Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

KINETICS OF AN AQUEOUS ALKALI OXIDATIONOF BOUNDEDLY WATER-SOLUBLE PRIMARY ALCOHOLSStaroverov D.V., Varlamova E.V., Suchkov Yu.P., Shvets V.F.D. Mendeleyev University of Chemical Technology of Russia,Miusskaya Sq. 9, 125047 Moscow, Russia;phone/fax: +7 495 978 95 54; E-mail: stardv@pxty.ruPP-I-14Oxidation of boundedly water-soluble primary alcohols, such as isoamyl alcohol,phenoxyethanol, phenylethanol and so on, with oxygen in aqueous alkali solutions on noblemetals is attractive method for preparation of some valuable acids:RCH 2 OH + O 2 + NaOH ⎯⎯→ RCOONa + 2 H 2 O.Kinetics of above reaction on the Pd/C catalyst has been studied by the examples ofisoamyl alcohol, and also such homologues as n-butyl and i-butyl alcohols. Though amongoxidation products in significant quantities there is an aldehyde and an ester of initial alcoholand a target acid, a main product is salt of a target acid (Fig. 1; t = 80°C, the catalyst of 2 %Pd/C; 1 — isoamyl alcohol, 2 — sodium isovalerate, 3 — isovaleraldehyde, 4 — isoamylisovalerate).0,8Fig. 110Fig. 2С, mol/l0,60,4120,2340,0 0,2 0,4 0,6 0,8Alcohol conversion X al, % molr 0·10 3 , mol/(l·min)86420,00 0,02 0,04 0,06 0,08 0,10C cat, kg/lSalt formation kinetics was investigated in batch reactor. Isoamyl alcohol oxidation ratelinearly grows with increase in the catalyst content, however curve quits not zero (Fig. 2;t = 80°C, С al,0 =0.87 mol/l, С NaOH,0 =0.9 mol/l). At the same time rate relation to the alcoholcontent in reaction mixture is complex (Fig. 3): the range 1 corresponds to complete watersolubilityof alcohol, and ranges 2 and 3 corresponds to presence of an organic phase. Thekind of relationship ‘rate vs catalyst content’ in a Fig. 2 is characteristic for range 3.237