WO2002068371A1 - Procede de fabrication d'aldehydes - Google Patents

Procede de fabrication d'aldehydes Download PDF

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Publication number
WO2002068371A1
WO2002068371A1 PCT/EP2002/001379 EP0201379W WO02068371A1 WO 2002068371 A1 WO2002068371 A1 WO 2002068371A1 EP 0201379 W EP0201379 W EP 0201379W WO 02068371 A1 WO02068371 A1 WO 02068371A1
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mixture
rhodium
radicals
reaction
olefinically unsaturated
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PCT/EP2002/001379
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German (de)
English (en)
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Hans Bohnen
Jürgen HERWIG
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Celanese Chemicals Europe Gmbh
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Publication of WO2002068371A1 publication Critical patent/WO2002068371A1/fr

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    • 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
    • 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
    • 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
    • B01J31/24—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
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/2471—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom
    • B01J31/2476—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • 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
    • 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
    • B01J2531/822—Rhodium

Definitions

  • the invention relates to an improved process for the hydroformylation of olefinically unsaturated compounds in using the unreacted olefins escaping from the hydroformylation zone with the exhaust gas.
  • Rhodium is used as a complex compound which, in addition to carbon monoxide, preferably contains phosphines as ligands. Rhodium as a metal makes it possible to work at low pressures, moreover, higher yields are achieved and the unbranched products which are more valuable for further processing are preferably formed when starting from straight-chain terminal olefins.
  • the reaction is not carried out until the olefinically unsaturated compounds are completely consumed, but is often satisfied with the conversion of only 60 to 95% of the starting material to the desired end compound.
  • the exhaust gas leaving the hydroformylation zone therefore contains unreacted olefinic feedstock which can be converted into valuable materials by differently designed processes.
  • the exhaust gas which contains olefin, optionally aldehyde, furthermore hydrogen, carbon monoxide and alkane by-product, is fed to a decoupled, ie separately operated, secondary rhodium-catalyzed hydroformylation process in which the exhaust gas is recirculated with liquid or gas together with added carbon monoxide and hydrogen for reaction brought.
  • the known method also allows the reaction of olefins, which are available as a mixture of terminal and internal olefinic compounds, such as. B. a mixture of isomeric butenes.
  • the terminal olefins contained in the exhaust gas are reacted and in the second reaction stage.
  • Such a process variant is particularly important, in which the second reaction stage is carried out under those reaction conditions under which the internal olefins are converted into the straight-chain aldehydes with high selectivity.
  • the conversion of internal olefins into the straight-chain aldehydes with high selectivity is known from EP-B1-0 213 639, in which special diphosphites are used as ligands.
  • diphosphite ligands are restricted by their lower stability compared to conventional phosphine ligands and their greater sensitivity to hydrolysis and traces of hydrolysis, and the phosphonous acids formed during the continuously operated hydroformylation process adversely affect the catalyst life and have to be removed from the process at great expense be, e.g. by treating the catalyst-containing solution with an alkaline ion exchanger before returning it to the hydroformylation process.
  • diphosphite ligands allow the hydroformylation of internal olefins to give straight-chain aldehydes with high selectivity, but due to their known sensitivity to hydrolysis, diphosphite ligands tend to form phosphonous acids, which can have a detrimental effect on the rhodium complex catalyst and thus lead to a shortening of the catalyst life.
  • the object was therefore to develop a process which, under economically justifiable conditions, allows olefinic compounds containing in the exhaust gas of a hydroformylation reaction to be converted with high selectivity to the straight-chain carbonyl compounds, the process to be provided being supposed to show an advantageously long catalyst life.
