhibited a narrow distribution of Pdδ- (based on XPS) nanoparticles in the size range 1-6 nm (mean size = 3 nm from STEM). Hydrogenation of the primary and secondary alkynols was observed to occur in a stepwise fashion (-C≡C- → -C=C- → -C-C-) while alkanol formation via direct -C≡C- → -C-C- bond transformation was in evidence in the conversion of 2-methyl-3-butyn-2-ol. Ketone formation via double bond migration was promoted to a greater extent in the transformation of secondary (vs. primary) alkynol. Hydrogenation rate increased in the order primary < secondary < tertiary. The selectivity and reactivity trends are accounted for in terms of electronic effects.
Original languageEnglish
Article number924
Number of pages12
JournalCatalysts
Volume9
Issue number11
DOIs
Publication statusPublished - 6 Nov 2019

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Hydrogenation
hydrogenation
Gases
vapor phases
catalysts
Catalysts
Ketones
food
purification
ketones
Drug products
Purification
liquid phases
X ray photoelectron spectroscopy
reactivity
selectivity
industries
routes
Nanoparticles
trends

Keywords

  • 2-methyl-3-butyn-2-ol
  • 3-butyn-1-ol
  • 3-butyn-2-ol
  • Alkenols
  • Alkynols
  • Gas phase hydrogenation
  • Pd/Al O
  • Triple bond electron charge

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Gonzalez Fernandez, Alberto ; Pischetola, Chiara ; Cardenas-Lizana, Fernando. / Gas Phase Catalytic Hydrogenation of C4 Alkynols over Pd/Al2O3. In: Catalysts. 2019 ; Vol. 9, No. 11.
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Gas Phase Catalytic Hydrogenation of C4 Alkynols over Pd/Al2O3. / Gonzalez Fernandez, Alberto; Pischetola, Chiara; Cardenas-Lizana, Fernando.

In: Catalysts, Vol. 9, No. 11, 924, 06.11.2019.

Research output: Contribution to journalArticle

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AU - Pischetola, Chiara

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AB - Alkenols are commercially important chemicals employed in the pharmaceutical and agro-food industries. The conventional production route via liquid phase (batch) alkynol hydrogenation suffers from the requirement for separation/purification unit operations to extract the target product. We have examined, for the first time, the continuous gas phase hydrogenation (P = 1 atm; T = 373 K) of primary (3-butyn-1-ol), secondary (3-butyn-2-ol) and tertiary (2-methyl-3-butyn-2-ol) C4 alkynols using a 1.2% wt. Pd/Al2O3 catalyst. Post-TPR, the catalyst exhibited a narrow distribution of Pdδ- (based on XPS) nanoparticles in the size range 1-6 nm (mean size = 3 nm from STEM). Hydrogenation of the primary and secondary alkynols was observed to occur in a stepwise fashion (-C≡C- → -C=C- → -C-C-) while alkanol formation via direct -C≡C- → -C-C- bond transformation was in evidence in the conversion of 2-methyl-3-butyn-2-ol. Ketone formation via double bond migration was promoted to a greater extent in the transformation of secondary (vs. primary) alkynol. Hydrogenation rate increased in the order primary < secondary < tertiary. The selectivity and reactivity trends are accounted for in terms of electronic effects.

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