WO2001014297A1 - Kontinuierliches verfahren zur hydroformylierung von olefinen mit 6 bis 20 kohlenstoffatomen - Google Patents
Kontinuierliches verfahren zur hydroformylierung von olefinen mit 6 bis 20 kohlenstoffatomen Download PDFInfo
- Publication number
- WO2001014297A1 WO2001014297A1 PCT/EP2000/008095 EP0008095W WO0114297A1 WO 2001014297 A1 WO2001014297 A1 WO 2001014297A1 EP 0008095 W EP0008095 W EP 0008095W WO 0114297 A1 WO0114297 A1 WO 0114297A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cobalt
- aqueous
- salt solution
- olefins
- reactor
- Prior art date
Links
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
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
-
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a process for Hydroformy ⁇ -regulation of olefins having 6 to 20 carbon atoms.
- the hydroformylation or oxo-process is an important industrial process ⁇ large and the manufacturing is of aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes can optionally be hydrogenated with hydrogen to give the corresponding alcohols in the same operation or subsequently in a separate hydrogenation step.
- the hydroformylation takes place in the presence of catalysts homogeneously dissolved in the reaction medium.
- the catalysts used are generally the carbonyl complexes of metals from subgroup VIII, in particular Co, Rh, Ir, Pd, Pt or Ru, which are unmodified or z.
- B. can be modified with ligands containing amine or phosphine.
- the known processes for separating and recycling the cobalt catalyst are based on two principles: (1) The cycle takes place without a change in valence, ie the cobalt remains formally negative during the entire cycle of hydroformylation, separation and recycling into the reactor monovalent form; and (2) during the cycle there is a change in valence at the central atom from the negative monovalent to the metallic or positive divalent cobalt.
- the prototype of the principle (1) is the so-called Kuhlmann process (cf. US 3,188,351).
- the homogeneous R e is fracsaustrag dissolved hydroformylation catalyst in the form of Kobaltcarbonylwasserstoff with the help of sodium carbonate solution in what be transferred ⁇ serlösliches sodium chloride and extracted in water.
- the volatile cobalt carbonyl hydrogen is released from the aqueous alkaline solution by reaction with dilute sulfuric acid, stripped with oxogas, taken up by the olefin to be reacted and returned to the reactor.
- this process principle requires a number of complex technical precautions.
- the processes based on principle (2) are simpler, in which the organic phase of the reactor discharge is freed from the cobalt carbonyl complexes by treatment with oxygen or air in the presence of weakly acidic water (cf. DE-AS 2404855).
- the cobalt catalyst is destroyed by oxidation and the central atom is formally transferred from oxidation state -1 to +2 and can then be removed by extraction with the aqueous solution. This step is also called "oxidative decobalization".
- the catalyst complex required for the hydroformylation can be restored from the aqueous cobalt (II) salt solution by reaction with carbon monoxide and hydrogen.
- the cobalt catalyst produced is then extracted from the aqueous phase with an organic phase, preferably the olefin to be hydroformylated.
- an organic phase preferably the olefin to be hydroformylated.
- the reaction and by-products of the hydroformylation can also be used for catalyst extraction.
- the olefins loaded with the cobalt catalyst are then hydroformylated in a reactor under elevated pressure and temperature.
- DE-OS 2139630 describes a process for the preparation of predominantly straight-chain aldehydes by hydroformylation of olefinically unsaturated compounds, aqueous cobalt salt solutions being treated with carbon monoxide and hydrogen in a first stage, the aqueous solution then being extracted with an organic phase in a second stage and the organic phase and a mixture of carbon monoxide and hydrogen are transferred to a third stage, where, if appropriate, after the addition of the olefinically unsaturated compounds, not used or only partially used for the extraction in the second stage - the hydroformylation takes place.
- EP 0,850,905 describes a hydroformylation process in which the formation of the cobalt catalyst, the extraction of the gebil ⁇ Deten cobalt catalyst into the organic phase and the hydroformylation of olefins in a 1-stage process are carried out in the hydroformylation l michsreaktor.
- the cobalt salt solution obtained after the decobalization is circulated.
- an aqueous cobalt acetate solution with 1% by weight cobalt, calculated as metal, is used as the aqueous cobalt (II) salt solution.
- the present invention is therefore based on the object of hydroformylating olefins having 6 to 20 carbon atoms using aqueous cobalt (II) salt solutions on an industrial scale continuously and in stable continuous operation with a high yield, the catalyst cycle being as simple as possible, largely lossless and environmentally friendly ,
- cobalt (II) formate has only a water solubility of about 1% by weight, calculated as cobalt metal, at ambient temperature, i.e. h
- the water solubility of cobalt (II) formate is less than one fifth that of cobalt (II) acetate. For a sufficient catalyst supply, however, more highly concentrated starting solutions are necessary.
