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Selective synthesis of isobutanol by means of the Guerbet reaction: Part 2. Reaction of methanol/ethanol and methanol/ethanol/n-propanol mixtures over copper based/MeONa catalytic systems
Authors:Carlo Carlini  Marco Di Girolamo  Alessandro Macinai  Mario Marchionna  Marilena Noviello  Anna Maria Raspolli Galletti  Glauco Sbrana
Institution:

a Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Risorgimento 35, 56126, Pisa, Italy

b Snamprogetti S.p.A., Via Maritano 26, 20097 San Donato, Milanese, MI, Italy

c Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126, Pisa, Italy

Abstract:The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst.
Keywords:Copper chromite  Sodium methoxide  Guerbet isobutanol synthesis  Condensation of methanol with higher alcohols
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