EP0031606A1
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EP
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Process for the co-production of carboxylic acids and carboxylic acid esters
Assignee: Shell Internationale Research Maatschappij BV
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Filing: 1980-12-01
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Granted: —
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Expires: 2000-12-01
Abstract
Abstract Process for the co-production of carboxylic acids of general formulae R 1 -COOH and R 2- COOH and carboxylic acid esters of general formulae R 1 -COOCH 2 R 2 and R 2- COOCH 2 R 1 from carboxylic acid esters of general formula R 1 -COOR 2 and/or ethers of general formula R 3 OR 4 [R 1 , R 2 , R 3 , R 4 representing (substituted) alkyl or (substituted) aryl, alkaryl or aralkyl, R 1 also representing H], carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a ruthenium compound, a further Group VIII metal compound and a Group II metal iodide and/or bromide or a transition metal iodide and/or bromide. The process is of special interest for the conversion of methyl acetate into ethylacetate and acetic acid in stoichiometrically amounts at pressures well below 100 bar.
Inventors
- 👤 Eit Drent
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-02 05:02
CPC Classifications
C; C07; C07C; C07C51/00; C07C51/10; C07C51/12; C07C67/00; C07C67/36; C07C67/37; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/582
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
290 words
A process for the co-production of carboxylic acids according to the general formulae R 1 -COOH and R 2 -COOH and carboxylic acid esters according to the general formulae R 1- COOCH 2 R 2 and R 2 -COOCH 2 R 1 , wherein the groups R and R which may be the same or different each represent an alkyl group having of from 1 to 20 carbon atoms which may be substituted by one or more inert substituents such as fluorine or chlorine containing moieties or hydroxy, alkoxy or alkanoyl groups or an aryl, alkaryl or aralkyl group which may be substituted by one or more inert substituents such as fluorine or chlorine containing moieties or alkoxy or alkanoyl groups whilst R 1 may also represent a hydrogen atom, characterized in that a carboxylic acid ester according to the general formula R 1 -COOR 2 and/or an ether according to the general formula R 3 OR 4 wherein R 1 and R 2 are as defined hereinbefore and R 3 and R which may be the same or different each represent an alkyl group having of from 1 to 20 carbon atoms which may be substituted by one or more inert substituents such as fluorine or chlorine containing moieties or hydroxy, alkoxy or alkanoyl groups or an aryl, alkaryl or aralkyl group which may be substituted by one or more inert substituents such as fluorine or chlorine containing moieties or alkoxy or alkanoyl groups, is reacted with carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a catalytic system which comprises a ruthenium compound, a Group II metal iodide and/or bromide or a transition metal iodide and/or bromide and a further Group VIII metal compound.
Claim 2
Dependent Claim
290 words
A process for the co-production of carboxylic acids according to the general formulae R 1 -COOH and R 2 -COOH and carboxylic acid esters according to the general formulae R 1- COOCH 2 R 2 and R 2 -COOCH 2 R 1 , wherein the groups R and R which may be the same or different each represent an alkyl group having of from 1 to 20 carbon atoms which may be substituted by one or more inert substituents such as fluorine or chlorine containing moieties or hydroxy, alkoxy or alkanoyl groups or an aryl, alkaryl or aralkyl group which may be substituted by one or more inert substituents such as fluorine or chlorine containing moieties or alkoxy or alkanoyl groups whilst R 1 may also represent a hydrogen atom, characterized in that a carboxylic acid ester according to the general formula R 1 -COOR 2 and/or an ether according to the general formula R 3 OR 4 wherein R 1 and R 2 are as defined hereinbefore and R 3 and R which may be the same or different each represent an alkyl group having of from 1 to 20 carbon atoms which may be substituted by one or more inert substituents such as fluorine or chlorine containing moieties or hydroxy, alkoxy or alkanoyl groups or an aryl, alkaryl or aralkyl group which may be substituted by one or more inert substituents such as fluorine or chlorine containing moieties or alkoxy or alkanoyl groups, is reacted with carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a catalytic system which comprises a ruthenium compound, a Group II metal iodide and/or bromide or a transition metal iodide and/or bromide and a further Group VIII metal compound.
Claim 3
Dependent Claim
112 words
A process according to claim 1 characterized in that as starting materials are used compounds according to the general formulae R 1 -COOR 2 and/or R 3 OR 4 wherein R 1 , R , R and R 4 which may be the same or different, each represent an alkyl group having of from 1 to 12 carbon atoms or an aryl, alkaryl or aralkyl group having up to 12 carbon atoms whilst R 1 may also represent a hydrogen atom, and preferably are the same and represent an alkyl group having of from 1 to 12 carbon atoms or an aryl, alkaryl or aralkyl group having up to 12 carbon atoms.