- the inventors have found that stable continuous operation can be achieved when using an aqueous cobalt (II) formate solution with a concentration of 1.1 to 1.7% by weight, based on cobalt, if it is kept under constant conditions below which the solubility limit of cobalt (II) formate in water is not exceeded.
- the invention accordingly relates to a continuous process for the hydroformylation of olefins having 6 to 20 carbon atoms, in which
- an aqueous cobalt (II) salt solution is brought into intimate contact with hydrogen and carbon monoxide to form a cobalt catalyst which is active in hydroformylation (hereinafter also simply referred to as "cobalt catalyst"), the aqueous phase containing the cobalt catalyst in at least one reaction zone with the Olefins and optionally an organic solvent and hydrogen and carbon monoxide are intimately contacted, the cobalt catalyst being extracted into the organic phase and the olefins being hydroformylated,
- step a) the aqueous cobalt (II) salt solution is returned unchanged to step a), which is characterized in that the cobalt (II) salt solution has a concentration of 1.1 to 1.7% by weight, based on cobalt , has and is kept constantly under conditions,
- Suitable, pressure-resistant reaction apparatus for hydroformylation are known to the person skilled in the art. These include the commonly used reactors for gas-liquid reactions, such as. B. tubular reactors, stirred tanks, gas circulation reactors, bubble columns, etc., which can be divided again if necessary by internals.
- a vertical high-pressure bubble column reactor for example, which is optionally provided with coaxial tubular internals, is suitable.
- Carbon monoxide and hydrogen are usually used in the form of a mixture, the so-called synthesis gas.
- the composition of the synthesis gas used in the process according to the invention can vary within wide ranges.
- the molar ratio of carbon monoxide and hydrogen is usually about 10: 1 to 1:10, in particular 2.5: 1 to 1: 2.5.
- a preferred ratio is about 1: 1.5.
- Inert hydrocarbons such as paraffin fractions, aromatic hydrocarbons, such as benzene, toluene or xylene, or an aldehyde and / or alcohol, but especially the hydroformylation product of the olefin used, are suitable as organic solvents which may be used.
- High-boiling hydroformylation by-products can also be used as solvents.
- the use of a solvent can, for. B. to reduce viscosity in long-chain olefins may be advantageous.
- the temperature in the hydroformylation is generally from 100 to 250 ° C., in particular 145 to 200 ° C.
- the reaction is preferably carried out at a pressure in the range from 100 to 400 bar, in particular 200 to 300 bar.
- the reaction discharge is usually taken off at the top of the reactor.
- the aqueous phase fed to the reaction zone which is necessary to achieve a sufficient catalyst concentration in the reaction zone, may not be completely removed in dissolved or suspended form with the reaction mixture taken off at the top. This can lead to the accumulation of aqueous phase in the reaction zone and to a gradual decline and possibly to a complete standstill of the hydroformylation reaction.
- the reaction is discharged both at the top of the er P- ß ß £ 3 rt f £ £ £ o ⁇ er ta w £ Pf rt D Pf ta 3 XI rt Pf 3 a Pf a TJ PD * «£ w ta ta
- the aqueous phase essentially cancel each other out so that a cobalt (II) salt solution with essentially the original concentration is obtained after the decobalization.
- the aqueous cobalt (II) salt solution is unchanged, i. H. without chemical workup or concentration, returned to the reaction zone or catalyst formation stage.
- the organic phase remaining after removal of the aqueous phase can then be suitably worked up, for. B. distilled and / or hydrogenated.
- olefins having 6 to 20 carbon atoms can be hydroformylated.
- the process according to the invention is particularly suitable for the hydroformylation of isomeric olefin mixtures which are prepared by oligomerizing lower olefins, such as propene and butenes.
- the typical oligomerizates which are suitable as starting products for the present process include, among others, di-, tri- and tetrapropene, di-, tri- and tetrabutene as well as mixed oligomerizates of propenes and butenes.
- the oligomerizates of butenes can be prepared by known oligomerization processes, e.g. B.
- Linear long-chain olefins with a terminal double bond which, for. B. are available by the SHOP® process or Ziegler process, or linear long-chain olefins with internal double bond can be hydroformylated.
- FIG. 1 is a schematic representation of a plant suitable for carrying out the method according to the invention. System details which are self-evident and which are not necessary for understanding the invention have been omitted for the sake of clarity.
- a vertical high-pressure reactor 1 which is equipped with facilities for intensive mixing of the reactants and for removing the heat of reaction, is fed via lines 2, 3 and 25 to olefins (> C 6 ), oxogas and aqueous cobalt formate solution with a Co content of 1.1 to 1.7 wt .-% supplied.
- the reactor discharge drawn off at the top reaches line 7 to post-reactor 8, which is also equipped with devices for heat dissipation.
- a pressure drop of 2 to 5 bar is set between the main and the post-reactor.
- part of the reactor contents is drawn off via line 5 and b combines it with the feed to the secondary reactor 8.
- This Sumpfa train consists, depending on the olefin used and the concentration of cobalt formate, from 10 to 80% of aqueous phase, with the balance being organic phase.