  • the invention therefore consists in a process for the hydroformylation of olefinically unsaturated compounds, the reaction in a first reaction stage in a homogeneous reaction system using organic phosphorus (III) compounds in complex bonds containing rhodium compounds as catalysts at pressures of 0.2 to 20 , 0 MPa and exhaust gas is bidet. It is characterized in that the offgas is fed to the first reaction stage of a second reaction stage in which amounts of the olefinically unsaturated compounds present in the offgas are present in a homogeneous reaction system in the presence of complex compounds of rhodium and diphosphines of the general formula (I)
  • R 1 and R 2 are each the same or different (C 1 -C 18 ) alkyl radicals, (C 6 -C 4 ) aryl radicals, (C 7 -C 2 ) aralkyl radicals or (C 7 - C 2 ) -Alkylaryl radicals
  • R 3 represents hydrogen or a -CHR a R b radical in which R a and R b are each the same or different hydrogen, (Ci-Ci 8 ) alkyl-, (C ⁇ -Ca) -Alkoxy radicals, unsubstituted or substituted with (C ⁇ -C ⁇ o) alkyl and / or (C ⁇ -C 10 ) alkoxy radicals (C 6 -C ⁇ 4 ) aryl radicals or (C 7 -C 24 ) - Aralkyl radicals, and R 4 (d-C ⁇ o) alkyl radicals, (C 6 -C 4 ) aryl radicals, (C 7 -C 24 )
  • diphosphines are derived from the xanthene scaffold as the base and attached oxaphosphine.
  • the diphosphines of the general formula I and their production process are the subject of a patent application filed on the same day, which is hereby expressly incorporated by reference (“incorporated by reference”).
  • diphosphines of the general formula I those diphosphines in which R 1 and R 2 are each the same or different are particularly suitable (C ⁇ -C 12) -alkyl radicals, (C 6 -C 10) -aryl residues, (C 7 -C ⁇ 0) aralkyl radicals or (C 7 - C ⁇ o) alkylaryl radicals,
  • R 3 represents hydrogen or a radical -CHR a R b , in which R a and R b are each identical or different hydrogen, (-CC 2 ) alkyl-, (CrC 4 ) -alkoxy radicals, unsubstituted or with (C ⁇ -C 8 ) alkyl and / or (-C-C 4 ) alkoxy radicals are substituted (C 6 -C 10 ) aryl radicals or (C 7 -C ⁇ 0 ) aralkyl radicals, and R 4 ( d- C 8 ) alkyl radicals, (C 6 -C 10 ) aryl radicals, (C 7 -C 10 ) aralkyl radicals or (C 7 -C 10 ) alkylaryl radicals.
  • the aryl radical is preferably in each case the phenyl or naphthyl radical, and the benzyl radical is preferably used as the aralkyl radical.
  • R 1 and R 2 are identical or different and are methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tertiary butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl , n-heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, naphthyl, tolyl or benzyl.
  • R 3 stands for example for methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, 3,3-dimethylbutyl, n-hexyl, i-hexyl, n-heptyl, i -Heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, naphthyl, tolyl or benzyl.
  • R 4 stands for example for methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tertiary butyl, n-pentyl, i-pentyl, 3,3-dimethylbutyl, n-hexyl, i-hexyl, n- Heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, naphthyl, tolyl or benzyl.
  • the new process ensures that the majority of the olefinic compounds not converted in the exhaust gas in the first stage are hydroformylated to give straight-chain aldehydes.
  • the starting material for the overall process is not only limited to olefinically unsaturated compounds with terminal double bonds.
  • the process according to the invention is also suitable for the hydroformylation of those starting olefins in which the terminal and internal Double bond is present in a molecule or are available in the art as a mixture of olefins with terminal and internal double bonds. Such a mixture is, for example, a mixture of isomeric butenes.
  • the new process succeeds in converting the olefinically unsaturated compounds contained in the exhaust gas with internal double bonds, which only react to a minor extent in the first stage, to linear aldehydes.
  • high selectivities to the desired straight-chain carbonyl compounds can also be achieved.
  • the high efficiency of the process according to the invention could not be predicted.
  • the olefinically unsaturated compounds in the exhaust gas are in considerable dilution and that their contents can be between 20 and 65% by weight, depending on the olefin used.
  • the second hydroformylation stage can be carried out with a high conversion.
