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US4113754A
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Isolation and regeneration of rhodium-containing catalysts from distillation residues of hydroformylation reactions
Assignee: BASF SE
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Filing: 1977-03-23
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Granted: 1978-09-12
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Expires: 1997-03-23
Abstract
Abstract The isolation and regeneration of catalysts of type I or II clRh(CO)(PR.sub.3).sub.2 I hrh(CO)(PR.sub.3).sub.3 II, where the R's are identical or different hydrocarbon radicals, to give the catalysts in a pure form, is effected by regenerating aqueous rhodium salt solutions, as obtained on treating distillation residues of hydroformylation mixtures with oxygen-containing mineral acids and peroxides, by a method wherein the said aqueous rhodium salt solutions are treated with a cation exchanger, the latter is then separated from the solution, the absorbed rhodium ions are desorbed with hydrochloric acid, the hexachlororhodate solutions, containing hydrochloric acid, are reacted, in the presence of a water-soluble organic solvent and a tertiary phosphine PR 3 , with carbon monoxide, or with compounds which eliminate carbon monoxide, at from 0° to 150° C and from 1 to 5 bars, and the resulting complexes I or, if the process is carried out under hydrogenating conditions, the resulting complexes II, are separated off.
Inventors
- 👤 Rudolf Kummer
- 👤 Heinz-Walter Schneider
- 👤 Kurt Schwirten
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 20:51
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/40; B01J31/4015; B01J31/4023; B01J31/4038; B01J31/4046; B01J31/16; B01J31/20; B01J31/24; B01J31/2404; C; C07; C07C; C07C45/00; C07C45/49; C07C45/50; B01J2231/00; B01J2231/30; B01J2231/32; B01J2231/321; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/822; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/582; Y02P20/584
Claims Analysis
Total Claims: 12
Claim 1
Independent Claim
144 words
A process for isolating and regenerating a catalyst of type I clRh(CO)(PR.sub.3).sub.2 I wherein the R 's are identical or different optionally halogen- or oxygen-substituted hydrocarbon radicals, in a pure form, by regenerating an aqueous rhodium salt solution as obtained on treating a distillation residue of a rhodium-catalyzed hydroformylation reaction product mixture with an oxygen-containing mineral acid and a peroxide, wherein the said aqueous rhodium salt solution is treated with a cation exchanger, the latter is then separated from the solution, the absorbed rhodium ions are desorbed with hydrochloric acid, the hexachlororhodate solution containing hydrochloric acid is reacted in the presence of a water-soluble organic solvent and a tertiary phosphine PR 3 and at from 0° to 150° C. and from 1 to 5 bars with carbon monoxide or with a compound which eliminates carbon monoxide, and the resulting complex I, is separated off.
Claim 2
Dependent Claim
144 words
A process for isolating and regenerating a catalyst of type I clRh(CO)(PR.sub.3).sub.2 I wherein the R 's are identical or different optionally halogen- or oxygen-substituted hydrocarbon radicals, in a pure form, by regenerating an aqueous rhodium salt solution as obtained on treating a distillation residue of a rhodium-catalyzed hydroformylation reaction product mixture with an oxygen-containing mineral acid and a peroxide, wherein the said aqueous rhodium salt solution is treated with a cation exchanger, the latter is then separated from the solution, the absorbed rhodium ions are desorbed with hydrochloric acid, the hexachlororhodate solution containing hydrochloric acid is reacted in the presence of a water-soluble organic solvent and a tertiary phosphine PR 3 and at from 0° to 150° C. and from 1 to 5 bars with carbon monoxide or with a compound which eliminates carbon monoxide, and the resulting complex I, is separated off.
Claim 3
Dependent Claim
36 words
A process as claimed in claim 1, wherein the cation exchanger is employed in an amount to provide 10 to 100 equivalents of acid per gram atom of Rh +++ in the aqueous rhodium salt solution.
Claim 4
Dependent Claim
18 words
A process as claimed in claim 1, wherein the cation exchanger is a sulfonated or carboxylated styrene-divinylbenzene resin.
Claim 5
Dependent Claim
36 words
A process as claimed in claim 1, wherein the adsorbed rhodium ions are desorbed by reaction with 1N to 5N hydrochloric acid in an amount of from 20 to 100 moles per gram atom of rhodium.
Claim 6
Dependent Claim
155 words
A process for isolating and regenerating a catalyst of type II hrh(CO)(PR.sub.3).sub.3 II, where the R's are identical or different optionally halogen- or oxygen-substituted hydrocarbon radicals, in a pure form, by regenerating an aqueous rhodium salt solution as obtained on treating a distillation residue of a rhodium-catalyzed hydroformylation reaction product mixture with an oxygen-containing mineral acid and a peroxide, wherein the said aqueous rhodium salt solution is treated with a cation exchanger, the latter is then separated from the solution, the abosorbed rhodium ions are desorbed with hydrochloric acid, the hexachlororhodate solution containing hydrochloric acid is reacted in the presence of a water-soluble organic solvent and a tertiary phosphine PR 3 at from 0° to 150° C and from 1 to 5 bars with carbon monoxide or with a compound which eliminates carbon monoxide, using under hydrogenation conditions hydrogen or hydride ions to form the complex II, and the resulting complex II is separated off.
Claim 7
Dependent Claim
155 words
A process for isolating and regenerating a catalyst of type II hrh(CO)(PR.sub.3).sub.3 II, where the R's are identical or different optionally halogen- or oxygen-substituted hydrocarbon radicals, in a pure form, by regenerating an aqueous rhodium salt solution as obtained on treating a distillation residue of a rhodium-catalyzed hydroformylation reaction product mixture with an oxygen-containing mineral acid and a peroxide, wherein the said aqueous rhodium salt solution is treated with a cation exchanger, the latter is then separated from the solution, the abosorbed rhodium ions are desorbed with hydrochloric acid, the hexachlororhodate solution containing hydrochloric acid is reacted in the presence of a water-soluble organic solvent and a tertiary phosphine PR 3 at from 0° to 150° C and from 1 to 5 bars with carbon monoxide or with a compound which eliminates carbon monoxide, using under hydrogenation conditions hydrogen or hydride ions to form the complex II, and the resulting complex II is separated off.
Claim 8
Dependent Claim
36 words
A process as claimed in claim 5, wherein the cation exchanger is employed in an amount to provide 10 to 100 equivalents of acid per gram atom of Rh +++ in the aqueous rhodium salt solution.
Claim 9
Dependent Claim
18 words
A process as claimed in claim 5, wherein the cation exchanger is a sulfonated or carboxylated styrene-divinylbenzene resin.
Claim 10
Dependent Claim
36 words
A process as claimed in claim 5, wherein the absorbed rhodium ions are desorbed by reaction with 1N to 5N hydrochloric acid in an amount of from 20 to 100 moles per gram atom of rhodium.
Claim 11
Dependent Claim
29 words
A process as claimed in claim 5 wherein said hydrogenating conditions are provided by using hydrogen at 0° to 150° C. and a pressure of 1 to 300 bars.
Claim 12
Dependent Claim
36 words
A process as claimed in claim 5 wherein said hydrogenating conditions are provided by using a reducing agent which yields hydride ions used at a temperature of from 0° to 100° C. and at atmospheric pressure.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-09-11 | 1982-03-13 | 1982-09-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-09-11 | 1986-03-13 | 1986-09-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-09-11 | 1990-03-13 | 1990-09-12 | $7700.00 | Window Closed / Lapsed |