- the phase control 6 ensures that a certain phase ratio is maintained (eg 50:50).
- the reaction mixture leaving the post-reactor 8 passes the cooler 10 and is expanded in expansion valve 11 from the R e- aktordruck (> 200 bar) to medium pressure (10 to 30 bar).
- air is fed via line 12 and line 13 of formic acid cobalt formate solution (cobalt content 1.1 to 1.7% by weight) to the reactor discharge.
- the three-phase mixture reaches the separation container 15 via line 14.
- the excess synthesis gas released leaves the system via line 16.
- the organic, essentially cobalt-free upper phase is drawn off via line 17 for further processing, and the water phase via line 18.
- the interface control 19 continuously adds as much water via line 20 as the organic reaction product discharges due to its water absorption capacity.
- the aqueous cobalt formate solution (cobalt content 1.1 to 1.7% by weight) is fed via line 13 to the decobalting stage and via line 23 to the high-pressure pump 24. Finally, the required amount (about 0.13% by weight, based on olefin) of the 1.1 to 1.7 percent cobalt formate solution is added to the reactor feed via line 25.
- the cobalt cycle is completely self-contained. It is self-sufficient. There is no need to branch off a partial stream and send it to a separate work-up or concentration. The minimal losses of at most about 3 ppm cobalt (based on the organic reaction product) carried off with the hydroformylation product must be supplemented by occasional addition of concentrated cobalt (II) salt solution, eg. B. 6 percent cobalt acetate solution can be compensated via line 21, as well as the loss of leakage, for. B. on pumps.
- concentrated cobalt (II) salt solution eg. B. 6 percent cobalt acetate solution can be compensated via line 21, as well as the loss of leakage, for. B. on pumps.
- the pH of the aqueous lower phase in the separation vessel 15 is subject to regular monitoring and is kept in the range between 2 and 4 by means of formic acid supplements via line 21, if necessary.
- the lines 18, 13, 23 and 25 and the pumps 22 and 24 are equipped with a trace heating, for. B. in the form of electrical heating tapes or with heating medium flowed through pipes.
- the method according to the invention is carried out in a technical installation which is constructed with reference to FIG. 1.
- the reactor 1 which is equipped with devices for heat dissipation and a mixing nozzle for mixing and for entering the reactants into a circulation system, has a usable reaction space of 11.5 m 3 , the corresponding reaction space of the post-reactor 8 is 8.5 m 3 ,
- the reaction conditions for the first reactor are 187 ° ⁇ 1 ° C and 275 bar.
- the temperature in the post-reactor is at the same level, the pressure is kept 3 bar below the pressure of the first reactor.
- Reactor 1 which was initially filled with crude nanol, is fed 4,500 kg per hour of an octane isomer mixture from butene dimerization using the IFP process, together with 420 kg of an aqueous cobalt formate solution containing 1.4% by weight cobalt and 1,460 kg of a synthesis gas mixture (39.5 mol. -% CO content) supplied.
- the main part of the reaction mixture leaves the reactor 1 overhead and then passes through the post-reactor 8. About 500 kg / h are continuously added to the reactor bottom. The reactor contents are removed via phase control 6 and mixed into the feed to the post-reactor. This bottom draw consists on average of 1/3 of the aqueous phase.
- the discharge from the post-reactor is cooled in the heat exchanger 10 to below 150 ° C. and expanded in the expansion valve 11 to about 20 bar.
- reaction product is about 4,000 kg / hour.
- Cobalt formate solution with an average pH of 3 and 21 kg / h. Air added.
- the released expansion gas is drawn off from the phase separation container 15.
- the floating organic upper phase with a residual cobalt content of 1 to 2 ppm is continuously discharged and, after hydrogenation and distillation, provides 4,940 kg of a pure i-nonyl alcohol mixture, corresponding to 85.4% of theory.
- the upper phase draws about 2% by weight of water from the aqueous catalyst system due to its water absorption capacity. This quantity has to be continuously added via the interface control 19 in order to keep the cobalt concentration at 1.4%.
- the watery under- phase from the separation container 15 supplies both the reactor discharge after the expansion with about 4,000 kg / hour via the pump 22. aqueous formate solution as well as the catalyst pump 24 with 420 kg of formate solution in order to form cobalt carbonyls therefrom in situ in the reactor.
- the amounts of cobalt discharged with the organic phase and leakage losses are compensated for by supplying 6% Co-containing aqueous cobalt acetate solution via line 21.
- the formic acid supplements are made via this line in order to keep the pH value of the formate solution in the range from 2 to 4 (on average about 5 kg / d of 100% formic acid).
- Example 2 The same system as in Example 1 is used and a formate solution is used which contains only 1% cobalt instead of 1.4%.
- the process according to the invention is carried out in the technical installation described in Example 1.
- the reaction conditions for the first reactor are 192 ⁇ 1 ° C and 275 bar.
