''Hydrogen-free'' hydrogenation of nitrobenzene over Cu/SiO2 via coupling with 2-butanol dehydrogenation

Maoshuai Li, Yufen Hao, Fernando Cardenas-Lizana, Humphrey H. P. Yiu, Mark A. Keane

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Abstract

The feasibility of a coupled reaction system for the simultaneous production of 2-butanone (from 2-butanol dehydrogenation) and aniline (from nitrobenzene hydrogenation) over Cu/SiO2 in continuous gas phase operation without an external H-2 supply has been established. Two (15.9 and 1.8 % w/w) Cu/SiO2 catalysts were prepared by deposition-precipitation and characterised in terms of N-2 physisorption, temperature programmed reduction (TPR), H-2 chemisorption, powder XRD, STEM and XPS analysis. Following TPR, the higher Cu loading showed a wider particle size distribution (1-15 nm, mean 7.8 nm) than 1.8 % w/w Cu/SiO2 (1-6 nm, mean 3.1 nm), where the latter exhibited a modified electronic character based on XPS measurements and a (fourfold) higher H-2 uptake capacity. The reactions showed antipathetic (dehydrogenation) and sympathetic (hydrogenation) structure sensitivity in terms of turnover frequency (TOF) dependence on Cu size. We have achieved, for the first time, 100 % yield to both target products (2-butanone and aniline) with appreciably (by a factor of 50) enhanced hydrogen utilisation in the coupled system relative to conventional nitrobenzene reduction using pressurised H-2. Our results establish in situ hydrogen generation via catalytic dehydrogenation as a viable hydrogenation route to commercially important products.

Original languageEnglish
Pages (from-to)149-158
Number of pages10
JournalTopics in Catalysis
Volume58
Issue number2-3
Early online date19 Dec 2014
DOIs
Publication statusPublished - Mar 2015

Keywords

  • 2-Butanol
  • 2-Butanone
  • Nitrobenzene
  • Aniline
  • Dehydrogenation-hydrogenation coupling
  • Cu/SiO2
  • SUPPORTED GOLD NANOPARTICLES
  • COGELLED XEROGEL CATALYSTS
  • GAS-PHASE HYDROGENATION
  • N-ALKYLATION
  • CYCLOHEXANOL DEHYDROGENATION
  • ETHYLBENZENE DEHYDROGENATION
  • SELECTIVE HYDROGENATION
  • HYDROXIDE CATALYSTS
  • ACTIVATED CARBON
  • SHIFT REACTION

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