WO1998037049A1 - Verfahren zur herstellung von carbonsäuren oder deren estern durch carbonylierung von olefinen - Google Patents
Verfahren zur herstellung von carbonsäuren oder deren estern durch carbonylierung von olefinen Download PDFInfo
- Publication number
- WO1998037049A1 WO1998037049A1 PCT/EP1998/000708 EP9800708W WO9837049A1 WO 1998037049 A1 WO1998037049 A1 WO 1998037049A1 EP 9800708 W EP9800708 W EP 9800708W WO 9837049 A1 WO9837049 A1 WO 9837049A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carboxylic acids
- preparation
- compound
- esters
- catalyst system
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
Definitions
- the present invention relates to a process for the preparation of carboxylic acids or their esters by reacting an olefin with carbon monoxide in the presence of water or alcohols and a halogen-free catalyst system, a mixture of nickel or a nickel compound, at least one noble metal or its compound and a non-metallic nitrogen, Arsenic or phosphorus compound, at a pressure of 30 to 100 bar and 100 to 270 ° C.
- GB-A 1 063 617 teaches the carbonylation of olefins with nickel and cobalt catalysts in the presence of boric acid. High pressures and temperatures are also required for this.
- Carbonylations of olefins can be carried out with noble metal catalysts at pressures of approx. 100 bar.
- EP-A 495 547 teaches catalysts which consist of a palladium source and bidentate phosphine ligands.
- catalysts are often deactivated after a short reaction time by deposition of metallic palladium; in particular, the phosphine ligands used are not thermally stable under the desired reaction conditions.
- DE-A 4 424 710 describes the carbonylation of olefins with a mixture of nickel or a nickel compound and a noble metal or a noble metal compound as a catalyst system.
- the method described is in terms of selectivity and activity with regard to the products to be produced. products, especially at pressures below 100 bar, are not yet satisfactory.
- the activity and selectivity compared to the catalyst system described in DE-A 4 424 710 could be considerably improved by the process according to the invention, in particular at low pressures up to 100 bar.
- the catalyst system used in the process according to the invention is so active even at low water concentrations of 0.5 to 5 mol water per mol olefin that the production of carboxylic acids is made possible which already have a water content of less than 1% in the reaction discharge, which means that the workup of the reaction product is considerably simplified.
- Suitable starting materials for the process according to the invention are aliphatic and cycloaliphatic alkenes with preferably 2 to 20, particularly preferably 2 to 7, carbon atoms.
- Examples include ethylene, propylene, isobutene, 1-butene, 2-butene and the isomers of pentene and hexene and cyclohexene, of which ethylene is preferred.
- olefins are reacted with water to produce carboxylic acids or with alcohols to produce carboxylic esters.
- alcohols include aliphatic and cycloaliphatic compounds with preferably 1 to 20 carbon atoms, particularly preferably with 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, iso-propanol, tert. -Butanol, stearyl alcohol, diols such as ethylene glycol, 1,2-propanediol and 1,6-hexanediol and cyclohexanol.
- diols are reacted, depending on the stoichiometric ratios selected, monoesters and diesters can be obtained, the diol and the olefin being used in a molar ratio of about 1: 2 for the preparation of diesters and the diol in excess for the preparation of the monoesters.
- the starting compounds mentioned are reacted with carbon monoxide, which can be used in pure form or diluted with inert gases such as nitrogen or argon.
- the molar ratios of the starting compounds olefin and water or alcohol can vary within wide limits, but generally at least an equimolar amount of water or alcohol is used. 0.5 to 10 mol of water per mol of olefin, preferably 0.5 to 5 mol, can be used in the production of carboxylic acids.
- the molar ratio of olefin to carbon monoxide can also be varied widely, a molar ratio of 5: 1 to 1: 5 mol of olefin per mol of carbon monoxide being preferred.
- the metals of the group chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or a compound of these metals and c) at least one non-metallic compound from the group of the tertiary or quaternary nitrogen, phosphorus or arsenic compounds and the nitrogen-containing heterocyclic compounds used.
- the active nickel compounds can form, compounds which are soluble therein, such as acetates, propionates, acetyl acetonates, hydroxides and carbonates or mixtures of these compounds, are expediently added to the reaction mixture.
- compounds which are soluble therein such as acetates, propionates, acetyl acetonates, hydroxides and carbonates or mixtures of these compounds, are expediently added to the reaction mixture.
- Ni (CO) and nickel metal it is also possible to add Ni (CO) and nickel metal to the reaction mixture. It is particularly preferred to enter the nickel component in the form of salts of the carboxylic acids formed in the reaction.
- These metals can, for example, be introduced into the reaction solution as salts, as indicated above for nickel, that is to say as acetates, propionates, acetylacetonates, hydroxides or carbonates.