- the temperature in the subsequent reactor is at the same level, the pressure is 3 bar lower than in the first reactor supported ⁇ th.
- Reactor 1 which was filled with crude tridecanol at the start, is fed 3,500 kg per hour of a dodecene isomer mixture from butene trimming according to the IFP process, together with 310 kg of an aqueous cobalt formate solution containing 1.5% by weight cobalt and 790 kg of a synthesis gas mixture (39.5 Mol .-% CO content) supplied.
- Example 1 The procedure is as in Example 1 and phase-controlled, about 500 kg of reactor content, 1/3 of which consists of water, are taken from the bottom of reactor 1. Otherwise, the procedure is analogous to Example 1.
- the organic upper phase After hydrogenation and distillation, the organic upper phase provides 3,350 kg of a pure tridecanol isomer mixture, corresponding to 80.4% of theory.
- the interface control system 19 for the separation container 15 automatically ensures that the cobalt concentration in the formate solution is maintained, in this case 1.5%, with slightly less due to the reduced water absorption capacity of the C 13 hydroformylation product Water needs to be replenished.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE50008524T DE50008524D1 (de) | 1999-08-20 | 2000-08-18 | Kontinuierliches verfahren zur hydroformylierung von olefinen mit 6 bis 20 kohlenstoffatomen |
US10/049,859 US6723884B1 (en) | 1999-08-20 | 2000-08-18 | Continuous process for hydroformylating olefins with 6 to 20 carbon atoms |
EP00958472A EP1204624B1 (de) | 1999-08-20 | 2000-08-18 | Kontinuierliches verfahren zur hydroformylierung von olefinen mit 6 bis 20 kohlenstoffatomen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19939491A DE19939491A1 (de) | 1999-08-20 | 1999-08-20 | Kontinuierliches Verfahren zur Hydroformylierung von Olefinen mit 6 bis 20 Kohlenstoffatomen |
DE19939491.1 | 1999-08-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001014297A1 true WO2001014297A1 (de) | 2001-03-01 |
Family
ID=7919008
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/008095 WO2001014297A1 (de) | 1999-08-20 | 2000-08-18 | Kontinuierliches verfahren zur hydroformylierung von olefinen mit 6 bis 20 kohlenstoffatomen |
Country Status (6)
Country | Link |
---|---|
US (1) | US6723884B1 (de) |
EP (1) | EP1204624B1 (de) |
CN (1) | CN1257140C (de) |
DE (2) | DE19939491A1 (de) |
ES (1) | ES2231245T3 (de) |
WO (1) | WO2001014297A1 (de) |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011115695A1 (en) | 2010-03-15 | 2011-09-22 | Exxonmobil Chemical Patents Inc. | Processes for the production of alcohols |
WO2012084914A1 (de) | 2010-12-23 | 2012-06-28 | Basf Se | Thermoplastische elastomer-zusammensetzung und verfahren zu deren herstellung |
US8247618B2 (en) | 2007-04-18 | 2012-08-21 | Exxonmobil Chemical Patents Inc. | Oxidative demetalling |
WO2016005357A1 (de) | 2014-07-08 | 2016-01-14 | Basf Se | Weichmacher-zusammensetzung, die aliphatische dicarbonsäureester und terephthalsäuredialkylester enthält |
WO2016005358A1 (de) | 2014-07-08 | 2016-01-14 | Basf Se | Formmassen enthaltend dicarbonsäureester und 1,2-cyclohexandicarbonsäureester |
WO2016026838A1 (de) | 2014-08-19 | 2016-02-25 | Basf Se | Weichmacher-zusammensetzung, die polymere dicarbonsäureester enthält |
DE102015207291A1 (de) | 2014-04-24 | 2016-03-10 | Basf Se | Weichmacher-Zusammensetzung, die Furanderivate und 1,2-Cyclohexandicarbonsäureester enthält |
WO2017055429A1 (de) | 2015-09-30 | 2017-04-06 | Basf Se | Weichmacher-zusammensetzung, die polymere dicarbonsäureester und 1,2-cyclohexandicarbonsäureester enthält |
WO2017055431A1 (de) | 2015-09-30 | 2017-04-06 | Basf Se | Weichmacher-zusammensetzung, die polymere dicarbonsäureester und dicarbonsäurediester enthält |
WO2017055432A1 (de) | 2015-09-30 | 2017-04-06 | Basf Se | Weichmacher-zusammensetzung, die polymere dicarbonsäureester und terephthalsäuredialkylester enthält |
