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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
  • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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  • B01J2219/00761—Details of the reactor
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  • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
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Definitions

• the invention relates to a method for carrying out a gas / liquid two-phase high-pressure reaction.
• the invention also relates to a method for adapting the reaction volume of a reactor suitable for carrying out a gas / liquid two-phase high-pressure reaction.
• the hydrogenation of organic compounds uses the reaction of a hydrogenatable compound with gaseous hydrogen. It is known to carry out the hydrogenation in a first backmixing zone and a second zone with limited backmixing. Backmixing in the first zone allows the heat of reaction to be dissipated expediently, while the second zone serves to complete the reaction conversion.
• WO 2009/153123 describes a continuous process for the hydrogenation of organic compounds in a multiphase system in the presence of a homogeneous or heterogeneous catalyst, the process being carried out in two stages, the first stage in a loop reactor with an external heat exchanger and the second stage in one Bubble column reactor with limited backmixing is carried out.
• EP 1 338 333 A1 describes a reactor cascade consisting of a closed main reactor and a closed secondary reactor, the secondary reactor being located in the interior of the main reactor vessel.
• EP 1 231 198 A1 describes a continuous process for the hydroformylation of olefins, in which a reactor is used which comprises two reaction spaces which can be flowed through in succession, wherein the second reaction space can have perforated plates.
• a volume flow is introduced into the reactor at any time and removed again at the reactor outlet. If the volume flow introduced is constant over time, the mean residence time of the reaction mixture in the reactor is also constant. The mean residence time is a measure of how much time the reaction mixture takes on average to flow through a reactor. If the volume flow is not constant over time, for example when there is a change in the volume of a starting material and / or a change in the demand for a reaction product, the mean residence time also changes. In many cases there is a undesired remaining of the reaction mixture in the reactor for too long, for example because undesired secondary reactions and / or decomposition can occur. In these cases it is desirable to be able to reversibly reduce the reaction volume of the reactor in a simple manner, in particular in the case of reactions which take place in the presence of a gas phase, but the actual conversion takes place in the liquid phase.
• displacers which are solid or closed on all sides can be introduced into the reactor. If these displacement bodies have internal cavities, the bodies must be designed to be pressure-resistant to the reaction pressure. A simpler, less expensive solution is desirable.
• the object is achieved by a process for carrying out a gas / liquid two-phase high-pressure reaction, in which a gas and a liquid are introduced into a backmixed zone of a reactor, and in the backmixed zone the gas in the liquid by stirring, pressing in gas and / or dispersing a jet of liquid, a reaction mixture flowing sequentially through the backmixed zone and a zone of limited backmixing, and withdrawing a liquid reaction product at a reaction product outlet of the limited backmixing zone, the reactor comprising: one of a cylindrical, vertically oriented, elongated jacket, a bottom and a hood formed interior, the interior being divided by internals in the backmixed zone, the zone of limited rearmixing and a cavity, a first cylindrical installation element which extends in the interior in the longitudinal direction of the reactor and which the Zone of limited backmixing delimited from the backmixed zone, backmixing-preventing second built-in elements in the form of packing elements, structured packings or liquid-permeable floors which are
• Extends reactor is open at the bottom and is preferably bounded at the top by the first cylindrical installation element, the third installation element forming the cavity in which gas bubbles collect and do not escape upwards, whereby the volume of the cavity cannot be taken up by liquid and the reaction volume is reduced.
• a high-pressure reaction is understood to mean a reaction which is carried out at a pressure which is higher than the ambient pressure, for example at least 5 bar absolute, at least 20 bar absolute or at least 50 bar absolute.
• the reactor comprises an interior formed by a cylindrical, vertically oriented, elongated jacket, a base and a hood.
• the ratio of length to diameter of the jacket is usually 2: 1 to 100: 1, preferably 5: 1 to 100: 1, particularly preferably 5: 1 to 50: 1, very particularly preferably 5: 1 to 30: 1.