  • diphosphine ligands of the general formula (I) used according to the invention in the second hydroformylation stage prove to be very stable. It is therefore possible to run the entire process over many catalytic cycles without a decrease in activity and selectivity. A frequent and expensive catalyst work-up after only a few catalytic cycles is therefore not necessary.
  • the first reaction stage of the new process is carried out in a homogeneous reaction system.
  • the term homogeneous reaction system stands for a homogeneous solution composed essentially of solvent, catalyst, olefinically unsaturated compound and reaction product.
  • the higher-boiling solvents have proven to be particularly effective solvents.
  • Examples of such compounds are aromatic hydrocarbons, such as benzene and toluene or the isomeric xylenes and mesitylene.
  • Other common solvents are paraffin oil, cyclohexane, n-hexane, n-heptane or n-octane, ethers such as tetrahydrofuran, ketones or Texanol® from Eastman.
  • the proportion of solvent in the reaction medium can be varied over a wide range and is usually between 20 and 90% by weight, preferably 50 to 80% by weight, based on the reaction mixture.
  • Rhodium complex compounds are used as catalysts, which contain organic Pho ⁇ pho ⁇ ll compounds as ligands. Such complexy compounds and their preparation are known (for example from US-A-3,527,809, US-A-4,148,830, US-A-4,247,486, US-A-4,283,562). They can be used as uniform complex compounds or as a mixture of different complex compounds.
  • the rhodium concentration in the reaction medium extends over a range from about 1 to about 1000 ppm by weight and is preferably 10 to 700 ppm by weight. In particular, rhodium is used in concentrations of 25 to 500 ppm by weight, based in each case on the homogeneous reaction mixture.
  • the stoichiometrically composed rhodium complex compound can be used as a catalyst. However, it has proven expedient to carry out the hydroformylation in the presence of a catalyst system composed of rhodium-phosphorus complex compound and free, ie excess phosphorus ligand which no longer forms a complex compound with rhodium.
  • the free phosphorus ligand can be the same as in the rhodium Complex compound, but ligands different from this can also be used.
  • the free ligand can be a single compound or consist of a mixture of different organophosphorus compounds. Examples of rhodium-phosphorus complex compounds which can be used as catalysts are described in US Pat. No. 3,527,809.
  • the preferred ligands in the rhodium complex catalysts include e.g. B. triarylphosphines such as triphenylphosphine, trialkylphosphines such as tri (n-octyl) phosphine, trilaurylphosphine, tri (cyclohexyl) phosphine, alkylphenylphosphines, cycloalkylphenylphosphines and organic diphosphites. Because of its easy accessibility, triphenylphosphine is used particularly frequently.
  • triarylphosphines such as triphenylphosphine
  • trialkylphosphines such as tri (n-octyl) phosphine, trilaurylphosphine, tri (cyclohexyl) phosphine, alkylphenylphosphines, cycloalkylphenylphosphines and organic diphosphites. Because of its easy
  • the molar ratio of rhodium to phosphorus is usually 1: 1 to 1: 1000 in the homogeneous reaction mixture, but the molar proportion of phosphorus in the form of organic phosphorus compounds can also be higher.
  • Rhodium and organically bound phosphorus are preferably used in molar ratios of 1: 3 to 1: 500.
  • rhodium to phosphorus molar ratios of 1:50 to 1: 300 have proven particularly useful. If trialkylphosphines are used as ligands, the molar ratio of rhodium to phosphorus is preferably 1: 3 to 1: 100.
  • the conditions under which the reaction takes place in the first reaction stage can vary within wide limits and can be adapted to the individual circumstances. They depend, among other things, on the feedstock, the catalyst system selected and the degree of conversion aimed for.
  • the hydroformylation of the starting materials is usually carried out at from 50 to 160.degree. Temperatures of from 60 to 150 ° C. and in particular from 75 to 140 ° C. are preferred.
  • the total pressure extends over a range from 0.2 to 20.0 MPa, preferably 1 to 12 MPa and in particular 1 to 7 MPa.