WO2017125458A1 (de) | 2016-01-20 | 2017-07-27 | Basf Se | Weichmacher-zusammensetzung, die aliphatische dicarbonsäureester und diester, die unter 1,2-cyclohexandicarbonsäureestern und terephthalsäureestern ausgewählt sind, enthält |
WO2017162723A2 (de) | 2016-03-23 | 2017-09-28 | Basf Se | Polymer-zusammensetzung, enthaltend einen cycloalkyl-alkyl-dicarbonsäurediester als weichmacher |
US9776949B2 (en) | 2014-04-22 | 2017-10-03 | Basf Se | Process for the production of carboxylic esters and use of these as plasticizers |
WO2018024597A1 (de) | 2016-08-01 | 2018-02-08 | Basf Se | Weichmacher-zusammensetzung |
WO2018024591A1 (de) | 2016-08-01 | 2018-02-08 | Basf Se | Weichmacher-zusammensetzung |
WO2018024594A1 (de) | 2016-08-01 | 2018-02-08 | Basf Se | Weichmacher-zusammensetzung |
US10030120B2 (en) | 2013-12-06 | 2018-07-24 | Basf Se | Softener composition which contains tetrahydrofuran derivatives and 1,2-cyclohexane dicarboxylic acid esters |
US10072133B2 (en) | 2014-01-09 | 2018-09-11 | Basf Se | Plasticizer composition containing furan derivatives and 1,2-cyclohexanedicarboxylic ester |
US10106486B2 (en) | 2013-10-31 | 2018-10-23 | Basf Se | Method for producing carboxylic acid esters and the use thereof as plasticizers |
WO2018210720A1 (de) | 2017-05-16 | 2018-11-22 | Basf Se | HYDROFORMYLIERUNGSVERFAHREN DIENEN DER GROßTECHNISCHEN HERSTELLUNG VON ALDEHYDEN UND/ODER ALKOHOLEN |
US10273345B2 (en) | 2014-09-04 | 2019-04-30 | Basf Se | Plasticizer composition which contains a polymer dicarboxylic acid ester |
US10287417B2 (en) | 2015-01-30 | 2019-05-14 | Basf Se | Plasticizer composition containing polymeric dicarboxylic acid esters and terephthalic acid dialkyl esters |
US10287415B2 (en) | 2014-10-09 | 2019-05-14 | Basf Se | Plasticizer composition which comprises cycloalkyl esters of saturated dicarboxylic acids and terephthalic esters |
US10315182B2 (en) | 2015-12-22 | 2019-06-11 | Basf Se | Cylindrical reactor and use thereof for continuous hydroformylation |
US10329402B2 (en) | 2014-10-09 | 2019-06-25 | Basf Se | Plasticizer composition which comprises cycloalkyl esters of saturated dicarboxylic acids and 1,2-cyclohexanedicarboxylic esters |
WO2019185409A1 (de) | 2018-03-29 | 2019-10-03 | Basf Se | Pvc-zusammensetzung, enthaltend wenigstens einen weichmacher der wenigstens eine carbonsäureestergruppe aufweist und wenigstens eine carbodiimidverbindung |
EP3747860A1 (de) | 2019-06-04 | 2020-12-09 | Basf Se | Neue weichmacher auf cyclohexanon-basis |
WO2024089254A1 (en) | 2022-10-28 | 2024-05-02 | Basf Se | Process for the manufacture of a c4-olefin-derived chemical of interest, in particular citral, from renewably-sourced ethanol |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10135906A1 (de) | 2001-07-24 | 2003-02-06 | Oxeno Olefinchemie Gmbh | Verfahren zur Hydroformylierung von höheren Olefinen mit Kobaltverbindungen als Katalysator |
US6960699B2 (en) | 2002-03-15 | 2005-11-01 | Oxeno Olefinchemie Gmbh | Method for the hydroformylation of olefins |
DE10220799A1 (de) * | 2002-05-10 | 2003-12-11 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von C13-Alkoholgemischen |
DE102004059292A1 (de) | 2004-12-09 | 2006-06-14 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von Alkoholen aus Olefinen durch Hydroformylierung und Hydrierung |
DE102004059293A1 (de) | 2004-12-09 | 2006-06-14 | Oxeno Olefinchemie Gmbh | Verfahren zur Hydroformylierung von Olefinen |
DE102007061648A1 (de) * | 2007-12-20 | 2009-07-02 | Evonik Oxeno Gmbh | Mehrstufiges kontinuierliches Verfahren zur Hydroformylierung von höheren Olefinen oder Olefingemischen |
DE102007061649A1 (de) * | 2007-12-20 | 2009-07-02 | Evonik Oxeno Gmbh | Einstufiges kontinuierliches Verfahren zur Hydroformylierung von höheren Olefinen oder Olefingemischen |
WO2009124922A1 (de) | 2008-04-10 | 2009-10-15 | Basf Se | Neuartige tenside für die tertiäre erdölförderung auf basis von verzweigten alkoholen |
US8541627B2 (en) * | 2008-08-29 | 2013-09-24 | Exxonmobil Chemical Patents Inc. | Hydroformylation process including catalyst recycle |
