US4151209A
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Reduction of catalyst deactivation in processes for hydroformylation of olefins with rhodium complex catalysts
Assignee: Celanese Corp
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Filing: 1977-10-28
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Granted: 1979-04-24
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Expires: 1997-10-28
Abstract
Abstract In a process for hydroformylating an olefin in the presence of a catalyst comprising rhodium in complex combination with carbon monoxide and a triorganophosphorus ligand, progressive deactivation of the catalyst, as well as loss of the ligand species through by-product formation, are reduced by continuously stripping the liquid reaction medium to a degree such that the content of high-boiling organophosphorus by-products therein is maintained at a low level such that the ratio of phosphorus contained in said high-boiling by-products to phosphorus contained in the ligand present in the reaction medium does not exceed about 0.2.
Inventors
- 👤 James L. Paul
- 👤 Wendell L. Pieper
- 👤 Leslie E. Wade
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 17:41
CPC Classifications
C; C07; C07C; C07C45/00; C07C45/49; C07C45/50
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
178 words
In a process for hydroformylating a hydrocarbon of 2 to about 20 carbon atoms having an ethylenic double bond in the alpha position by reacting said hydrocarbon at about 80° C. to 150° C. with carbon monoxide and hydrogen in admixture with a liquid reaction medium containing as hydroformylation catalyst a complex of rhodium with a triorganophosphorus ligand and carbon monoxide to produce a liquid reaction product comprising said ligand, an aldehyde derivative of said hydrocarbon, and reaction by-products, the improvement which comprises: continuously stripping said liquid reaction medium, by gas stripping, distillation, or evaporation during the course of said hydroformylation reaction, to such a degree that the ratio of (a) phosphorus contained in said liquid reaction medium in the form of high-boiling organophosphorus reaction by-products excluding alkyl-substituted derivatives of said ligand formed by substitution of said olefin into said ligand molecule and also excluding oxides of said ligand and of said alkyl-substituted derivatives to (b) phosphorus contained in said reaction medium in the form of said ligand is maintained at a value not greater than about 0.2.
Claim 2
Dependent Claim
178 words
In a process for hydroformylating a hydrocarbon of 2 to about 20 carbon atoms having an ethylenic double bond in the alpha position by reacting said hydrocarbon at about 80° C. to 150° C. with carbon monoxide and hydrogen in admixture with a liquid reaction medium containing as hydroformylation catalyst a complex of rhodium with a triorganophosphorus ligand and carbon monoxide to produce a liquid reaction product comprising said ligand, an aldehyde derivative of said hydrocarbon, and reaction by-products, the improvement which comprises: continuously stripping said liquid reaction medium, by gas stripping, distillation, or evaporation during the course of said hydroformylation reaction, to such a degree that the ratio of (a) phosphorus contained in said liquid reaction medium in the form of high-boiling organophosphorus reaction by-products excluding alkyl-substituted derivatives of said ligand formed by substitution of said olefin into said ligand molecule and also excluding oxides of said ligand and of said alkyl-substituted derivatives to (b) phosphorus contained in said reaction medium in the form of said ligand is maintained at a value not greater than about 0.2.
Claim 3
Dependent Claim
29 words
The improvement of claim 1 wherein the triorganophosphorus ligand is triphenylphosphine and wherein said liquid reaction medium contains at least about one mole of triphenylphosphine per atom of rhodium.
Claim 4
Dependent Claim
20 words
The improvement of claim 2 wherein said liquid reaction medium comprises an inert liquid which is less volatile than triphenylphosphine.
Claim 5
Dependent Claim
20 words
The improvement of claim 2 wherein said alpha-olefinic hydrocarbon is an alkene having from 2 to about 20 carbon atoms.
Claim 6
Dependent Claim
16 words
The improvement of claim 4 wherein the alkene has from 3 to about 10 carbon atoms.
Claim 7
Dependent Claim
41 words
The improvement of claim 5 wherein said hydroformylation reaction is conducted and under a partial pressure of about 4 to 20 atmospheres of hydrogen and carbon monoxide combined, the molar ratio of hydrogen to carbon monoxide being about 0.5:1 to 10:1.
Claim 8
Dependent Claim
26 words
The improvement of claim 6 wherein the liquid reaction medium contains about 0.01 to 1.0% rhodium by weight and about 20 to 80% triphenylphosphine by weight.