  • the molar ratio of hydrogen to carbon monoxide usually ranges between 1:10 and 10: 1, Mixtures which contain hydrogen and carbon monoxide in a molar ratio of 3: 1 to 1: 3, in particular about 1: 1, are particularly suitable.
  • the catalyst is usually formed from the components rhodium or rhodium compound, organic phosphorus compound and synthesis gas under the conditions of the hydroformylation reaction in the reaction mixture. However, it is also possible to first preform the catalyst and then to feed it to the actual hydroformylation stage.
  • the preforming conditions generally correspond to the hydroformylation conditions.
  • the reaction conditions in the first stage can be selected so that the olefinically unsaturated compounds with terminal double bonds are reacted in a targeted manner.
  • the reaction conditions are expediently set so that the conversion to the straight-chain aldehydes takes place with the highest possible selectivity.
  • the selectivities to be achieved for the straight-chain aldehydes are, however, particularly influenced by the ligands containing phosphorus.
  • Olefins with a terminal double bond are preferably implemented.
  • the unreacted olefins, mostly those with an internal double bond, are therefore enriched in the exhaust gas of the first reaction stage.
  • the reaction product of the first reaction stage is separated off from the catalyst, for example distilled off.
  • the residue containing the catalyst after removal of the aldehyde is returned to the reaction zone, if appropriate after addition of fresh catalyst and removal of part of the aldehyde condensation products formed in the course of the reaction.
  • the waste gas escaping from the first reaction stage is composed of the waste gas which is taken directly from the reactor (reactor waste gas) in order to avoid an accumulation of inert substances in the circulated gas mixture and the gaseous components which are present in the separation of catalyst and crude reaction product, e.g. in the distillation of the aldehyde from the reaction product. (Product gas).
  • the exhaust gas stream essentially consists of unreacted olefinic compound, carbon monoxide, carbon dioxide, hydrogen and the hydrogenation products of the olefin.
  • the exhaust gas stream only contains residual amounts of olefinically unsaturated compound, depending on whether partial conversion or almost complete conversion is aimed for in the first stage. If the starting material for the process according to the invention contains olefins with internal double bonds, these are only converted to a minor extent in the first stage and are therefore enriched in the exhaust gas stream.
  • the exhaust gas stream is generally without further intermediate treatment, in particular without purification, but if necessary after admixing
  • Hydrogen alone or in a mixture with carbon monoxide as a feed of a second hydroformylation step may prove expedient to clean the exhaust gas stream before use in the second hydroformylation stage.
  • the second hydroformylation stage is decoupled, i.e. operated independently of the first hydroformylation stage with a catalyst different from the first hydroformylation stage.
  • the amounts of olefinically unsaturated compounds present in the exhaust gas stream are also reacted in a homogeneous reaction system with carbon monoxide and hydrogen.
  • Those solvents are used as solvents which have also proven themselves in the first reaction stage.
  • Rhodium complex compounds which contain diphosphines of the general formula (I) as ligands are used as catalysts.
  • diphosphines of the general formula I those diphosphines are particularly suitable as ligands which, on the one hand, are readily soluble in the reaction mixture, so that there are no precipitations of the diphosphine itself under process conditions, even over many catalytic cycles.
  • the diphosphines and the rhodium complex compounds derived from them must have high long-term stability under the hydroformylation conditions and thus ensure homogeneous reaction control even over many catalytic cycles.
  • diphosphines are particularly suitable: 2,7-bis (3,3-dimethylbutyl) -9,9-dimethyl-4,5-bis (2,7-dimethyl-10-phenoxaphosphino) xanthene (II), 2, 7,9-trimethyl-9-n-nonyl-4,5-bis (2J-dimethyl-10-phenoxaphos- phino) xanthene (III), 2,7-di-n-decyl-9,9-dimethyl-4,5-bis (2,7-dimethyl-10-phenoxaphosphino) xanthene (IV), 2,7-di- n-hexyl-9,9-dimethyl-4,5-bis (2,7-dimethyl-10-phenoxaphosphino) xanthene (V), 2,7- (3,3-dimethylbutyl) -9,9-dime - thyl-4,5-bis [2,7-di (3,3-dimethylbutyl
  • the increase in carbon atoms is not a criterion by which the solubility behavior can be read off. Furthermore, the solubility of the xanthene skeleton without phenoxaphosphine substituents does not indicate the solubility behavior of the ligand with phenoxaphosphine substituents.