KR101379989B1 (ko) * | 2010-07-09 | 2014-04-01 | 주식회사 엘지화학 | 올레핀으로부터의 알데히드 제조 방법, 및 이에 사용되는 반응 장치 |
US8907019B2 (en) | 2010-12-21 | 2014-12-09 | Basell Polyolefine Gmbh | Polypropylene composition with high elasticity and transparency |
US9115069B2 (en) | 2013-11-18 | 2015-08-25 | Basf Se | Process for hydroformylation of olefins |
KR20160089405A (ko) * | 2013-11-18 | 2016-07-27 | 바스프 에스이 | 올레핀의 히드로포르밀화 방법 |
CN106533313B (zh) * | 2016-11-28 | 2018-10-23 | 青岛大学 | 电动汽车用永磁同步电机的极限学习机命令滤波控制方法 |
CN109894147B (zh) * | 2019-02-21 | 2022-03-11 | 中科合成油技术股份有限公司 | 一种负载型钴基催化剂及其制备方法和使用方法 |
EP4093722A1 (de) * | 2020-01-24 | 2022-11-30 | ExxonMobil Chemical Patents Inc. | Verfahren zur erhöhung der vorformungsraten von hydroformylierungskatalysatoren |
WO2021197953A1 (en) | 2020-04-03 | 2021-10-07 | Basf Se | Method for the hydroformylation of olefins |
CN114656343B (zh) * | 2020-12-23 | 2024-05-17 | 中国石油化工股份有限公司 | 一种制备醛和醇的方法 |
CN113385236B (zh) * | 2021-06-16 | 2023-02-03 | 上海华谊(集团)公司 | 烯烃氢甲酰化催化剂组合物和氢甲酰化方法 |
CN115701418B (zh) * | 2021-08-02 | 2024-05-17 | 中国石油化工股份有限公司 | 醛醇组合物及其制备方法、一种连续制备醛、醇的方法 |
CN116063168A (zh) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | 一种烯烃氢甲酰化反应的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2139630A1 (de) * | 1971-08-07 | 1973-02-22 | Basf Ag | Verfahren zur herstellung von vorwiegend geradkettigen aldehyden |
DE2404855A1 (de) * | 1974-02-01 | 1975-08-21 | Basf Ag | Verfahren zur verhinderung von emulsionsbildung bei der aufbereitung von butyraldehyden und kobalt enthaltenden reaktionsgemischen |
EP0850905A1 (de) * | 1996-12-24 | 1998-07-01 | Hüls Aktiengesellschaft | Verfahren zur Herstellung von höheren Oxo-Alkoholen |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1223381A (fr) | 1958-12-17 | 1960-06-16 | Ets Kuhlmann | Perfectionnements au procédé de fabrication de composés oxygénés par synthèse oxo |
BE787274A (fr) * | 1971-08-07 | 1973-02-07 | Basf Ag | Procede de preparation d'aldehydes a structure preponderante lineaire |
DE2237373C3 (de) * | 1972-07-29 | 1981-12-10 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von vorwiegend geradkettigen Aldehyden |
-
1999
- 1999-08-20 DE DE19939491A patent/DE19939491A1/de not_active Withdrawn
-
2000
- 2000-08-18 WO PCT/EP2000/008095 patent/WO2001014297A1/de active Search and Examination
- 2000-08-18 CN CNB008118434A patent/CN1257140C/zh not_active Expired - Fee Related
- 2000-08-18 ES ES00958472T patent/ES2231245T3/es not_active Expired - Lifetime
- 2000-08-18 US US10/049,859 patent/US6723884B1/en not_active Expired - Lifetime
- 2000-08-18 EP EP00958472A patent/EP1204624B1/de not_active Revoked
- 2000-08-18 DE DE50008524T patent/DE50008524D1/de not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2139630A1 (de) * | 1971-08-07 | 1973-02-22 | Basf Ag | Verfahren zur herstellung von vorwiegend geradkettigen aldehyden |
DE2404855A1 (de) * | 1974-02-01 | 1975-08-21 | Basf Ag | Verfahren zur verhinderung von emulsionsbildung bei der aufbereitung von butyraldehyden und kobalt enthaltenden reaktionsgemischen |
EP0850905A1 (de) * | 1996-12-24 | 1998-07-01 | Hüls Aktiengesellschaft | Verfahren zur Herstellung von höheren Oxo-Alkoholen |
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8247618B2 (en) | 2007-04-18 | 2012-08-21 | Exxonmobil Chemical Patents Inc. | Oxidative demetalling |
WO2011115695A1 (en) | 2010-03-15 | 2011-09-22 | Exxonmobil Chemical Patents Inc. | Processes for the production of alcohols |
WO2012084914A1 (de) | 2010-12-23 | 2012-06-28 | Basf Se | Thermoplastische elastomer-zusammensetzung und verfahren zu deren herstellung |
US9365715B2 (en) | 2010-12-23 | 2016-06-14 | Styrolution Europe Gmbh | Thermoplastic elastomer composition and method for the production thereof |
US10106486B2 (en) | 2013-10-31 | 2018-10-23 | Basf Se | Method for producing carboxylic acid esters and the use thereof as plasticizers |
