Patent US4135911A successfully refreshed from Google Patents.
US4135911A
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US
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Rhodium recovery from hydroformylation still heel with triaryl phosphite ligand
Assignee: EIDP Inc
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Filing: 1978-05-12
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Granted: 1979-01-23
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Expires: 1998-05-12
Abstract
Abstract A process for recovering rhodium present in a still heel from the hydroformylation of an unsaturated hydrocarbon wherein rhodium and a triaryl phosphite ligand were used by a process comprising (a) pretreating the still heel with a compatible organic solvent or a mixture thereof, at least 5 ml of water per 100 g of still heel, oxygen gas or a precursor thereof and sufficient base to produce a pH of 2 to 7 in the reaction mixture after rhodium precipitation; (b) heating to a temperature of from 0° to 80° C to oxidize the triaryl phosphite ligand to the corresponding phosphate compound; (c) heating the mixture from (b) for from about 15 minutes to about 120 minutes at about 115° C to about 175° C to precipitate zero valent rhodium; and optionally purifying the precipitated rhodium from (c) by (d) separating the rhodium precipitate; (e) washing the rhodium precipitate with a solvent-acid solution at a pH of 3 to 4; (f) treating the rhodium precipitate with an alkaline reducing solution to reduce the trivalent rhodium impurity to zero valent rhodium; (g) quenching the rhodium with glacial acetic acid; (h) separating the rhodium; (i) washing the rhodium with an acid solution at a pH of 3 to 4; (j) drying the rhodium in an inert atmosphere at from 250° to 400° C; and (k) oxidizing the rhodium at a temperature of from 300° to 900° C to convert the rhodium to Rh 2 O 3 .
Inventors
- 👤 Jean L. Balmat
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 20:04
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/40; B01J31/4015; B01J31/4023; B01J31/4038; B01J31/4046; B01J31/16; B01J31/18; B01J31/1845; B01J31/185; B01J31/20; C; C01; C01G; C01G55/00; C01G55/001; C22; C22B; C22B11/00; C22B11/04; C22B3/00; C22B3/20; C22B3/26; C22B3/32; C22B3/38; C22B3/383; C22B3/384; C22B3/3846; B01J2231/00; B01J2231/30; B01J2231/32; B01J2231/321; B01J23/00; B01J23/38; B01J23/40; B01J23/46; B01J23/464; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/822; B01J31/02; B01J31/0201; Y; Y02; Y02P; Y02P10/00; Y02P10/20; Y02P20/00; Y02P20/50; Y02P20/584
Claims Analysis
Total Claims: 42
Claim 1
Independent Claim
157 words
A process for recovering rhodium that is present in a still heel from the hydroformylation of an unsaturated hydrocarbon, said still heel comprising rhodium triaryl phosphite complex catalyst, triaryl phosphite ligand and high boilers, said process comprising (a) pretreating the still heel with a mixture of (1) methanol, methyl ethyl ketone, acetone, ethanol, propanol, isopropanol, diethyl ketone, methyl propyl ketone, ethyl propyl ketone or mixtures thereof, (2) at least 5 ml of water per 100 g of still heel, (3) oxygen gas or a precursor thereof and (4) sufficient base to adjust the pH of the still heel after rhodium precipitation to from 2 to 7; (b) heating the mixture from (a) to a temperature of from 0° to 85° C. until the triaryl phosphite is oxidized to the corresponding phosphate compound; and (c) heating the mixture from (b) for from 15 minutes to 120 minutes at from 115° to 175° C. to precipitate zero valent rhodium.
Claim 2
Dependent Claim
157 words
A process for recovering rhodium that is present in a still heel from the hydroformylation of an unsaturated hydrocarbon, said still heel comprising rhodium triaryl phosphite complex catalyst, triaryl phosphite ligand and high boilers, said process comprising (a) pretreating the still heel with a mixture of (1) methanol, methyl ethyl ketone, acetone, ethanol, propanol, isopropanol, diethyl ketone, methyl propyl ketone, ethyl propyl ketone or mixtures thereof, (2) at least 5 ml of water per 100 g of still heel, (3) oxygen gas or a precursor thereof and (4) sufficient base to adjust the pH of the still heel after rhodium precipitation to from 2 to 7; (b) heating the mixture from (a) to a temperature of from 0° to 85° C. until the triaryl phosphite is oxidized to the corresponding phosphate compound; and (c) heating the mixture from (b) for from 15 minutes to 120 minutes at from 115° to 175° C. to precipitate zero valent rhodium.
Claim 3
Dependent Claim
12 words
The process of claim 1 wherein the compatible organic solvent is methanol.
Claim 4
Dependent Claim
17 words
The process of claim 1 wherein the pH of the solution in (b) is 3.0 to 6.0.
Claim 5
Dependent Claim
16 words
The process of claim 1 wherein the temperature in (b) is from 20° to 85° C.
Claim 6
Dependent Claim
16 words
The process of claim 1 wherein the temperature in (c) is from 150° to 165° C.
Claim 7
Dependent Claim
21 words
The process of claim 1 wherein at least 90% by weight of the rhodium present in the still heel is recovered.
Claim 8
Dependent Claim
21 words
The process of claim 1 wherein at least 99% by weight of the rhodium present in the still heel is recovered.
Claim 9
Dependent Claim
16 words
The process of claim 1 wherein the heating in (c) is done under an inert atmosphere.