• the interior of the reactor is divided by internals into a back-mixed zone, a zone of limited back-mixing and a cavity.
• the reaction mixture can flow through the backmixed zone and the zone of limited backmixing in succession.
• a first cylindrical installation element extends in the interior in the longitudinal direction of the reactor and delimits the zone of limited backmixing from the backmixed zone.
• a third installation element which extends in the interior in the longitudinal direction of the reactor, forms a cavity which is open at the bottom. Gas bubbles collect in the cavity and cannot escape upwards. When the cavity is completely gas-filled, the volume of the cavity can no longer be taken up by liquid. The reaction volume is reduced and the average residence time of the reaction mixture is shortened.
• the third installation element has a fluid outlet, in particular a gas outlet, via which the gas volume in the cavity can be adjusted.
• the third installation element does not have to be designed to be pressure-resistant.
• the third installation element is preferably a cylindrical installation element, so that the cavity has a circular horizontal cross section.
• the cylindrical installation element is arranged concentrically with the jacket.
• the third installation element is preferably arranged such that its lower end is at a distance from the floor which is in the range from 10 to 30%, particularly preferably 10 to 20% and very particularly preferably 10 to 15% of the height of the casing.
• the volume ratio of backmixed zone to zone of limited backmixing is preferably in the range from 0.25: 1 to 4: 1, particularly preferably in the range from 0.3: 1 to 3: 1.
• the volume ratio of back-mixed zone to cavity is preferably in the range from 0.5: 1 to 10: 1, particularly preferably in the range from 1: 1 to 5: 1.
• the volume ratio of back-mixed zone to gas space is preferably in the range from 1: 1 to 30: 1, particularly preferably in the range from 3: 1 to 10: 1.
• a reactor with volume ratios in this area allows optimal use of the reactor space.
• gas collects in the upper part of the back-mixed zone and forms a gas phase, while a liquid phase is present in the lower part of the back-mixed zone.
• the gas is dispersed in the liquid by stirring, pressing in gas and / or a liquid jet.
• Suitable stirring means include all stirrers known to those skilled in the art, such as propeller stirrers.
• Gas is injected into the liquid via a gas nozzle located below the liquid level.
• a jet nozzle generates a liquid jet which allows the gas phase to be dispersed and mixed within the backmixed zone.
• Gas and liquid are preferably introduced via a jet nozzle.
• the jet nozzle is designed in particular as a two-component nozzle. In the case of two-component nozzles, the gas with the liquid is fed to the back-mixed zone and dispersed.
• Gas and liquid can be supplied through a jet nozzle for gas and liquid at any point in the back-mixed zone, in particular an injection nozzle arranged below the liquid level.
• the gas and the liquid over a in the bottom of the Reactor located two-component jet nozzle up into the back-mixed zone.
• the backmixed zone is suitably designed as a buoyancy-free jet reactor which allows large-scale circulation of the contents of the backmixed zone by means of a punctiform or linear fluid injection.
• the backmixed zone is preferably essentially free of internals such as baffles, stirrers and the like.
• the back-mixed zone is preferably designed as a loop reactor. Examples of loop reactors are tubular reactors with internal and external loops.
• the loop reactor generally has an external circuit (external loops).
• an external circuit external loops
• the delivery device is preferably a pump, which is why the external circuit is usually referred to as a pumping circuit.
• pumps are centrifugal pumps or rotary piston pumps, such as rotary lobe pumps, rotary vane pumps, rotary lobe pumps or gear pumps. Centrifugal pumps are particularly preferably used as the delivery device.
• a heat exchanger is preferably located in the external circuit of the loop reactor.
• a loop reactor designed in this way is referred to in the context of this invention as a loop reactor with an external heat exchanger.
• the heat exchanger is, for example, a tube bundle heat exchanger, double tube heat exchanger, plate heat exchanger or spiral heat exchanger.
