EP0072055A1
Expired / Lapsed
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: 1982-07-09
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Granted: —
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Expires: 2002-07-09
Abstract
Abstract Process for the co-production of carboxylic acids of the general formula R'-COOH and R 2 -COOH and carboxylic acid esters of general formula R 1 -COOCH 2 R 2 and R 2 -COOCH 2 R 1 from carboxylic acid esters of general formula R 1 -COOR 2 an/or ethers of general formula R 3 0R 4 (R 1 , R 2 , R 3 R 4 representing (substituted) alkyl or (substituted) aryl, alkaryl or aralkyl, R' also representing H), carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a ruthenium compound and a further Group VIII metal compound, hydrogen iodide, hydrogen bromide, elemental iodine and/or elemental bromine being added to the reaction mixture. The process is of special interest for the selective conversion of methyl acetate into ethyl acetate and acetic acid at pressures well below 100 bar.
Inventors
- 👤 Eit Drent
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-30 14:06
CPC Classifications
C; C07; C07C; C07C51/00; C07C51/10; C07C51/12
Claims Analysis
Total Claims: 13
Claim 1
Independent Claim
291 words
A process for the co-production of carboxylic acids of the general formula R 1 -COOH and R 2 -COOH and carboxylic acid esters of the general formula R 1- COOCH 2 R 2 and R 2- COOCH 2 R 1 , wherein each of the groups R 1 and R 2 , which may be the same or different, represents an alkyl group having 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 of the general formula R 1 -COOR 2 and/or an ether of the general formula R 3 0R 4 wherein R 1 and R 2 are as defined hereinbefore and each of R 3 and R 4 , which may be the same or different, represents an alkyl group having 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 and a further Group VIII metal compound,hydrogen iodide, hydrogen bromide, elemental iodine and/or elemental bromine being added to the reaction mixture.
Claim 2
Dependent Claim
291 words
A process for the co-production of carboxylic acids of the general formula R 1 -COOH and R 2 -COOH and carboxylic acid esters of the general formula R 1- COOCH 2 R 2 and R 2- COOCH 2 R 1 , wherein each of the groups R 1 and R 2 , which may be the same or different, represents an alkyl group having 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 of the general formula R 1 -COOR 2 and/or an ether of the general formula R 3 0R 4 wherein R 1 and R 2 are as defined hereinbefore and each of R 3 and R 4 , which may be the same or different, represents an alkyl group having 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 and a further Group VIII metal compound,hydrogen iodide, hydrogen bromide, elemental iodine and/or elemental bromine being added to the reaction mixture.
Claim 3
Dependent Claim
112 words
A process according to claim 1 characterized in that as starting materials are used compounds of the general formula R 1- C00R 2 and/or R 3 0R 4 wherein each of R 1 , R 2 , R 3 and R 4 which may be the same or different, represents an alkyl group having 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 from 1 to 12 carbon atoms or an aryl, alkaryl or aralkyl group having up to 12 carbon atoms.
Claim 4
Dependent Claim
38 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
20 words
A process according to claim 4, characterized in that a rhodium compound is used as further Group VIII metal compound.
Claim 7
Dependent Claim
37 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 50:1 and 1:20, preferably between 10:1 and 1:5.
Claim 8
Dependent Claim
32 words
A process according to any one of the preceding claims characterized in that additionally an organo-phosphorus, organo-arsenic, organo-antimony, organo-nitrogen, organo-sulphur or organo-oxygen compound is present in the reaction mixture as a promotor.
Claim 9
Dependent Claim
31 words
A process according to claim 7, in which an amine or a phosphine is present in the reaction mixture in an amount less than 0.5 moles per gram atom of ruthenium.
Claim 10
Dependent Claim
35 words
A process according to any one of the preceding claims characterized in that the reaction is carried out at a temperature in the range of from 50°C to 200°C, and especially between 125°C and 175°C.
Claim 11
Dependent Claim
26 words
A process according to any one of the preceding claims characterized in that the process is carried out using a pressure between 20 and 100 bar.
Claim 12
Dependent Claim
15 words
A process according to claim 1, carried out substantially as described in the Example herein.
Claim 13
Dependent Claim
67 words
A carboxylic ester of formula R l C0 2 CH 2 R 2 or R 2 CO 2 CH 2 R 1 or a carboxylic acid of formula R l C0 2 H or R 2 C0 2 H, where R 1 and R 2 have the meanings given in claim 1, whenever prepared by a process as claimed in any one of claims 1 to 11.
References Cited (Backward Citations)
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