- carbonyl compounds in particular chromium hexacarbonyl, molybdenum hexacarbonyl, tungsten hexacarbonyl, dirhenium decacarbonyl, triruthenium dodecacarbonyl, triosmium dodecacarbonyl and carbonyl compounds which carry further ligands such as rhodium dicarbonylacetylacetonate or by donor ligands and arylases such as phosphines, and nitrogenous arenes such as phosphine.
- Platinum can also be used as dibenzalacetone platinum.
- Ruthenium is preferably used as acetylacetonate.
- the metals are present in the reaction mixture in solution or in suspension depending on the solubility ratios.
- the metals or compounds of these metals of the catalyst component b) can also be used on organic or inorganic inert supports, such as, for example, activated carbon, graphite, aluminum oxide, zirconium oxide and silicon oxide.
- At least one non-metallic compound from the group of the tertiary or quaternary nitrogen, phosphorus or arsenic compounds and the nitrogen-containing heterocyclic compounds serves as the third catalyst component.
- Quaternary nitrogen, phosphorus or arsenic compounds are understood to mean the quaternary ammonium, arsonium and phosphonium salts.
- the third catalyst component c) preferably contains a compound of the general formula (I) as the quaternary nitrogen, arsenic or phosphorus compound
- R 1 , R 2 , R 3 and R 4 are aliphatic Residues such as alkyl groups, which preferably carry 1 to 18 carbon atoms and are straight-chain or branched, particularly preferably Ci to C 8 alkyl groups such as methyl, ethyl, n-propyl, n-butyl and octyl.
- R 1 , R 2 , R 3 and R 4 can also represent a cycloaliphatic radical such as cyclopentyl or cyclohexyl, an aromatic radical such as phenyl or an aromatic radical substituted by alkyl groups such as tolyl or an araliphatic radical such as benzyl.
- a cycloaliphatic radical such as cyclopentyl or cyclohexyl
- an aromatic radical such as phenyl or an aromatic radical substituted by alkyl groups such as tolyl or an araliphatic radical such as benzyl.
- the third catalyst component c) preferably contains a compound of the general formula (II) as tertiary nitrogen, phosphorus or arsenic compound
- Suitable nitrogen-containing heterocyclic compounds are suitable as the third catalyst component c) pyridine, pyridine, quinoline, isoquinoline, pyrimidine, pyridazine, pyrazine, pyrazole, imidazole, thiazole and oxazole, preferably optionally by, substituted by C 1 -C 4 -alkyl Ci to C alkyl monosubstituted pyridine, quinoline, isoquinoline, pyrimidine, Pyridazine, pyrazine, pyrazole, imidazole, thiazole and oxazole and their nitrogen-N-Ci to C -alkylated or N, N-C ⁇ to C -dialkylated salts with halogen-free anions X ", where X" has the meaning given above, preferably pyridine, N-methylpyridinium salts, imidazole and N, N-dimethylimidazolinium salts.
- the molar ratio of the nickel contained in the first component a) of the catalyst system to the second catalyst component b) is 1: 1 to 100,000: 1, preferably 100: 1 to 50,000: 1.
- the content of the catalytically active metals of components a) and b) in the reaction solution is a total of 0.1 to 5% by weight, calculated as metal.
- the molar ratio of the nickel of component a) to the third non-metallic catalyst component c) is generally from 2: 1 to 1:20, preferably from 1: 1 to 1:10.
- the content of the non-metallic catalyst component c) in the reaction solution is 1 to 50% by weight.
- the reaction can be carried out without or with a solvent.
- Solvents such as acetone, ether, dioxane, dirthhoxyethane, tetraethylene glycol dimethyl ether, aprotic polar solvents such as N-methylpyrrolidone and aromatic hydrocarbons such as toluene are also suitable. It is preferred to carry out the reaction for the preparation of carboxylic acids in 20 to 95% by weight, preferably 50 to 80% by weight, aqueous carboxylic acid.
- the preparation of the carboxylic acid esters by the process according to the invention is preferably carried out in the respective alcohol, which can contain 1 to 5% by weight of water, as solvent.
- the reaction is generally carried out at 100 to 270 ° C., preferably 170 to 250 ° C. and pressures of 30 to 100 bar, preferably 30 to 80 bar, particularly preferably 40 to 60 bar.
- the starting compounds olefin, water and the catalyst system can, if appropriate, be mixed in a solvent in a reactor before the reaction. You can then click on the
- Reaction temperature are heated, the reaction pressure is adjusted by pressing on carbon monoxide or, if short-chain olefins are used, by pressing on a mixture of this olefin and carbon monoxide.