Claim 4
Dependent Claim
37 words
A process according to claim 1 or 2 characterized in that as ruthenium. compound is used ruthenium(III) chloride, ruthenium (III) chloride trihydrate, ruthenium (IV) chloride, ruthenium (III) bromide, ruthenium oxide or an organic ruthenium salt or complex.
Claim 5
Dependent Claim
89 words
A process according to any one of the preceding claims characterized in that as further Group VIII metal compound is used a rhodium compound such as rhodium oxide, rhodium (III) hydroxide, rhodium (III) chloride, rhodium (III) chloride trihydrate, rhodium (III) bromide, rhodium (III) iodide or an organic rhodium salt or complex, preferably rhodium (III) chloride trihydrate, or a palladium compound such as palladium chloride, palladium chloride dihydrate, palladium bromide, palladium iodide, palladium oxide or an organic palladium salt or complex, preferably palladium chloride, palladium chloride dihydrate or palladium acetate.
Claim 6
Dependent Claim
67 words
A process according to any one of the preceding claims, characterized in that the ruthenium compound and the further Group VIII metal compound are used in a ratio between 20:1 and 1:20, preferably between 5:1 and 1:5 and in an.amount of at least 0.001 %w and preferably in an amount in the range of from 0.01-10 %w, calculated on carboxylic acid ester and/or ether to be converted.
Claim 7
Dependent Claim
59 words
A process according to any one of the preceding claims, characterized in that the catalytic system comprises one or more of the compounds magnesium bromide and/or iodide, chromium(III) iodide, cobalt (II) iodide, cobalt (II) bromide, nickel (II) iodide, nickel (II) bromide, copper (II) iodide, zinc iodide and zinc bromide, and preferably cobalt (II) iodide, zinc iodide or zinc bromide.
Claim 8
Dependent Claim
79 words
A process according to any one of the preceding claims characterized in that additionally an organo-phosphorus compound such as tertiary phosphine or phospite, especially tri-n-butyl phosphine or triphenylphosphine, an organo-arsenic compound, an organo-antimony compound, an organo-nitrogen compound such as pyridine or an alkyl-substituted pyridine, especially alpha-picoline, an organic-sulphur compound or an organic-oxygen compound is present in the reaction mixture which compound is capable of forming a co-ordination compound with a Group VIII metal moiety present in the catalytic system.
Claim 9
Dependent Claim
42 words
A process according to any one of the preceding claims characterized in that the reaction is carried out at a temperature up to 300°C, preferably at a temperature in the range of from 50°C to 200°C, and especially between 125°C and 175°C.
Claim 10
Dependent Claim
30 words
A process according to any one of the preceding claims characterized in that the process is carried out using a low pressure, preferably a pressure between 20 and 100 bar.
Claim 11
Dependent Claim
55 words
A process according to any one of the preceding claims characterized in that the reaction is carried out in the presence of a solvent such as a carboxylic acid, a carboxylic acid ester, a cyclic ether, an (a)cyclic sulphone such as dimethyl sulphone, sulfolane, 2-methylsulfolane or 3-methylsulfolane or a sulphoxide such as dimethylsulphoxide or diethylsulphoxide.
Claim 12
Dependent Claim
74 words
A process according to any one of the preceding claims, characterized in that as starting material is used a carboxylic acid ester which has been obtained by reacting an alkanoic acid and an alkanol, especially acetic acid and methanol, in the presence of an acidic catalyst and wherein optionally the alkanoic acid produced, especially acetic acid, is recycled to the starting material and the carboxylic acid ester obtained is subjected to a trans-esterification process.
Claim 13
Dependent Claim
45 words
A catalytic system characterized by a ruthenium compound, especially ruthenium (III) chloride trihydrate, a further Group VIII metal compound, especially a rhodium compound or a palladium compound, and a Group II metal iodide and/or bromide or a transition metal iodide and/or bromide, especially zinc iodide.
Claim 14
Dependent Claim
45 words
A catalytic system characterized by a ruthenium compound, especially ruthenium (III) chloride trihydrate, a further Group VIII metal compound, especially a rhodium compound or a palladium compound, and a Group II metal iodide and/or bromide or a transition metal iodide and/or bromide, especially zinc iodide.
References Cited (Backward Citations)
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