• a shell-and-tube heat exchanger is preferably used; at higher pressures, one or more double-tube heat exchangers connected in series are preferably used.
• the loop reactor with an external heat exchanger is usually operated in such a way that part of the reaction mixture from the backmixed zone is conveyed through the external pumping circuit in which the external heat exchanger is located, the reaction mixture conveyed by the heat exchanger being cooled. The reaction mixture is finally returned to the backmixed zone by means of the gas and liquid introduction means.
• External pumping generally mixes and circulates the reaction mixture vigorously in the first reaction stage, so that the residence time in the first stage usually corresponds to that of a completely backmixed stirred tank (CSTR).
• CSTR completely backmixed stirred tank
• fresh gas and fresh liquid are metered into the pumping circuit and, together with the current already in the pumping circuit, fed to the back-mixed zone as a reaction mixture.
• the backmixed zone has a gas outlet. Unreacted gas can be withdrawn via this.
• the gas outlet is preferably located at the upper end of the cylindrical jacket.
• the reactor is advantageously designed in such a way that the withdrawn, unreacted gas can at least partially be fed back into the reaction mixture in the back-mixed zone via the means for introducing gas and liquid.
• the unreacted gas can be led from the gas outlet via an external gas line to the means for introducing gas and liquid.
• the reactor comprises at least a fourth installation element which is arranged in the upper half of the back-mixed zone and has a surface which supports the tendency of foaming media to coalesce.
• Suitable built-in elements that support the tendency of foaming media to coalesce include elements for chemical, thermal or mechanical foam destruction. Pahl et al. in Chem. -Ing. -Tech. 67: 300-312 (1995).
• the reactor comprises mechanical foam destroyers, such as rotating elements, or internals for sprinkling with the liquid of its own kind.
• the reactor therefore preferably comprises a riser pipe, the lower end of which is arranged within the backmixed zone and the upper end of which opens into the zone of limited backmixing, so that liquid rises through the riser pipe from the backmixed zone into the zone of limited backmixing can.
• the riser pipe is arranged so that its lower end is immersed in the liquid phase during the gas / liquid two-phase high pressure reaction.
• the riser tube is suitably immersed so deeply in the liquid that essentially no foam can penetrate the riser tube. This essentially prevents contamination of downstream processing steps or subsequent reactions with foam.
• the lower end of the riser is spaced from the floor.
• the lower end of the riser pipe is at a distance from the floor which is in the range from 10 to 95%, particularly preferably 30 to 90% and very particularly preferably 70 to 80% of the level of the liquid.
• the riser tube usually has a diameter which is in the range from 1 to 90%, preferably 2 to 50%, very particularly preferably 5 to 20% of the diameter of the zone of limited backmixing.
• the reactor preferably comprises a fifth installation element arranged at the lower end of the riser pipe, which essentially prevents the entry of gas into the riser pipe.
• the shape and arrangement of the fifth installation element essentially prevent gas bubbles rising in the reaction mixture from entering the riser pipe.
• the fifth installation element is preferably selected from a deflection weir and a U-tube, and a deflection weir is particularly preferred.
• the backmixing in the zone of limited backmixing is limited by second built-in elements preventing backmixing. By installing such devices, the circulation and thus the
• the proportion of the gas phase in the reaction mixture in the zone of limited backmixing is preferably reduced in comparison to the backmixed zone.
• This effect can be achieved, for example, by using a riser pipe and possibly a fifth installation element, which essentially prevents gas from entering the riser pipe.
• the liquid holdup of the limited backmixing zone can be increased and the residence time of the liquid phase in the limited backmixing zone can be increased. Since high-pressure reactions essentially take place in the liquid phase, the reaction space is optimally used in this way.
• the limitation of the backmixing in the zone of limited backmixing can be realized by installing different internals.
• the backmixing is limited by the installation of several, firmly arranged soils in the zone of limited backmixing.
• Each of the individual segments usually acts like a single, back-mixed stirred tank reactor.
