US4273936A
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Rhodium-catalyzed oxidation process for producing carboxylic acids
Assignee: Union Carbide Corp
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Filing: 1980-06-16
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Granted: 1981-06-16
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Expires: 2000-06-16
Abstract
Abstract A one-step process is disclosed for forming a carboxylic acid and its anhydride directly from the corresponding olefin which comprises reacting the olefin with carbon monoxide, hydrogen and oxygen in the presence of a stable rhodium complex catalyst. The rhodium catalyst is stabilized by a pentavalent Group V ligand, such as a phosphine oxide. The reaction is preferably conducted in an inert organic solvent. In an alternate embodiment, a carboxylic acid may be obtained by oxidation of an aldehyde (produced, for example, by hydroformylation of the corresponding olefin) in the presence of a rhodium complex catalyst stabilized by a pentavalent Group V ligand. This reaction is also preferably conducted in an inert organic solvent.
Inventors
- 👤 Rocco A. Fiato
- 👤 Roy L. Pruett
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 22:04
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/16; B01J31/18; B01J31/1895; B01J31/1845; B01J31/1875; C; C07; C07C; C07C45/00; C07C45/49; C07C45/50; C07C51/00; C07C51/10; C07C51/145; C07C51/16; C07C51/21; C07C51/23; C07C51/235; B01J2231/00; B01J2231/30; B01J2231/32; B01J2231/321; B01J2231/70; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/822
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
112 words
A process for preparing at least one of a carboxylic acid and its anhydride directly from an olefin comprising reacting the olefin with carbon monoxide, hydrogen and oxygen in the presence of a rhodium complex catalyst consisting essentially of rhodium stabilized by a pentavalent Group V ligand represented by the formula ##STR2## wherein R 1 , R 2 and R 3 , which may be the same or different, each represents a member selected from the group consisting of an alkyl group, an aryl group, an alkyl-substituted aryl group and an aryl-substituted alkyl group; and wherein M represents a Group V element selected from the group consisting of phosphorus, arsenic and antimony.
Claim 2
Dependent Claim
112 words
A process for preparing at least one of a carboxylic acid and its anhydride directly from an olefin comprising reacting the olefin with carbon monoxide, hydrogen and oxygen in the presence of a rhodium complex catalyst consisting essentially of rhodium stabilized by a pentavalent Group V ligand represented by the formula ##STR2## wherein R 1 , R 2 and R 3 , which may be the same or different, each represents a member selected from the group consisting of an alkyl group, an aryl group, an alkyl-substituted aryl group and an aryl-substituted alkyl group; and wherein M represents a Group V element selected from the group consisting of phosphorus, arsenic and antimony.
Claim 3
Dependent Claim
20 words
A process according to claim 1, wherein said olefin is a mono-olefin having from two to about twenty carbon atoms.
Claim 4
Dependent Claim
12 words
A process according to claim 2 wherein said mono-olefin is an alpha-olefin.
Claim 5
Dependent Claim
13 words
A process according to claim 2, wherein said mono-olefin is an internal olefin.
Claim 6
Dependent Claim
50 words
A process according to claim 1, wherein each of said R 1 , R 2 and R 3 contains no more than 15 carbon atoms and wherein the total number of carbon atoms in said R 1 , R 2 and R 3 is no more than 30 carbon atoms.
Claim 7
Dependent Claim
31 words
A process according to claim 5, wherein each of said R 1 , R 2 and R 3 comprises a saturated straight-chain hydrocarbon group having from 5 to 8 carbon atoms.
Claim 8
Dependent Claim
10 words
A process according to claim 6, wherein M represents phosphorus.
Claim 9
Dependent Claim
12 words
A process according to claim 1, wherein said ligand is trioctylphosphine oxide.
Claim 10
Dependent Claim
35 words
A process according to claim 1, wherein the temperature and total pressure of said reaction are about 95° to about 110° C. and from about 250 to about 350 lbs. per square inch absolute, respectively.
