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Vapour phase transfer hydrogenation of α,β-unsaturated carbonyl compounds. Thermodynamic and experimental studies

Paper ID Volume ID Publish Year Pages File Format Full-Text
38979 45799 2016 10 PDF Available
Title
Vapour phase transfer hydrogenation of α,β-unsaturated carbonyl compounds. Thermodynamic and experimental studies
Abstract

•Transfer hydrogenation (TH) of α,β-unsatd. carbonyl compounds over MgO is studied.•The 1st thermodynamic description of hydrogenation/transfer hydrogenation is given.•The formation of unsaturated alcohols is not favoured thermodynamically.•Very high chemoselectivity towards allyl alcohol was noted in TH of acrolein.•Reactivity of 2-PrOH highly exceeded that of EtOH in TH, except with acrolein.

This paper presents the first systematic thermodynamic study of the vapour phase transfer hydrogenation of α,β-unsaturated carbonyl compounds at temperatures: 423.15–723.15 K. Calculations were made for four compounds, namely: acrolein, α-methylacrolein, β-methylacrolein and methyl vinyl ketone. The Gibbs free energies and equilibrium mole fractions (EMFs) were calculated for transfer hydrogenation with ethanol and 2-propanol as hydrogen donors. It was noted that for transfer hydrogenation and hydrogenation with hydrogen the formation of the unsaturated alcohol (UOL) is the least thermodynamically favoured reaction and that saturated alcohol (SOL) and saturated aldehyde or ketone (SAL or SON) are the main products.A set of eight carbonyl compounds have been transfer hydrogenated with ethanol and 2-propanol in the presence of MgO as the catalyst. The main conclusions are that: (a) the reduction of a carbonyl group into a carbinol group occurs with a very high selectivity, (b) for almost all carbonyl compounds, except acrolein, the reactivity of 2-propanol highly exceeded that shown by ethanol and (c) the high chemoselectivity of transfer hydrogenation of acrolein with alcohols resulted from the kinetic control caused by the presence of magnesium oxide.

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Keywords
A, hydrogen acceptor; CTH, catalytic transfer hydrogenation; D, hydrogen donor; D/A, donor/acceptor molar ratio; EMF, equilibrium mole fraction; SAL, saturated aldehyde; SOL, saturated alcohol; SON, saturated ketone; UAL, unsaturated aldehyde; UOL, unsatu
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Vapour phase transfer hydrogenation of α,β-unsaturated carbonyl compounds. Thermodynamic and experimental studies
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Publisher
Database: Elsevier - ScienceDirect
Journal: Applied Catalysis A: General - Volume 511, 5 February 2016, Pages 131–140
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
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