• the residence time distribution of such a cascade generally approaches the residence time of a tubular reactor.
• the number of individual segments formed in this way is preferably 2 to 20, particularly preferably 2 to 10, particularly preferably 3 to 6.
• the volume of the individual segments formed is usually essentially the same.
• the floors are preferably designed as liquid-permeable floors.
• the bottoms are particularly preferably designed as perforated plates.
• the backmixing is limited by the installation of fillers.
• the fillers can have different shapes and are usually about 2 to 15 mm in size. Known examples are spherical and cylindrical solid bodies, Raschig rings (hollow cylinders), Pall rings, Hiflow rings, Intalox saddles and the like.
• the fillers are preferably full bodies.
• the packing can be ordered, but also randomly (as a bed) in the zone of limited backmixing. Glass, ceramics, metal and plastics can be used as the material.
• the backmixing is limited by the installation of structured packings.
• Structured packings are a further development of the orderly packing. They exhibit a regular shape Structure on.
• packs such as fabric or sheet metal packs.
• Metal, plastic, glass and ceramic can be used as the material.
• the first installation element is preferably arranged concentrically with the casing, so that the zone of limited backmixing has a circular horizontal cross section.
• the ratio of length to diameter of the zone of limited backmixing is usually 2: 1 to 100: 1, preferably 5: 1 to 50: 1, particularly preferably 7: 1 to 25: 1.
• a gas and a liquid are introduced into the backmixed zone in a reactor as described above, and liquid is allowed to rise from the backmixed zone into the zone of limited backmixing, preferably through a riser pipe unreacted gas at least partially from the gas outlet, and withdraws a reaction product at the reaction product outlet.
• the unreacted gas is at least partially fed back into the reaction mixture in the back-mixed zone via an injection nozzle, for example via an external gas line.
• the process is a process for preforming a homogeneous rhodium hydride catalyst which contains at least one CO ligand. It is a pretreatment process with a gas mixture containing carbon monoxide and hydrogen.
• the liquid preferably comprises a dissolved CO-deficient rhodium hydrogenation catalyst and the gas contains hydrogen and carbon monoxide, a hydrogenation-active rhodium hydrogenation catalyst being obtained from the reaction of the CO-deficient rhodium hydrogenation catalyst with the gas.
• the reaction product of the preforming which is the hydrogenation-active rhodium hydrogenation catalyst
• the reaction product of the preforming can then be fed together with a substrate to be hydrogenated to an asymmetric hydrogenation reaction, whereby a hydrogenation reaction mixture is obtained.
• the residue is returned to the preforming with CO-deficient rhodium hydrogenation catalyst.
• the hydrogenation product can be carried out by processes known per se to the person skilled in the art, such as, for. B. by distillation and / or flash evaporation, separate from the hydrogenation mixture, the hydrogenation-active rhodium hydrogenation catalyst losing CO and a CO-deficient rhodium hydrogenation catalyst remaining.
• the substrate to be hydrogenated is cis-citral.
• the hydrogenation product of cis-Citral is R-Citronellal.
• the rhodium catalysts used have at least one CO ligand, at least in a form which is run through in the catalytic cycle or in a preform preceding the actual catalytic cycle, it being irrelevant whether this catalyst form having at least one CO ligand represents the actual catalytically active catalyst form.
• the rhodium catalyst usually has at least one optically active ligand.
• Such catalysts can be obtained, for example, by reacting a suitable rhodium compound which is soluble in the hydrogenation mixture with an optically active ligand which has at least one phosphorus and / or arsenic atom.
• rhodium compounds which can be used are: RhCh, Rh (OAc) 3, [Rh (cod) CI] 2, Rh (CO) 2acac, [Rh (cod) OH] 2, [Rh (cod) OMe] 2, Rh 4 (CO) i2, Rh6 (CO) i6, where "acac” stands for an acetylacetonate and "cod” for a cyclooctadiene ligand.
