Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1996-09-13
1999-07-06
Dees, Jose G.
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568444, C07C 4500
Patent
active
059199873
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a process for the preparation of alcohols and/or aldehydes by hydroformylation of olefins of more than 3 carbon atoms, comprising hydroformylation by means of a rhodium catalyst homogeneously dissolved in the reaction medium, the separation of the rhodium catalyst from the mixture discharged from the hydroformylation reaction and the recycling of the rhodium separated from the discharged hydroformylation mixture to the hydroformylation stage.
The hydroformylation of olefins with carbon monoxide and hydrogen in the presence of transition metal catalysts is known. While .alpha.-olefins can be very readily hydroformylated with rhodium-containing, phosphine-modified catalysts (cf. J. Falbe, Ed: New Syntheses With Carbon Monoxide, Springer, Berlin 1980, page 55 et seq.), this catalyst system is not very suitable for internal and internal, branched olefins and for olefins of more than 7 carbon atoms (cf. Falbe, page 95 et seq.). Thus, internal carbon-carbon double bonds are only very slowly hydroformylated in the presence of such a catalyst. Since the separation of the hydroformylation product from the catalyst dissolved homogeneously in the reaction system is generally effected by distillation and the boiling point of the aldehyde formed in the hydroformylation increases with the increasing number of carbon atoms and chain length to temperatures at which the rhodium-containing catalyst decomposes, this hydroformylation method is not economical for the hydroformylation of olefins of more than 7 carbon atoms. In the hydroformylation of polymeric olefins, for example of polyisobutene, the catalyst containing noble metal cannot be recovered in a reusable form.
On the other hand, internal and internal, branched olefins can advantageously be hydroformylated with uncomplexed rhodium, ie. with rhodium compounds dissolved homogeneously in the hydroformylation medium and not modified with phosphorus-containing ligands, such as phosphines or phosphites. Such rhodium catalysts not modified with phosphines or phosphites and the suitability thereof as catalysts for the hydroformylation of the above-mentioned classes of olefins are known (cf. Falbe, page 38 et seq.). The terms uncomplexed rhodium and uncomplexed rhodium catalysts are used in this application for rhodium hydroformylation catalysts which, in contrast to conventional rhodium hydroformylation catalysts, are not modified with ligands, in particular not with phosphorus-containing ligands, such as phosphine or phosphite ligands, under the conditions of the hydroformylation. Ligands in this context are not understood as including carbonyl or hydrido ligands. In the technical literature (cf. Falbe, page 38 et seq.), it is assumed that the rhodium compound HRh(CO).sub.4 is the catalytically active rhodium species in the hydroformylation with uncomplexed rhodium catalysts, although this has not been unambiguously proven owing to the many chemical mechanisms proceeding side by side in the hydroformylation reaction zone. We make use of this assumption in this application only for the sake of simplicity without as a result restricting the scope of protection of the present application if in the future a rhodium species other than the stated one should prove to be the actual catalytically active species. Under the conditions of the hydroformylation reaction, the uncomplexed rhodium catalysts are formed from rhodium compounds, for example rhodium salts, such as rhodium(III) chloride, rhodium(III) nitrate, rhodium(III) acetate, rhodium(II) acetate, rhodium(III) sulfate or rhodium(III) ammonium chloride, from rhodium chalcogenides, such as rhodium(III) oxide or rhodium(III) sulfide, from salts of rhodium oxo acids, for example the rhodates, from rhodium carbonyl compounds, such as Rh.sub.4 (CO).sub.12 and Rh.sub.6 (CO).sub.16, or from organorhodium compounds, such as dicarbonylrhodium acetonylacetonate or cyclooctadienylrhodium acetate or chloride, in the presence of CO/H.sub.2 mixtures, which are referred to generally as synthesis gas. For car
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Aron Maik
Harder Wolfgang
Kneuper Heinz-Josef
Korgitzsch Frank-Michael
Nilles Michael
Badio Barbara
BASF - Aktiengesellschaft
Dees Jos,e G.
Shurtleff John H.
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