Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1998-07-15
2000-08-22
Richter, Johann
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568451, 568455, C07C 4550
Patent
active
061075248
DESCRIPTION:
BRIEF SUMMARY
DESCRIPTION
The invention relates to a process for the preparation of aldehydes or aldehydes and alcohols by hydroformylation of olefins containing more than 3 carbon atoms and recovery of the catalyst by a combination of (1) recycling the distillation bottoms following the removal, by distillation, of the hydroformylation products and (2) extracting the catalyst complex with aqueous solutions of weak acids whose polydentate nitrogenous ligand additionally contains at least one tertiary nitrogen radical protonizable with weak acids.
The hydroformylation of olefins with carbon monoxide and hydrogen in the presence of transition metal catalysts is well known. While .alpha.-olefins are capable of hydroformylation to a high degree using rhodium-containing catalysts (cf J. Falbe, Ed.: New Syntheses With Carbon Monoxide, Springer, Berlin 1980, pp. 55 et seq), this catalyst system is less suitable for internal and internal, branched-chain olefins and also for olefins containing more than 7 carbon atoms (cf Falbe, pp. 95 et seq). Thus internal carbon-carbon double bonds are hydroformylated in the presence of such a catalyst only very slowly. Since the separation of the hydroformylation product from the homogeneous catalyst dissolved in the reaction system usually takes place by distillation and the boiling point of the aldehyde formed during hydroformylation increases with increasing carbon number and chain length to temperatures at which the rhodium-containing catalyst decomposes, this hydroformylation method is uneconomical for the hydroformylation of olefins containing more than 7 carbon atoms. In the hydroformylation of polymeric olefins such as polyisobutene, the noble metal-containing catalyst cannot be recovered in a reusable form.
On the other hand internal and internal, branched-chain olefins can be advantageously hydroformylated with so-called "bare" rhodium, ie with homogeneous rhodium compounds dissolved in the hydroformylation medium and not modified with phosphorous ligands such as phosphines or phosphites. Such rhodium catalysts not modified with phosphines or phosphites and their suitability as catalysts for the hydroformylation of the aforementioned classes of olefins are known (cf Falbe, pp. 38 et seq). The terms "bare rhodium" or "bare rhodium catalysts" are used in this application for rhodium hydroformylation catalysts which are not modified, under the conditions of the hydroformylation, with ligands and particularly not with phosphorous ligands such as phosphine or phosphite ligands, unlike conventional rhodium hydroformylation catalysts. Carbonyl or hydrido ligands are not to be regarded as ligands in this context. It is assumed in the technical literature (cf Falbe, pp. 38 et seq), that the rhodium compound HRh(CO).sub.4 is the catalytically active rhodium species in the hydroformylation using "bare rhodium catalysts", although this is not absolutely proven on account of the many chemisms concurrently taking place in the hydroformylation reaction zone. Only for the sake of simplicity do we also go by this assumption in the present application, without this imposing any restriction on the scope of the invention, if at some time in the future a rhodium species other than that stated should turn out to be the actual catalytically active species. The "bare rhodium catalysts" form under the conditions of the hydroformylation reaction from rhodium compounds, eg 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 chalkogenides, such as rhodium(III) oxide or rhodium(III) sulfide, from salts of rhodium oxyacids, 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 rhodium dicarbonyl acetylacetonate, cyclooctadiene rhodium acetate or chloride in the presence of CO/H.sub.2 mixtures, generally designated as synthesis gas. For information on the execution of hydroformylations
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Geissler Bernhard
Kneuper Heinz-Josef
Paciello Rocco
Roper Michael
BASF - Aktiengesellschaft
Padmanabhan Sreeni
Richter Johann
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