• the rhodium compounds mentioned are brought into contact with a further compound which is optically active, preferably essentially enantiomerically pure (i.e. has an enantiomeric excess of at least about 99%) and has at least one phosphorus and / or arsenic atom, preferably at least one phosphorus atom.
• This compound called chiral ligand, forms the rhodium catalyst with the rhodium compound used.
• Those chiral ligands which have two phosphorus atoms and form chelate complexes with rhodium are particularly preferred.
• Suitable chiral ligands in the context of the present invention are compounds such as those described, for example, in: I. Ojima (ed.), Catalytic Asymmetry Synthesis, Wiley-VCh, 2nd edition, 2000 or in EN Jacobsen, A. Pfaltz, H. Yamamoto (ed.), Comprehensive Asymmetrie Catalysis, 2000, Springer or in W. Tang, X. Zhang, Chem. Rev. 2003, 103, 3029-3069.
• Preferred ligands are chiral bidentate bisphosphine ligands, in particular those of the general formulas (I) to (III)
• R 5 , R 6 each independently represent an unbranched, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which is saturated or can have one or more, usually 1 to about 4, non-conjugated, ethylenic double bonds and the is unsubstituted or carries one or more, usually 1 to 4, identical or different substituents which are selected from OR 13 , NR 14 R 15 , halogen, C 6 -Cio-aryl and Cs-Cg-hetaryl, or
• R 5 and R 6 together can mean a 2 to 10-membered alkylene group or a 3 to 10-membered cycloalkylene group, in which 1, 2, 3 or 4 non-adjacent CH groups can be replaced by O or NR 13 , the alkylene group and the cycloalkylene group is saturated or has one or two non-conjugated ethylenic double bonds, and the alkylene group and the cycloalkylene group are unsubstituted or carry one or more identical or different substituents which are selected from C 1 -C 4 -alkyl; R 7 , R 8 each independently represent hydrogen or straight-chain or branched Ci-C 4 alkyl and
• R 9 , R 10 , R 11 , R 12 are identical or different and represent C 6 -Cio-aryl which is unsubstituted or carries one or more substituents which are selected from Ci-C 6 -alkyl, C3-C6- Cycloalkyl, C 6 -Cio aryl, Ci-C 6 alkoxy and amino;
• R 13 , R 14 , R 15 each independently of one another denote hydrogen, Ci-C4-alkyl, C 6 -Cio-aryl, C7-Ci2-aralkyl or C7-Ci2-alkylaryl, where R 14 and R 15 also together form an alkylene chain 2 to 5 carbon atoms, which can be interrupted by N or O, can mean.
• R 5 , R 6 each independently represent C 1 -C 4 -alkyl or
• R 5 and R 6 together represent a Cs-Cs-alkanediyl radical, C3-C7-alkenediyl radical, C5-C7-cycloalkanediyl radical or a C5-C7-cycloalkenediyl radical, the four aforementioned radicals being unsubstituted or carry one or more identical or different substituents which are selected from C 1 -C 4 -alkyl;
• R 7 , R 8 are each independently hydrogen or C 1 -C 4 -alkyl
• R 9 , R 10 , R 11 , R 12 each represent phenyl. Because of their easy availability, particularly preferred chiral, bidentate bisphosphine ligands are compounds of the formula obtainable under the name "Chiraphos":
• the chiral ligands are advantageously used in an amount of about 0.9 to about 10 mol, preferably about 1 to about 4 mol, per mol of rhodium compound used.
• the optically active rhodium catalyst is suitably generated by reacting an achiral rhodium compound and a chiral, bidentate bisphosphine ligand in situ.
• the term "in situ" means that the catalyst is generated directly before the hydrogenation. It has been found that the presence of monodentate ligands can increase the activity of the catalyst.