  • diphosphines of the general formula I and in particular the diphosphines of the formulas II to VII are used, a concentration of diphosphine in the reaction solution which is sufficient for the continuous reaction in the hydroformylation can be set.
  • the diphosphines II, IV, V and VI have excellent solubility in the reaction mixture.
  • the complex compounds obtained from rhodium and diphosphines of the general formula I can be used as uniform complex compounds or as a mixture of different complex compounds.
  • the rhodium concentration ranges from 1 to 1000 ppm by weight and is preferably 50 to 500 ppm by weight.
  • rhodium is used in concentrations of 100 to 300 ppm by weight, based in each case on the homogeneous reaction mixture. Due to their solubility, the phosphorus (HO concentration in the form of the diphosphines can be adjusted to a value of 4 mol P (III) per kilogram of homogeneous reaction solution.
  • the phosphorus (III) content in the reaction mixture usually ranges from 10 to 400 mmol P (III), preferably 10-100 mmol P (III) and in particular 10-50 mmol P (III) per kilogram of reaction mixture.
  • the stoichiometrically composed rhodium complex compound can be used as the catalyst.
  • the free diphosphine can be the same as in the rhodium complex compound, but diphosphines other than this can also be used as ligands.
  • the free ligand can be a single compound or consist of a mixture of different diphosphines.
  • phosphorus Preferably 1 to 20 mol of phosphorus is used per mol of rhodium in the form of the diphosphines, but the molar proportion of the phosphorus can also be higher. Due to the good solubility of the diphosphines used according to the invention, a higher molar ratio of up to 80 mol phosphorus per mol rhodium can also be set. However, it is expedient to work with lower molar ratios of up to 20 mol of phosphorus per mol of rhodium. When using
  • the reaction pressure in the second stage of the overall process is in the range of 0.2 to 20.0 MPa. It has proven particularly useful to maintain pressures between 1 and 12 MPa and in particular between 1 and 5 MPa.
  • the composition of the synthesis gas for the second hydroformylation stage can vary over a wide range. In general, the molar ratio of carbon monoxide to hydrogen is between 1:10 and 10: 1. Mixtures containing carbon monoxide and hydrogen in a molar ratio of 1: 2 and 2: 1 are particularly suitable. In particular, it has proven to be advantageous to use synthesis gas with a slight excess of hydrogen.
  • reaction temperatures in the second stage of the new process are 50 to 160 ° C. Temperatures of 60 to 150 ° C and in particular 75 to - 140 ° C are preferred.
  • Rhodium is used either as a metal or as a compound. In metallic form, it is used either as finely divided particles or deposited in a thin layer on a support such as activated carbon, calcium carbonate, aluminum silicate, alumina.
  • Suitable rhodium compounds are salts of aliphatic mono- and polycarboxylic acids, such as rhodium 2-ethylhexanoate, rhodium acetate, rhodium oxalate, rhodium propionate or rhodium malonate.
  • Rhodium salts of inorganic hydrogen and oxygen acids such as rhodium nitrate or rhodium sulfate, the various rhodium oxides or rhodium carbonyl compounds such as Rh 3 (CO) ⁇ 2 or Rh 6 (CO) ⁇ 6 or complex compounds of rhodium, for example cyclopentadienylrhodium compounds or rhodium acetylacetonate, can also be used , Rhodium halogen compounds are less suitable because of their corrosive behavior of the halide ions.
  • Rhodium oxide and in particular rhodium acetate and rhodium 2-ethylhexanoate are preferred.
