EP0055618A1
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EP
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Carbonylation process employing a catalyst stabilised in soluble form
Assignee: Cessione bp Chemicals Ltd
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Filing: 1981-12-24
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Granted: —
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Expires: 2001-12-24
Abstract
Abstract The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system that contains (a) a rhodium component, and (b) an iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases, and unreacted olefin, alcohol, or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the system of a stabilizer component selected from (1) N,N,N min ,N min - tetramethyl-o-phenylenediamine and 2,3 min dipyridyl, (2) a substituted diphosphine having the formula <CHEM> wherein R1, R2, R4 and R5 are alkyl or aryl substituted alkyl having 1 to 20 carbon atoms or in which R1, R2, R4 and R5 are aryl or alkyl substituted aryl radicals having 6 to 20 carbon atoms; and R3 is a polymethylene group having 1-3 atoms, (3) a dibasic or polybasic carboxylic acid having the formula <CHEM> r
Inventors
- 👤 Thomas Clark Singleton
- 👤 Wilbert Herbert Urry
- 👤 Frank Edward Paulik
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-03 16:50
CPC Classifications
C; C07; C07C; C07C51/00; C07C51/10; C07C51/14; C07C51/12
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
306 words
A carbonylation process wherein at least one reactant selected from the group consisting of an alcohol, an ester derivative of said alcohol, a halide derivative of said alcohol and an ether derivative of said alcohol is (1) reacted with carbon monoxide in a liquid phase in a reaction zone and in the presence of a catalyst system that contains (a) a rhodium component, and (b) an iodine or bromine component, (2) passing at least a portion of the liquid reaction mass in which.the carbon monoxide has been depleted from the reaction zone to a separation zone, and (3) recycling the remaining liquid reaction mass from the separation zone to said reaction zone, characterized by adding to the process an amount of a stabilizer component selected from (1) N,N,N',N'- tetramethyl-o-phenylenediamine and 2,3'-dipyridyl, (2) a substitued diphosphine having the formula wherein R l , R 2 , R 4 and R 5 are alkyl or aryl substituted alkyl radicals having 1 to 20 carbon atoms or in which R 1 ,R 2 ,R 4 and R 5 are aryl or alkyl substituted aryl radicals having 6 to 20 carbon atoms; and R 3 is a polymethylene group having 1-3 carbon atoms, (3) a dibasic or polybasic carboxylic acid having the formula wherein Y1 is of the formula (CX 1 X 2 ) m in which m is 2 to 10 and wherein Y 2 , Y 3 , Y 4 and Y 5 are of the formula (CX 1 X 2 ) n in which n is 1 to 10, and X 1 and X 2 are independently selected from hydrogen, a halogen, lower alkyl, aryl, hydroxyl, carboxyl, amino, hydroxy-substituted alkyl and carboxy-substituted alkyl, or (4) a compound of germanium, antimony, tin, or an alkali metal, said amount being sufficient to maintain the rhodium component in soluble form.
Claim 2
Dependent Claim
306 words
A carbonylation process wherein at least one reactant selected from the group consisting of an alcohol, an ester derivative of said alcohol, a halide derivative of said alcohol and an ether derivative of said alcohol is (1) reacted with carbon monoxide in a liquid phase in a reaction zone and in the presence of a catalyst system that contains (a) a rhodium component, and (b) an iodine or bromine component, (2) passing at least a portion of the liquid reaction mass in which.the carbon monoxide has been depleted from the reaction zone to a separation zone, and (3) recycling the remaining liquid reaction mass from the separation zone to said reaction zone, characterized by adding to the process an amount of a stabilizer component selected from (1) N,N,N',N'- tetramethyl-o-phenylenediamine and 2,3'-dipyridyl, (2) a substitued diphosphine having the formula wherein R l , R 2 , R 4 and R 5 are alkyl or aryl substituted alkyl radicals having 1 to 20 carbon atoms or in which R 1 ,R 2 ,R 4 and R 5 are aryl or alkyl substituted aryl radicals having 6 to 20 carbon atoms; and R 3 is a polymethylene group having 1-3 carbon atoms, (3) a dibasic or polybasic carboxylic acid having the formula wherein Y1 is of the formula (CX 1 X 2 ) m in which m is 2 to 10 and wherein Y 2 , Y 3 , Y 4 and Y 5 are of the formula (CX 1 X 2 ) n in which n is 1 to 10, and X 1 and X 2 are independently selected from hydrogen, a halogen, lower alkyl, aryl, hydroxyl, carboxyl, amino, hydroxy-substituted alkyl and carboxy-substituted alkyl, or (4) a compound of germanium, antimony, tin, or an alkali metal, said amount being sufficient to maintain the rhodium component in soluble form.
Claim 3
Dependent Claim
18 words
The process of Claim 1 characterized wherein the catalyst system contains a rhodium component and an iodine component.
Claim 4
Dependent Claim
12 words
The process of Claim 2 characterized wherein methanol is-carbonylated to acetic acid.
Claim 5
Dependent Claim
24 words
The process of Claim 3 characterized wherein said inhibitor is present in a molar ratio of at least about 0.5 to the rhodium component.
Claim 6
Dependent Claim
11 words
The process of Claim 4 characterized wherein the diphosphine is bis(1,2-diphenylphosphino)ethane.
Claim 7
Dependent Claim
11 words
The process of Claim 4 characterized wherein the diphosphine is bis(1,2-di-p-tolylphosphino)ethane.
Claim 8
Dependent Claim
11 words
The process of Claim 4 characterized wherein the diphosphine is bis(1,3-di-phenylphosphino)propane.
Claim 9
Dependent Claim
12 words
The process of Claim 4 characterized wherein the acid is citric acid.
Claim 10
Dependent Claim
12 words
The process of Claim 4 characterized wherein the acid is succinic acid.
Claim 11
Dependent Claim
12 words
The process of Claim 4 characterized wherein the acid is ethylenediaminetetraacetic acid.
Claim 12
Dependent Claim
26 words
The process of Claim 4 characterized wherein the stabilizer compound is the halide or acetate of the element selected from germanium, antimony or an alkali metal.
Claim 13
Dependent Claim
13 words
The process of Claim 11 characterized wherein the stabilizer is GeI 4 .
Claim 14
Dependent Claim
13 words
The process of Claim 11 characterized wherein the stabilizer is SbCl 3 .
Claim 15
Dependent Claim
12 words
The process of Claim 11 characterized wherein the stabilizer is lithium acetate.
Claim 16
Dependent Claim
12 words
The process of Claim 11 characterized wherein the stabilizer is potassium iodide.
References Cited (Backward Citations)
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