- the reaction is usually complete after 0.5 to 3 hours. It can be carried out continuously or batchwise in reactors such as boilers, bubble columns, tubular reactors or circulation reactors.
- the reaction product is depressurized to isolate the process products.
- Nickel carbonyl is then discharged from the liquid by passing gases such as air or nitrogen through it.
- Nickel carbonyl can be separated from the inert gas and worked up to a nickel compound, which can then be returned to the reaction.
- the liquid phase of the reaction product which in addition to the process product contains soluble or suspended catalyst, is worked up by distillation, the process product being isolated, if appropriate after a subsequent fine distillation.
- the catalyst-containing distillation bottoms are returned to the reaction.
- catalyst constituents which have been separated off before the distillation and volatile catalyst constituents which have been separated off as low boilers or as a side stream of a distillation can also be recycled after appropriate work-up.
- the process according to the invention allows the production of the process products in high space-time yield with high selectivity.
- Example 1 Batch tests for the production of propionic acid
- PA propionaldehyde
- Examples 1 and 2 a catalyst made of nickel, ruthenium and tetrabutylammonium hydroxide or triethylamine at 60 bar was able to achieve significantly higher space-time yields and selectivities than in Comparative Experiment A with the two metallic catalyst components alone.
- Comparative examples B and C illustrate that the addition of tetrabutylammonium hydroxide to one of the two catalyst metals does not result in an active catalyst system.
- Experiments 1, 2, A and C show that the nitrogen components added accelerate above all the carbonylation reaction, but far less the formation of the by-products ethane, propionaldehyde and diethyl ketone.
- Example 4 A solution of 2.13 g of basic nickel carbonate and 12 mg of ruthenium acetyl acetonate in a mixture of 60 g of propionic acid and 40 g of water was placed in the autoclave described in Example 3. A pre-pressure of 30 bar was then set with a gas mixture of 50% by volume CO and 50% by volume ethylene and the reaction solution was heated to 200.degree. After the reaction temperature had been reached, the final pressure was set at 75 bar and kept constant by continuously pressing in the CO / ethene gas mixture. After two hours, the mixture was cooled to room temperature, the pressure was released and the reaction product was examined by titrimetry and gas analysis. The result is summarized in Table 2.
- Example 4 A solution of 2.13 g of basic nickel carbonate and 12 mg of ruthenium acetyl acetonate in a mixture of 60 g of propionic acid and 40 g of water was placed in the autoclave described in Example 3. A pre-pressure of 30 bar was then set with a gas mixture
- Example 2 The test was carried out as described in Example 3, but at a pressure of 55 bar. The result is summarized in Table 2.
- Example 2 The experiment was carried out as described in Example 3, but with 60 g of propionic acid, 25 g of a 40% aqueous tetrabylammonium hydroxide solution and 15 g of water as solvent and a pressure of 55 bar. The result is summarized in Table 2.
- Example D The test was carried out as described in Example D, but at a pressure of 55 bar. The result is summarized in Table 2.
- PA Propionaldekyd, by-product
- reaction solution heated to 200 ° C. After the reaction temperature had been reached, the final pressure was set at 100 bar and maintained by pressing in the CO / ethene gas mixture for half an hour. After two hours, the mixture was cooled to room temperature and let down. 126 g of liquid reaction product were obtained.
- Examples 6 and 7 illustrate that the catalyst system consisting of a nickel compound, a ruthenium compound and a nitrogen-containing compound such as triethylamine or tetrabutylammonium hydroxide has a high activity even at very low water concentrations.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98906940A EP0970034A1 (de) | 1997-02-21 | 1998-02-09 | Verfahren zur herstellung von carbonsäuren oder deren estern durch carbonylierung von olefinen |