  • Rhodium metal and the rhodium compounds suitable for catalyst production for the second reaction stage can also be used for catalyst production in the first reaction stage.
  • the catalyst is usually formed from the components rhodium or rhodium compound, the diphosphine or the diphosphines of the general formula I and synthesis gas under the conditions of the hydroformylation reaction in the reaction mixture. However, it is also possible to first preform the catalyst and then to feed it to the actual hydroformylation stage.
  • the preforming conditions generally correspond to the hydroformylation conditions.
  • the crude aldehyde of the first reaction stage is passed in countercurrent to a fresh synthesis gas in a stripping column.
  • heat is transferred from the aldehyde to the synthesis gas and the olefinic compound dissolved in the aldehyde is expelled from the crude product and returned to the reaction together with the heated synthesis gas.
  • the implementation can be carried out batchwise or continuously.
  • the reaction product of the second reaction stage is distilled off from the catalyst. It can be combined with the product of the first stage and further processed, for example distilled.
  • the catalyst-containing distillation residue of the second stage is returned to the second hydroformylation stage.
  • the reaction of the olefinically unsaturated compounds contained in the exhaust gas stream in the second reaction stage in the presence of the rhodium-diphosphine complex compounds according to the invention gives the desired linear aldehydes with excellent selectivity. Furthermore, the catalyst system used according to the invention in the second hydroformylation stage is distinguished by a long catalyst service life.
  • the second stage is generally carried out to a partial conversion in order to ensure a high selectivity for the straight-chain aldehydes and to avoid excessive damage to the catalyst and excess ligand.
  • the new process makes it possible to convert olefinically unsaturated compounds into the linear aldehydes with high selectivity and excellent selectivity.
  • the new process opens up the possibility of the proportions of n- and iso-compounds adapt to the respective requirements in the reaction product via the overall process.
  • the ratio of n- and iso compound in the overall process can also be influenced by the addition of olefin to the exhaust gas mixture which is fed to the second hydroformylation stage.
  • suitable starting materials are both olefins having an internal and also a terminal double bond, and straight-chain and branched olefins.
  • the olefins can also contain functional groups, in particular those which are not changed in the course of the reaction.
  • Polyunsaturated compounds, such as 1, 3-butadiene or 1, 3 pentadiene, are also suitable as starting materials. Mixtures of olefinically unsaturated compounds with terminal and internal double bonds are also suitable.
  • the mixture of butene-1 and butene-2 available in the art also referred to as raffinate II, a butene-1-depleted raffinate II, which is also referred to as raffinate III, or an octene-2 and / or octene C 8 -olefin mixture containing 3 can be used as starting compound in the process according to the invention.
  • the process according to the invention is particularly suitable for the hydroformylation of olefinically unsaturated hydrocarbons having 4 to 12 carbon atoms.
  • Suitable olefinically unsaturated compounds are, for example, butene-2, mixtures containing butene-2 and butene-1, octene-3, undecene-3, hexene-2, heptene-3, dimeric butenes, trimerpropylene, technically available olefin mixtures such as Dimersol® or Octol®.
  • a further embodiment of the present invention relates to a process for the preparation of carboxylic acids, alcohols or amines from olefinically unsaturated compounds, the olefinically unsaturated compounds being hydroformylated by the process according to the invention and the aldehydes thus obtained being oxidized to carboxylic acids in a manner known per se, to give alcohols reduced or reductively aminated to amines.
  • the oxidation of the aldehydes obtained according to the invention from olefinically unsaturated compounds can be carried out in a conventional manner, for example by the oxidation of the aldehydes with atmospheric oxygen or oxygen in accordance with the methods, as described, for example, in Ullmann 's Encyclopedia of Industrial Chemistry, ⁇ . , Vol. A5, p. 239, VCH Verlagsgesellschaft, Weinheim, 1986.
  • the catalytic hydrogenation of the aldehydes obtained from olefinically unsaturated compounds by the process according to the invention to alcohols can be carried out in a manner known per se, for example by the processes of Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A1, p. 279, VCH publishing company, Weinheim, 1985 or GH Ludwig, Hydrocarbon Processing, March 1993, p.67.