Claim 10
Dependent Claim
50 words
The process of claim 1 wherein the rhodium precipitate is separated from the mixture, washed with a solvent-acid solution with a pH of from 3 to 4 and oxidized with oxygen at a temperature of from 300° to 900° C. to convert the rhodium to Rh 2 O 3 .
Claim 11
Dependent Claim
20 words
The process of claim 9 wherein at least 90% by weight of the rhodium in the still heel is recovered.
Claim 12
Dependent Claim
25 words
The process of claim 9 wherein at least 95% by weight of the oxidized rhodium is dissolved in a triaryl phosphite ligand and carbon monoxide.
Claim 13
Dependent Claim
156 words
The process of claim 1 wherein (d) the rhodium precipitate is separated from the mixture; (e) the rhodium precipitate is washed with a solvent-acid solution having a pH of from 3 to 4 to remove residual still heel; (f) the rhodium precipitate from (e) is treated with an alkaline reducing solution that will reduce the trivalent rhodium impurity to zero valent rhodium; (g) the rhodium from (f) is quenched with glacial acetic acid to destroy any residual reducing solution; (h) the rhodium from (g) is separated; (i) the rhodium from (h) is washed with an aqueous acetic acid solution with a pH of from 3 to 4; (j) the rhodium from (i) is dried in an inert atmosphere at a temperature of from 250° to 400° C.; and (k) the rhodium from (j) is oxidized with oxygen at a temperature of from 300° to 900° C. to convert the rhodium to Rh 2 O 3 .
Claim 14
Dependent Claim
14 words
The process of claim 12 wherein the compatible organic solvent in (a) is methanol.
Claim 15
Dependent Claim
14 words
The process of claim 12 wherein the acid in (e) is glacial acetic acid.
Claim 16
Dependent Claim
12 words
The process of claim 12 wherein the solvent in (e) is methanol.
Claim 17
Dependent Claim
14 words
The process of claim 15 wherein the acid in (e) is glacial acetic acid.
Claim 18
Dependent Claim
12 words
The process of claim 12 wherein the solvent in (e) is acetone.
Claim 19
Dependent Claim
14 words
The process of claim 17 wherein the acid in (e) is glacial acetic acid.
Claim 20
Dependent Claim
17 words
The process of claim 12 wherein the pH of the solution in (b) is 3 to 6.
Claim 21
Dependent Claim
16 words
The process of claim 12 wherein the temperature in (b) is from 20° to 85° C.
Claim 22
Dependent Claim
15 words
The process of claim 12 wherein the reducing solution is a solution of sodium borohydride.
Claim 23
Dependent Claim
18 words
The process of claim 12 wherein the drying is at a temperature of from 325° to 350° C.
Claim 24
Dependent Claim
18 words
The process of claim 12 wherein the oxidizing is at a temperature of from 625° to 650° C.
Claim 25
Dependent Claim
26 words
The process of claim 12 wherein at least 90% by weight of the rhodium from (k) is dissolved in a triaryl phosphite ligand and carbon monoxide.
Claim 26
Dependent Claim
25 words
The process of claim 12 wherein at least 95% by weight of the rhodium from (k) is dissolved in a triaryl phosphite and carbon monoxide.
Claim 27
Dependent Claim
17 words
The process of claim 12 wherein the heating in (c) is done under an atmosphere of nitrogen.
Claim 28
Dependent Claim
14 words
The process of claim 26 wherein the compatible organic solvent in (a) is methanol.
Claim 29
Dependent Claim
12 words
The process of claim 26 wherein the solvent in (e) is methanol.
Claim 30
Dependent Claim
14 words
The process of claim 26 wherein the acid in (e) is glacial acetic acid.
Claim 31
Dependent Claim
12 words
The process of claim 26 wherein the solvent in (e) is acetone.
Claim 32
Dependent Claim
14 words
The process of claim 28 wherein the acid in (e) is glacial acetic acid.
Claim 33
Dependent Claim
14 words
The process of claim 30 wherein the acid in (e) is glacial acetic acid.
Claim 34
Dependent Claim
17 words
The process of claim 26 wherein the pH of the solution in (b) is 3 to 6.
Claim 35
Dependent Claim
15 words
The process of claim 26 wherein the temperature in (b) is 20° to 85° C.
Claim 36
Dependent Claim
16 words
The process of claim 26 wherein the temperature in (c) is from 150° to 175° C.
Claim 37
Dependent Claim
15 words
The process of claim 26 wherein the reducing solution is a solution of sodium borohydride.
Claim 38
Dependent Claim
18 words
The process of claim 26 wherein the drying is at a temperature of from 325° to 350° C.
Claim 39
Dependent Claim
18 words
The process of claim 26 wherein the oxidizing is at a temperature of from 625° to 650° C.
Claim 40
Dependent Claim
21 words
The process of claim 26 wherein at least 90% by weight of the rhodium present in the still heel is recovered.
Claim 41
Dependent Claim
25 words
The process of claim 26 wherein at least 90% by weight of the rhodium from (k) is dissolved in a triaryl phosphite and carbon monoxide.
Claim 42
Dependent Claim
25 words
The process of claim 26 wherein at least 95% by weight of the rhodium from (k) is dissolved in a triaryl phosphite and carbon monoxide.
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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) | 1982-01-22 | 1982-07-24 | 1983-01-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-01-22 | 1986-07-24 | 1987-01-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-01-22 | 1990-07-24 | 1991-01-23 | $7700.00 | Window Closed / Lapsed |