Catalytic Oxidation of Glycerol

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Helsinki University of Technology | Diplomityö
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Date

2004

Department

Kemian tekniikan osasto

Major/Subject

Teknillinen kemia

Mcode

Kem-40

Degree programme

Language

en

Pages

vii + 73 s. + liitt. 10

Series

Abstract

The catalytic oxidation of glycerol is an economical and environmentally friendly way to produce its value-added oxygenates. Very few studies have been published on this topic, however. Heterogenerous catalysts like platinum supported on activated carbon can be used for the oxidation of glycerol. Some value-added products like dihydroxyacetone and glyceric acid can be obtained by oxidation. The resulting oxidation products depend highly on the catalyst and the reaction conditions. The aim of the experimental part of this thesis was to study homogeneous copper complexes used in the oxidation of alcohols and their effectiveness in the oxidation of glycerol. Different ligands and copper ligand ratios were studied to optimize the conversion of glycerol and the selectivity to desired products (glyceric acid and tartronic acid). Copper (II) ion catalyst was active in the oxidation of glycerol with molecular oxygen in alkaline solution. The addition of certain Iigands, 1,10-phenanthroline and 4,4'-dihydroxy-2,2'-bipyridine, improved both the conversion of glycerol and the selectivities to the desired products. The optimal copper ligand molar ratio was 1:2. The selectivity to glyceric acid was high at the beginning of the reaction, but decreased with time. The best yield of glyceric acid was 24.7% in 5 hours and the best yield of tartronic acid was 29.5% in 22 hours. The selectivities to undesired products (formic acid and oxalic acid) increased with time. High alkalinity of the solvent (over pH 10) was needed for the reactions. The optimal solvent was 0.25 mol/kg NaOH when glycerol was 100 mmol/kg and catalyst 0.2 mmol/kg. The reactions were dependent on reaction temperature and oxygen pressure. The reference catalyst (Co-sulphosalen) was totally inactive.

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Supervisor

Krause, Outi

Thesis advisor

Sippola, Väinö

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Permanent link to this item

https://urn.fi/URN:NBN:fi:aalto-2020120451464

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[dipl] Teknillinen korkeakoulu / TKK