  • the reductive amination of the aldehydes obtained from olefinically unsaturated compounds by the process according to the invention can be carried out in a manner known per se, for example according to 1985 from Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A2, S1, VCH Verlagsgesellschaft, Weinheim , Ammonia, primary CrC 2 o-amines or secondary C 2 -C 2 o-amines can be used as starting compounds for the production of amines.
  • the new process is particularly suitable for the hydroformylation of mixtures containing butene-1 and butene-2, which are used as refinery by-products in the manufacture of automotive fuels and in the manufacture of ethylene by thermal decomposition of higher hydrocarbons inevitably arise in considerable quantities. They are obtained from the C - crack cuts of the pyrolysis product by extraction of the butadiene with a selective solvent and subsequent separation of the isobutene, preferably by conversion to methyl tert-butyl ether.
  • the pyrolysis product freed from butadiene is referred to as raffinate 1. If isobutene is also removed, this is referred to as raffinate II.
  • butadiene instead of extracting the butadiene, it can also be partially hydrogenated to butenes in the C-crack cut.
  • a butene-1 / butene-2 mixture is obtained, which can be converted into n-valeraldehyde with high selectivity by the new process.
  • the first homogeneous hydroformylation stage is operated under conditions in which the butene-1 contained in the butene mixture is converted as far as possible to give n-valeraldehyde while the i-valeraldehyde formation is still largely absent.
  • the butene-1 conversion can be up to 95%, the valeraldehyde obtained after the first stage containing 90% and more n-valeraldehyde, while the rest is i-valeraldehyde.
  • unreacted olefin which mainly consists of butene-2 and which is often also referred to as raffinate III, is reacted in a homogeneous manner in the second stage in accordance with the new process.
  • the olefin conversions are up to 90%, the resulting aldehyde mixture containing up to 90% by weight of n-valeraldehyde.
  • a further embodiment of the process according to the invention consists in the production of C 10 -carboxylic acids and C-io alcohols from a butene Mixture containing 1 and butene-2, which is converted to Cs-aldehydes by the process according to the invention.
  • the combined Cs-aldehyde mixture of the first and second hydroformylation stages is first aldolized in a conventional manner in the presence of basic catalysts.
  • a pretreatment of the aldehydes eg a special cleaning, is not necessary.
  • Alkali carbonates or alkali metal hydroxides, in particular compounds of sodium or potassium and amines, preferably tertiary amines, such as triethylamine, tri-n-propylamine, tri-n-butylamine, are used as catalysts.
  • the reaction time is from a few minutes to several hours and is particularly dependent on the type of catalyst and the reaction temperature. Due to its higher reaction rate, mainly n-valeraldehyde aldolizes with itself or with isomeric valeraldehydes to decenals, but condensation of 2-methylbutanal or isoveraldehyde with each other completely disappears into the background. /
  • the aldehyde mixture obtained by condensation can either be partially reduced to decanal or completely to decyl alcohol.
  • the partial hydrogenation to the decanal and the subsequent oxidation with air or atmospheric oxygen to the decan carboxylic acid takes place in a known manner, for example analogously to the process for the preparation of 2-, known from Ulimann's Encyclopedia of Industrial Chemistry, 4th edition 1975, volume 9, p. ethylhexanoic.
  • the decan carboxylic acid obtained has a high content of 2-propylheptanoic acid.
  • phthalic acid is known, for example, from Ullmann, Encyclo Georg- der der Technische Chemie, 1979, Vol. 18, page 536 ff. It is expedient to react phthalic anhydride with the decyl alcohol mixture in a molar ratio of 1: 2 in one step.
  • the reaction rate can be increased by catalysts and / or by increasing the reaction temperature. In order to shift the equilibrium in the direction of the ester formation, it is necessary to remove the water formed from the reaction mixture.