JP53621298A JP2001512469A (ja) | 1997-02-21 | 1998-02-09 | オレフィンのカルボニル化によりカルボン酸またはそのエステルを製造する方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19706876.6 | 1997-02-21 | ||
DE19706876A DE19706876A1 (de) | 1997-02-21 | 1997-02-21 | Verfahren zur Herstellung von Carbonsäuren oder deren Estern durch Carbonylierung von Olefinen |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998037049A1 true WO1998037049A1 (de) | 1998-08-27 |
Family
ID=7821034
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/000708 WO1998037049A1 (de) | 1997-02-21 | 1998-02-09 | Verfahren zur herstellung von carbonsäuren oder deren estern durch carbonylierung von olefinen |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0970034A1 (de) |
JP (1) | JP2001512469A (de) |
KR (1) | KR20000075494A (de) |
CN (1) | CN1250432A (de) |
DE (1) | DE19706876A1 (de) |
WO (1) | WO1998037049A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1555353A (zh) * | 2001-08-03 | 2004-12-15 | 伊斯曼化学公司 | 采用金催化剂的汽相羰基化工艺 |
EP1414777A1 (de) * | 2001-08-03 | 2004-05-06 | Eastman Chemical Company | Dampfphasencarbonylierungsverfahren unter verwendung von iridium-gold co-katalysatoren |
EP2673085B1 (de) * | 2011-02-11 | 2015-03-04 | Dow Global Technologies LLC | Heterogener katalysator und seine verwendung |
CN108003022B (zh) * | 2016-11-02 | 2020-01-07 | 中国科学院大连化学物理研究所 | 一种制备酯类化合物的方法 |
CN108003023B (zh) * | 2016-11-02 | 2019-10-18 | 中国科学院大连化学物理研究所 | 一种制备丙酸甲酯的方法 |
CN108003024B (zh) * | 2016-11-02 | 2019-10-18 | 中国科学院大连化学物理研究所 | 一种丙酸甲酯的制备方法 |
CN109761811B (zh) * | 2019-02-26 | 2021-12-31 | 浙江师范大学 | 一种羧酸酯的制备方法 |
CN116328761B (zh) * | 2021-12-23 | 2024-05-28 | 上海浦景化工技术股份有限公司 | 一种乙烯羰基化制丙酸甲酯的催化剂及其制备方法和应用 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE868150C (de) * | 1941-09-21 | 1953-02-23 | Basf Ag | Verfahren zur Herstellung von Carbonsaeuregemischen |
DE2161460A1 (de) * | 1970-12-24 | 1972-07-13 | Denki Kagaku Kogyo K.K., Tokio | Verfahren zur Herstellung von Äthylen-1,2-dicarbonsäuren oder deren Derivaten |
US4257973A (en) * | 1971-11-05 | 1981-03-24 | E. I. Du Pont De Nemours And Company | Process of making acids or esters from unsaturated compounds |
GB2089803A (en) * | 1980-12-24 | 1982-06-30 | Halcon Sd Group Inc | Preparation of carboxylic acids |
US4588834A (en) * | 1984-10-04 | 1986-05-13 | Texaco Inc. | Process for carbonylation of olefins to carboxylic acids and esters |
DE4424710A1 (de) * | 1994-07-13 | 1996-01-18 | Basf Ag | Verfahren zur Carbonylierung von Olefinen |
EP0737669A1 (de) * | 1993-12-22 | 1996-10-16 | Union Carbide Chemicals & Plastics Technology Corporation | Reduktive Aminierung zur selektiven Herstellung von Aminoethylethanolamin |
-
1997
- 1997-02-21 DE DE19706876A patent/DE19706876A1/de not_active Withdrawn
-
1998
- 1998-02-09 CN CN98803397A patent/CN1250432A/zh active Pending
- 1998-02-09 WO PCT/EP1998/000708 patent/WO1998037049A1/de not_active Application Discontinuation
- 1998-02-09 EP EP98906940A patent/EP0970034A1/de not_active Withdrawn
- 1998-02-09 JP JP53621298A patent/JP2001512469A/ja active Pending
- 1998-02-09 KR KR1019997007553A patent/KR20000075494A/ko not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE868150C (de) * | 1941-09-21 | 1953-02-23 | Basf Ag | Verfahren zur Herstellung von Carbonsaeuregemischen |
DE2161460A1 (de) * | 1970-12-24 | 1972-07-13 | Denki Kagaku Kogyo K.K., Tokio | Verfahren zur Herstellung von Äthylen-1,2-dicarbonsäuren oder deren Derivaten |
US4257973A (en) * | 1971-11-05 | 1981-03-24 | E. I. Du Pont De Nemours And Company | Process of making acids or esters from unsaturated compounds |
GB2089803A (en) * | 1980-12-24 | 1982-06-30 | Halcon Sd Group Inc | Preparation of carboxylic acids |
US4588834A (en) * | 1984-10-04 | 1986-05-13 | Texaco Inc. | Process for carbonylation of olefins to carboxylic acids and esters |
EP0737669A1 (de) * | 1993-12-22 | 1996-10-16 | Union Carbide Chemicals & Plastics Technology Corporation | Reduktive Aminierung zur selektiven Herstellung von Aminoethylethanolamin |
DE4424710A1 (de) * | 1994-07-13 | 1996-01-18 | Basf Ag | Verfahren zur Carbonylierung von Olefinen |
Also Published As
Publication number | Publication date |
---|---|
KR20000075494A (ko) | 2000-12-15 |
EP0970034A1 (de) | 2000-01-12 |
JP2001512469A (ja) | 2001-08-21 |
DE19706876A1 (de) | 1998-08-27 |
CN1250432A (zh) | 2000-04-12 |
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