US10030120B2 (en) | 2013-12-06 | 2018-07-24 | Basf Se | Softener composition which contains tetrahydrofuran derivatives and 1,2-cyclohexane dicarboxylic acid esters |
US10072133B2 (en) | 2014-01-09 | 2018-09-11 | Basf Se | Plasticizer composition containing furan derivatives and 1,2-cyclohexanedicarboxylic ester |
US9776949B2 (en) | 2014-04-22 | 2017-10-03 | Basf Se | Process for the production of carboxylic esters and use of these as plasticizers |
DE102015207291A1 (de) | 2014-04-24 | 2016-03-10 | Basf Se | Weichmacher-Zusammensetzung, die Furanderivate und 1,2-Cyclohexandicarbonsäureester enthält |
WO2016005358A1 (de) | 2014-07-08 | 2016-01-14 | Basf Se | Formmassen enthaltend dicarbonsäureester und 1,2-cyclohexandicarbonsäureester |
WO2016005357A1 (de) | 2014-07-08 | 2016-01-14 | Basf Se | Weichmacher-zusammensetzung, die aliphatische dicarbonsäureester und terephthalsäuredialkylester enthält |
US10266672B2 (en) | 2014-08-19 | 2019-04-23 | Basf Se | Plasticizer composition comprising polymeric dicarboxylic esters |
WO2016026838A1 (de) | 2014-08-19 | 2016-02-25 | Basf Se | Weichmacher-zusammensetzung, die polymere dicarbonsäureester enthält |
US10273345B2 (en) | 2014-09-04 | 2019-04-30 | Basf Se | Plasticizer composition which contains a polymer dicarboxylic acid ester |
US10287415B2 (en) | 2014-10-09 | 2019-05-14 | Basf Se | Plasticizer composition which comprises cycloalkyl esters of saturated dicarboxylic acids and terephthalic esters |
US10329402B2 (en) | 2014-10-09 | 2019-06-25 | Basf Se | Plasticizer composition which comprises cycloalkyl esters of saturated dicarboxylic acids and 1,2-cyclohexanedicarboxylic esters |
US10287417B2 (en) | 2015-01-30 | 2019-05-14 | Basf Se | Plasticizer composition containing polymeric dicarboxylic acid esters and terephthalic acid dialkyl esters |
WO2017055429A1 (de) | 2015-09-30 | 2017-04-06 | Basf Se | Weichmacher-zusammensetzung, die polymere dicarbonsäureester und 1,2-cyclohexandicarbonsäureester enthält |
WO2017055431A1 (de) | 2015-09-30 | 2017-04-06 | Basf Se | Weichmacher-zusammensetzung, die polymere dicarbonsäureester und dicarbonsäurediester enthält |
WO2017055432A1 (de) | 2015-09-30 | 2017-04-06 | Basf Se | Weichmacher-zusammensetzung, die polymere dicarbonsäureester und terephthalsäuredialkylester enthält |
US10315182B2 (en) | 2015-12-22 | 2019-06-11 | Basf Se | Cylindrical reactor and use thereof for continuous hydroformylation |
WO2017125458A1 (de) | 2016-01-20 | 2017-07-27 | Basf Se | Weichmacher-zusammensetzung, die aliphatische dicarbonsäureester und diester, die unter 1,2-cyclohexandicarbonsäureestern und terephthalsäureestern ausgewählt sind, enthält |
US10550242B2 (en) | 2016-01-20 | 2020-02-04 | Basf Se | Plasticiser composition containing aliphatic dicarboxylic acid esters and diesters selected from 1,2-cyclohexane dicarboxylic acid esters and terephthalic acid esters |
WO2017162723A2 (de) | 2016-03-23 | 2017-09-28 | Basf Se | Polymer-zusammensetzung, enthaltend einen cycloalkyl-alkyl-dicarbonsäurediester als weichmacher |
EP3686238A1 (de) | 2016-03-23 | 2020-07-29 | Basf Se | Polymer-zusammensetzung, enthaltend einen cycloalkyl-alkyl-dicarbonsäurediester als weichmacher |
US10787565B2 (en) | 2016-03-23 | 2020-09-29 | Basf Se | Polymer composition containing a cycloalkyl alkyl dicarboxylic acid diester as a plasticizer |
WO2018024594A1 (de) | 2016-08-01 | 2018-02-08 | Basf Se | Weichmacher-zusammensetzung |
WO2018024597A1 (de) | 2016-08-01 | 2018-02-08 | Basf Se | Weichmacher-zusammensetzung |
WO2018024591A1 (de) | 2016-08-01 | 2018-02-08 | Basf Se | Weichmacher-zusammensetzung |
WO2018210720A1 (de) | 2017-05-16 | 2018-11-22 | Basf Se | HYDROFORMYLIERUNGSVERFAHREN DIENEN DER GROßTECHNISCHEN HERSTELLUNG VON ALDEHYDEN UND/ODER ALKOHOLEN |
US11014863B2 (en) | 2017-05-16 | 2021-05-25 | Basf Se | Hydroformylation method for the large-scale production of aldehydes and/or alcohols |
WO2019185409A1 (de) | 2018-03-29 | 2019-10-03 | Basf Se | Pvc-zusammensetzung, enthaltend wenigstens einen weichmacher der wenigstens eine carbonsäureestergruppe aufweist und wenigstens eine carbodiimidverbindung |