Claim 11
Dependent Claim
16 words
A process according to claim 1, wherein said reaction is conducted in an inert organic solvent.
Claim 12
Dependent Claim
17 words
A process according to claim 10, wherein said inert organic solvent is an aliphatic or aromatic hydrocarbon.
Claim 13
Dependent Claim
55 words
A process according to claim 10, wherein said inert organic solvent is a member selected from the group consisting of a saturated aliphatic hydrocarbon having from about 9 to about 20 carbon atoms, benzene and an aromatic hydrocarbon substituted by at least one saturated aliphatic hydrocarbon group having from 1 to about 15 carbon atoms.
Claim 14
Dependent Claim
36 words
A process according to claim 10, wherein said reaction is conducted by exposing a liquid reaction mixture comprising said solvent and said rhodium complex catalyst to a gas stream comprising oxygen, carbon monoxide, olefin and hydrogen.
Claim 15
Dependent Claim
19 words
A process according to claim 13, wherein the molar ratio oxygen:carbon monoxide:olefin:hydrogen in said gas stream is about 1-5:30-70:5-35:5-35.
Claim 16
Dependent Claim
31 words
A process according to claim 13, wherein the concentration of catalytically active rhodium in said solvent is from about 25 to about 1200 parts per million, calculated as the free metal.
Claim 17
Dependent Claim
34 words
A process according to claim 13, wherein the concentration of said ligand in said liquid reaction medium is from about 0.0008 to about 0.08 Molar, based on the total volume of liquid reaction medium.
Claim 18
Dependent Claim
33 words
A process according to claim 13, wherein said solvent also contains from about 0.5 to about 5 weight percent, based on the weight of the total liquid reaction medium, of said carboxylic acid.
Claim 19
Dependent Claim
96 words
A single-step process for preparing at least one of a carboxylic acid and its anhydride having from 3 to 21 carbon atoms directly from a mono-olefin having correspondingly from 2 to 20 carbon atoms comprising reacting said olefin with carbon monoxide, hydrogen and oxygen in an inert organic solvent and in the presence of a rhodium complex catalyst consisting essentially of rhodium stabilized by a pentavalent phosphorus ligand represented by the formula ##STR3## wherein R 1 , R 2 and R 3 each represents a saturated straight-chain hydrocarbon group having from 5 to 8 carbon atoms.
Claim 20
Dependent Claim
96 words
A single-step process for preparing at least one of a carboxylic acid and its anhydride having from 3 to 21 carbon atoms directly from a mono-olefin having correspondingly from 2 to 20 carbon atoms comprising reacting said olefin with carbon monoxide, hydrogen and oxygen in an inert organic solvent and in the presence of a rhodium complex catalyst consisting essentially of rhodium stabilized by a pentavalent phosphorus ligand represented by the formula ##STR3## wherein R 1 , R 2 and R 3 each represents a saturated straight-chain hydrocarbon group having from 5 to 8 carbon atoms.
Claim 21
Dependent Claim
11 words
A process according to claim 18, wherein said olefin is ethylene.
Claim 22
Dependent Claim
55 words
A process according to claim 18, wherein said inert organic solvent is a member selected from the group consisting of a saturated aliphatic hydrocarbon having from about 9 to about 20 carbon atoms, benzene and an aromatic hydrocarbon substituted with at least one saturated aliphatic hydrocarbon group having from 1 to about 15 carbon atoms.
Claim 23
Dependent Claim
13 words
A process according to claim 19, wherein said inert organic solvent is toluene.
Claim 24
Dependent Claim
14 words
A process according to claim 21, wherein said pentavalent phosphorus ligand is trioctylphosphine oxide.
Claim 25
Dependent Claim
36 words
A process according to claim 22, wherein said liquid reaction medium also initially includes from about 0.5 to about 5 weight percent, based on the total weight of the liquid reaction medium, of said carboxylic acid.
Claim 26
Dependent Claim
15 words
A process according to claim 23, wherein the molar ratio oxygen:carbon monoxide:ethylene:hydrogen is about 2-3:50-60:20-30:20-30.
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