• Z in formula (IV) represents a group CHR 18 R 19 and in which the variables R 16 , R 17 , R 18 , R 19 independently and in particular together have the following meanings :
• R 16 , R 17 are identical or different and stand for phenyl which is unsubstituted or carries 1, 2 or 3 substituents which are selected from methyl and methoxy, where R 16 and R 17 each stand in particular for unsubstituted phenyl;
• R 18 represents C to C 4 alkyl, in particular methyl
• a compound of the formula (IV) in which
• R 16 , R 17 stand for unsubstituted phenyl;
• R 18 represents methyl;
• the carbon atom which carries the radicals R 18 and R 19 can have an (R) or (S) configuration.
• These compounds of the general formula (IV) can exist as pure (R) or pure (S) stereoisomers or as mixtures thereof.
• the pure (R) and (S) stereoisomers will be used in these cases, and any stereoisomer mixtures are also suitable for use in the present process.
• a pure stereoisomer is understood here and below to mean chiral substances which have an enantiomeric excess (ee) of at least 80% ee, in particular at least 90% ee and especially at least 95% ee with respect to the desired stereoisomer.
• Chiraphos is used as the chiral ligand and (2- (diphenylphosphoryl) -1-methylpropyl) diphenylphosphine (chiraphos monoxide) as the monodentate binding compound.
• R-Chiraphos is used as the chiral ligand and (R, R) -chiraphosmonooxide and / or (S, S) -chiraphosmonooxide is used as the monodentate binding compound.
• S-Chiraphos is used as the chiral ligand and (R, R) -chiraphosmonooxide and / or (S, S) -chiraphosmonooxide as the monodentate binding compound.
• the compound of the formula (IV) is generally used in an amount of 0.01 to 1 mol, preferably 0.02 to 0.8 mol, particularly preferably 0.03 to 0.7 mol and in particular in an amount of 0 , 04 to 0.6 moles per mole of rhodium.
• the hydrogenation catalyst and the monodentate ligand are described in US 2018/0057437 A1, WO 2006/040096 A1 and WO 2008/132057 A1.
• the selected rhodium compound and the selected chiral ligand are usually dissolved in a suitable solvent or solvent medium which is inert under the reaction conditions, such as, for example, ether, tetrahydrofuran, methyltetrahydrofuran, toluene, xylenes, chlorobenzene, octadecanol, biphenyl ether, Texanol, Marlotherm, Oxoöl 9N (hydroformylation products from isomeric octenes, BASF Aktiengesellschaft), citronellal and the like.
• the hydrogenation product or any high-boiling by-products that may occur during the reaction can also serve as the solution medium.
• the resulting solution is injected in the reactor according to the invention at a pressure of usually about 5 to about 350 bar, preferably from about 20 to about 200 bar and particularly preferably from about 50 to about 100 bar, which contains hydrogen and carbon monoxide.
• Preforming is preferably carried out using a gas mixture which contains about 30 to 99% by volume of hydrogen,
• a particularly preferred gas mixture for preforming is so-called synthesis gas, which usually consists of about 35 to 55% by volume of carbon monoxide in addition to hydrogen and traces of other gases.
• the preforming of the catalyst is usually carried out at temperatures from about 25 ° C. to about 100 ° C., preferably at about 40 ° C. to about 80 ° C.
• Preforming is usually complete after about 1 hour to about 24 hours, often after about 1 to about 12 hours.
• the asymmetric hydrogenation of a selected substrate is preferably carried out.
• the selected substrate can generally be carried out successfully with or without the addition of additional carbon monoxide.
• a preforming as described is advantageously carried out and additional carbon monoxide is added to the reaction mixture during the asymmetric hydrogenation.
• the above-mentioned preforming of the catalyst precursor with a gas mixture comprising 20 to 90% by volume of carbon monoxide, 10 to 80% by volume of hydrogen and 0 to 5% by volume of further gases, the volume parts mentioned being 100% by volume .-% add, carried out at a pressure of 5 to 100 bar.