EP3747860A1 (de) | 2019-06-04 | 2020-12-09 | Basf Se | Neue weichmacher auf cyclohexanon-basis |
WO2024089254A1 (en) | 2022-10-28 | 2024-05-02 | Basf Se | Process for the manufacture of a c4-olefin-derived chemical of interest, in particular citral, from renewably-sourced ethanol |
WO2024089256A1 (en) | 2022-10-28 | 2024-05-02 | Basf Se | Process for the manufacture of isononanol from renewably-sourced ethanol |
Also Published As
Publication number | Publication date |
---|---|
EP1204624B1 (de) | 2004-11-03 |
CN1257140C (zh) | 2006-05-24 |
US6723884B1 (en) | 2004-04-20 |
DE50008524D1 (de) | 2004-12-09 |
EP1204624A1 (de) | 2002-05-15 |
CN1370137A (zh) | 2002-09-18 |
DE19939491A1 (de) | 2001-02-22 |
ES2231245T3 (es) | 2005-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1204624B1 (de) | Kontinuierliches verfahren zur hydroformylierung von olefinen mit 6 bis 20 kohlenstoffatomen | |
EP1127864B1 (de) | Verbessertes Verfahren zur Hydroformylierung von Olefinen durch Reduzierung der Ameisensäurekonzentration | |
EP0850905B1 (de) | Verfahren zur Herstellung von höheren Oxo-Alkoholen | |
DE60002526T2 (de) | Herstellung von Tricyclodecandicarbaldehyd, Pentacyclopentadecandicarbaldehyd und der entsprechenden Dimethanole | |
EP2188236B1 (de) | Einstufiges kontinuierliches verfahren zur hydroformylierung von höheren olefinen oder olefingemischen | |
EP1485341A2 (de) | Verfahren zur hydroformylierung von olefinen | |
DE3205464A1 (de) | Verfahren zur herstellung von n-octanol | |
DE3017682A1 (de) | Verfahren zur herstellung von alkoholen | |
EP1694621A1 (de) | Verfahren zur herstellung von tricyclodecandialdehyd | |
DE2715685A1 (de) | Kontinuierliches verfahren zur herstellung von aldehyden durch hydroformylierung von alpha-olefinen | |
DE3125228C2 (de) | Verfahren zur Herstellung von Ethylenglykol durch Hydrierung von Glykolaldehyd mit Wasserstoff | |
DE3232557A1 (de) | Verfahren zur herstellung eines alkohols durch hydroformylierung | |
WO2009080395A1 (de) | Mehrstufiges kontinuierliches verfahren zur hydroformylierung von höheren olefinen oder olefingemischen | |
DE2826676C2 (de) | ||
DE102008007080A1 (de) | Verfahren zur Herstellung von C9-Alkohol aus C8-Olefinen | |
EP0510358B1 (de) | Verfahren zur Wiedergewinnung von Rhodium aus den Rückständen der Destillation von Produkten der Oxosynthese | |
DE2802923C2 (de) | Verfahren zur kontinuierlichen Herstellung von Butyraldehyden | |
DE10227995A1 (de) | Verfahren zur Hydroformylierung von Olefinen | |
EP0042928B1 (de) | Verfahren zur Herstellung von Fettsäureestern | |
EP0795533B1 (de) | Verfahren zur Herstellung von Aldehyden mittels eines Rhodium und substituierte Diphenyldiphosphane enthaltenden Katalysatorsystems | |
EP0475036A1 (de) | Verfahren zur Wiedergewinnung von Rhodium aus den Rückständen der Destillation von Produkten der Oxosynthese | |
DE3107873C2 (de) | Verfahren zur Herstellung von α-Acetoxy- oder α-Propionyloxypropionaldehyd | |
DE1165568B (de) | Verfahren zur Herstellung sauerstoffhaltiger Verbindungen durch Carbonylierung von Olefin-Kohlenwasserstoffen | |
AT206423B (de) | Verfahren zur Herstellung von gesättigten organischen Verbindungen, insbesondere Alkoholen, durch Carbonylierung bzw. Oxosynthese | |
EP0032525A2 (de) | Verfahren zur hydrierenden Aufarbeitung der bei der Hydrocarboxylierung eingesetzten kobalthaltigen Katalysatoren |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CN JP KR SG US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2000958472 Country of ref document: EP Ref document number: 10049859 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 008118434 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 2000958472 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWG | Wipo information: grant in national office |
Ref document number: 2000958472 Country of ref document: EP |
|
DPE2 | Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101) |