Claim 9
Dependent Claim
183 words
In a process for hydroformylating a hydrocarbon of 2 to about 20 carbon atoms having an ethylenic double bond in the alpha position by reacting said hydrocarbon at about 80° C. to 150° C. with carbon monoxide and hydrogen in admixture with a liquid reaction medium containing as hydroformylation catalyst a complex of rhodium with a triorganophosphorus ligand and carbon monoxide to produce a liquid reaction product comprising said ligand, an aldehyde derivative of said hydrocarbon, and reaction by-products, the improvement which comprises: continuously stripping said liquid reaction medium during the course of said hydroformylation reaction, by passing a gas comprising said hydrogen and carbon monoxide therethrough, to such a degree that the ratio of (a) phosphorous contained in said liquid reaction medium in the form of high-boiling organophosphorus reaction by-products excluding alkyl-substituted derivatives of said ligand formed by substitution of said olefin into said ligand molecule and also excluding oxides of said ligand and of said alkyl-substituted derivatives to (b) phosphorus contained in said reaction medium in the form of said ligand is maintained at a value not greater than about 0.2.
Claim 10
Dependent Claim
183 words
In a process for hydroformylating a hydrocarbon of 2 to about 20 carbon atoms having an ethylenic double bond in the alpha position by reacting said hydrocarbon at about 80° C. to 150° C. with carbon monoxide and hydrogen in admixture with a liquid reaction medium containing as hydroformylation catalyst a complex of rhodium with a triorganophosphorus ligand and carbon monoxide to produce a liquid reaction product comprising said ligand, an aldehyde derivative of said hydrocarbon, and reaction by-products, the improvement which comprises: continuously stripping said liquid reaction medium during the course of said hydroformylation reaction, by passing a gas comprising said hydrogen and carbon monoxide therethrough, to such a degree that the ratio of (a) phosphorous contained in said liquid reaction medium in the form of high-boiling organophosphorus reaction by-products excluding alkyl-substituted derivatives of said ligand formed by substitution of said olefin into said ligand molecule and also excluding oxides of said ligand and of said alkyl-substituted derivatives to (b) phosphorus contained in said reaction medium in the form of said ligand is maintained at a value not greater than about 0.2.
Claim 11
Dependent Claim
19 words
The improvement of claim 8 wherein said hydrocarbon is an alkene having from 3 to about 10 carbon atoms.
Claim 12
Dependent Claim
185 words
In a process for hydroformylating a hydrocarbon of 2 to about 20 carbon atoms having an ethylenic double bond in the alpha position by reacting said hydrocarbon at about 80° C. to 150° C. with carbon monoxide and hydrogen in admixture with a liquid reaction medium containing as hydroformylation catalyst a complex of rhodium with a triorganophosphorus ligand and carbon monoxide to produce a liquid reaction product comprising said ligand, aldehyde derivative of said hydrocarbon, and reaction by-products, the improvement which comprises: continuously stripping said liquid reaction medium during the course of said hydroformylation reaction, by continuously distilling vapors comprising said aldehyde derivative out of said liquid reaction medium, to such a degree that the ratio of (a) phosphorus contained in said liguid reaction medium in the form of high-boiling organophosphorus reaction by-products excluding alkyl-substituted derivatives of said ligand formed by substitution of said olefin into said ligand molecule and also excluding oxides of said ligand and of said alkyl-substituted derivatives to (b) phosphorus contained in said reaction medium in the form of said ligand is maintained at a value not greater than about 0.2.
Claim 13
Dependent Claim
185 words
In a process for hydroformylating a hydrocarbon of 2 to about 20 carbon atoms having an ethylenic double bond in the alpha position by reacting said hydrocarbon at about 80° C. to 150° C. with carbon monoxide and hydrogen in admixture with a liquid reaction medium containing as hydroformylation catalyst a complex of rhodium with a triorganophosphorus ligand and carbon monoxide to produce a liquid reaction product comprising said ligand, aldehyde derivative of said hydrocarbon, and reaction by-products, the improvement which comprises: continuously stripping said liquid reaction medium during the course of said hydroformylation reaction, by continuously distilling vapors comprising said aldehyde derivative out of said liquid reaction medium, to such a degree that the ratio of (a) phosphorus contained in said liguid reaction medium in the form of high-boiling organophosphorus reaction by-products excluding alkyl-substituted derivatives of said ligand formed by substitution of said olefin into said ligand molecule and also excluding oxides of said ligand and of said alkyl-substituted derivatives to (b) phosphorus contained in said reaction medium in the form of said ligand is maintained at a value not greater than about 0.2.
Claim 14
Dependent Claim
19 words
The improvement of claim 10 wherein said hydrocarbon is an alkene having from 3 to about 10 carbon atoms.
References Cited (Backward Citations)
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1982-04-23 | 1982-10-23 | 1983-04-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-04-23 | 1986-10-23 | 1987-04-24 | $3760.00 | Window Closed / Lapsed |
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