• excess carbon monoxide is separated off from the catalyst thus obtained before use in the asymmetric hydrogenation.
• Excess carbon monoxide is to be understood as meaning carbon monoxide which is contained in the reaction mixture obtained in gaseous or dissolved form and is not bound to the rhodium catalyst or its precursor.
• the excess carbon monoxide which is not bound to the catalyst is at least largely removed, ie to an extent that any residual amounts of dissolved carbon monoxide do not have a disruptive effect in the subsequent hydrogenation. This is usually ensured if about 90%, preferably about 95% or more, of the carbon monoxide used for the preforming is separated off.
• the excess carbon monoxide is preferably removed completely from the catalyst obtained by preforming.
• the excess carbon monoxide can be separated off from the catalyst obtained or from the reaction mixture containing the catalyst in various ways.
• the catalyst or the mixture containing the catalyst obtained by preforming is preferably depressurized to a pressure of up to about 5 bar (absolute), preferably, especially when the preforming is carried out in the pressure range from 5 to 10 bar, to a pressure of less than 5 bar (absolute), preferably to a pressure in the range from about 1 bar to about 5 bar, preferably 1 to less than 5 bar, particularly preferably to a pressure in the range from 1 to 3 bar, very particularly preferably to a pressure in the Range from about 1 to about 2 bar, particularly preferably at normal pressure, so that gaseous, unbound carbon monoxide escapes from the product of the preforming.
• the above-mentioned expansion of the preformed catalyst can be carried out, for example, using a high-pressure separator, as is known to the person skilled in the art.
• a high-pressure separator as is known to the person skilled in the art.
• Such separators in which the liquid is in the continuous phase are described, for example, in: Perry's Chemical Engineers' Handbook, 1997, 7th edition, McGraw-Hill, pp. 14.95 and 14.96; the prevention of a possible droplet drought is described on pages 14.87 to 14.90.
• the preformed catalyst can be expanded in one or two stages until the desired pressure is reached in the range from 1 bar to about 5 bar, the temperature usually falling to 10 to 40 ° C.
• excess carbon monoxide can be separated off by stripping the catalyst or the mixture containing the catalyst with a gas, advantageously with a gas which is inert under the reaction conditions.
• stripping is understood by the person skilled in the art to mean the introduction of a gas into the catalyst or the reaction mixture containing the catalyst, for example in WRA Vauck, HA Müller, Basic Operations of Chemical Process Engineering, German Publisher for Basic Chemicals Leipzig, Stuttgart, 10th Edition, 1984, page 800 , described.
• Suitable inert gases may be mentioned as examples: hydrogen, helium, neon, argon, xenon, nitrogen and / or CO 2, preferably hydrogen, nitrogen, argon.
• the feed can be carried out in various ways:
• the carbon monoxide can be mixed with the hydrogen used for the asymmetric hydrogenation or can be metered directly into the reaction solution in gaseous form.
• the carbon monoxide is preferably admixed with the hydrogen used for the asymmetric hydrogenation.
• the asymmetric hydrogenation is preferably carried out with hydrogen which has a carbon monoxide content in the range from 50 to 3000 ppm, in particular in the range from 100 to 2000 ppm, especially in the range from 200 to 1000 ppm and very particularly in the range from 400 to 800 ppm.
• the hydrogenation product can be carried out by processes known per se to the person skilled in the art, such as, for. B. by distillation and / or flash evaporation, separate from the hydrogenation mixture and use the remaining catalyst in further reactions.
• the addition of solvents is advantageously dispensed with and the reactions mentioned are carried out in the substrate or the product to be reacted and, if appropriate, in high-boiling by-products as the dissolving medium. Continuous reaction control with reuse or recycling of the homogeneous catalyst stabilized according to the invention is particularly preferred.
• a prochiral a, b-unsaturated carbonyl compound is hydrogenated.
• a prochiral a, b-unsaturated carbonyl compound can form a chiral center by addition reaction to the olefinic double bond.
• the double bond carries four different substituents.
• the prochiral a, b-unsaturated carbonyl compound is preferably selected from compounds of the general formula (V)
• R 1 , R 2 are different from one another and each represent an unbranched, branched or cyclic hydrocarbon radical having 1 to 25 Are carbon atoms, which is saturated or has one or more non-conjugated ethylenic double bonds, and which is unsubstituted or carries one or more identical or different substituents which are selected from OR 4 , NR 5a R 5b , halogen, C 6 -Cio- Aryl and hetaryl with 5 to 10 ring atoms,
• R 3 represents hydrogen or an unbranched, branched or cyclic hydrocarbon radical having 1 to 25 carbon atoms, which is saturated or has one or more non-conjugated ethylenic double bonds and which is unsubstituted or carries one or more identical or different substituents which are selected are under OR 4 , NR 5a R 5b , halogen, C 6 -Cio-aryl and hetaryl with 5 to 10 ring atoms, or
• R 3 together with one of the radicals R 1 or R 2 also has a 3 to 25-membered group
• R 53 , R 5b each independently of one another are hydrogen, C 1 -C 6 -alkyl, C 6 -cio-aryl,
• Ci-Cio-alkyl-C6-Ci4-aryl mean or
• R 5a and R 5b together can also mean an alkylene chain with 2 to 5 carbon atoms, which can be interrupted by N or O; and R 5c represents hydrogen, Ci-C 6 alkyl, C 6 -Cio-aryl, C6-Ci4-aryl-Ci-Cio-alkyl or Ci-Cio-alkyl-C6-Ci4-ary-.
• the prochiral a, b-unsaturated carbonyl compound is selected from compounds of the general formulas (Va) and (Vb)
• R 1 , R 2 each represent an unbranched or branched hydrocarbon radical having 2 to 25 carbon atoms, which is saturated or has 1, 2, 3, 4 or 5 non-conjugated ethylenic double bonds.
• a particularly preferred embodiment relates to a process for the production of optically active citronellal of the formula (VI) where * denotes the center of asymmetry; by asymmetric hydrogenation of geranial of the formula (Va-1) or of neral of the formula (Vb-1)
• optically active citronellal of formula (VI) thus obtainable can be cyclized to optically active isopulegol and the optically active isopulegol can be hydrogenated to optically active menthol.
• a method is also provided for adapting the reaction volume of a reactor suitable for carrying out a gas / liquid two-phase high-pressure reaction, in which an installation element is arranged in such a way that it forms a cavity which is open at the bottom.
• the installation element is a installation element according to the third installation element described above, including the embodiments described in this regard.
• Fig. 1 shows schematically a reactor which is suitable for performing the method according to the invention.
• the reactor comprises a backmixed zone 101, a zone of limited backmixing 102, the backmixing of which is limited by built-in trays, a gas space 103 and a cavity 104.
• a gas and a liquid from line 105 of the backmixed zone are passed through an injection nozzle (not shown) 101 fed.
• the back-mixed zone 101 has a gas outlet 106 through which unreacted gas is carried out. Liquid rises from the backmixed zone 101 through a liquid passage (not shown) into the restricted backmixing zone 102. Reaction product is carried out via the reaction product outlet 107.
• the reactor comprises a backmixed zone 201, a zone of limited backmixing 202, the backmixing of which is limited by built-in trays, a gas space 203 and a cavity 204.
• a gas and a liquid from line 205 of the backmixed zone are passed through an injection nozzle (not shown) 201 fed.
• the backmixed zone 201 has a gas outlet 206 through which unreacted gas is carried out. Liquid rises from the backmixed zone 201 into the zone of limited backmixing 202 via the riser pipe 207, the lower end of which is arranged below the liquid level. Reaction product is carried out via the reaction product outlet 108.
• the reactor comprises a deflection weir 209, which essentially prevents the entry of gas into the riser pipe 207.

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