  • raffinate III Reaction of the exhaust gas resulting from the first stage (hereinafter referred to as raffinate III) with a composition of 38.8% by volume of butanes, 3.9% by volume of 1-butene and 57% by volume of ice and trans 2-butenes 2,7- bis (3,3-dimethyl-butyl) -9,9-dimethyl-4,5-bis- (2,7-dimethyl-10-phenoxa-phosphino) xanthene (II) as a diphosphine ligand
  • raffinate II was hydroformylated analogously to the first stage of example 1 according to the invention.
  • the resulting exhaust gas with a composition of 38% by volume of butanes, 3.9% by volume of 1-butene and 57% by volume of ice and trans 2-butenes was then batch-processed in the second stage under unmodified high-pressure conditions at 250 bar and hydroformylated at 160 ° C.
  • Rhodium 2-ethylhexanoate served as the rhodium source and was pumped into the system as a concentrated solution (rhodium content approx. 5000 ppm in 2-ethylhexanol).
  • a butene-II mixture can be converted to the straight-chain aldehydes by the two-stage procedure according to the invention with a significantly higher selectivity than by the known procedure in which the second stage works under the known unmodified process under high pressure.
  • the diphosphines used according to the invention are also characterized by a long catalyst life.

Abstract

La présente invention concerne un procédé d'hydroformylation en deux étapes. Selon ledit procédé, la première étape est réalisée de manière homogène avec utilisation de catalyseurs complexes rhodium dissous, et les gaz rejetés sont alimentés dans une deuxième étape d'hydroformylation consistant à hydroformyler les composés à insaturation oléfinique contenus dans les gaz rejetés, dans le système de réaction homogène en présence de diphosphines sur la base de la structure xanthène.
PCT/EP2002/001379 2001-02-22 2002-02-09 Procede de fabrication d'aldehydes WO2002068371A1 (fr)

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WO2005042458A2 (fr) * 2003-10-21 2005-05-12 Basf Aktiengesellschaft Procede de production en continu d'aldehydes
RU2561171C1 (ru) * 2014-09-12 2015-08-27 Открытое акционерное общество "Нефтяная компания "Роснефть" Способ непрерывного двухступенчатого гидроформилирования олефинов с3, с4 и технологическая установка для его осуществления
CN105749969A (zh) * 2014-12-18 2016-07-13 中国科学院大连化学物理研究所 一种氢甲酰化固体催化剂的制备方法及催化剂和应用

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DE102009027978A1 (de) 2009-07-23 2011-01-27 Evonik Oxeno Gmbh Verfahren zur Herstellung von Decancarbonsäuren
DE102010041821A1 (de) 2010-09-30 2012-04-05 Evonik Oxeno Gmbh Einsatz von Supported Ionic Liquid Phase (SILP) Katalysatorsystemen in der Hydroformylierung von olefinhaltigen Gemischen zu Aldehydgemischen mit hohem Anteil von in 2-Stellung unverzweigten Aldehyden
SG11201502756PA (en) 2012-10-12 2015-05-28 Evonik Industries Ag Stable long-term method for producing c5-aldehydes
DE102013020320B4 (de) 2013-12-05 2019-04-04 Oxea Gmbh Verfahren zur Herstellung von 2-Methylbuttersäure mit einem vermindertem Gehalt an 3-Methylbuttersäure aus den bei der Herstellung von Pentansäuren anfallenden Nebenströmen
DE102013020322B4 (de) 2013-12-05 2019-04-18 Oxea Gmbh Verfahren zur Gewinnung von 2-Methylbutanal aus den bei der Herstellung von Gemischen isomerer a,ß-ungesättigter Decenale anfallenden Nebenströmen
DE102013020323B3 (de) 2013-12-05 2015-01-08 Oxea Gmbh Verfahren zur Herstellung von isomeren Hexansäuren aus den bei der Herstellung von Pentanalen anfallenden Nebenströmen
DE102013113724A1 (de) 2013-12-09 2015-06-11 Oxea Gmbh Verfahren zur Herstellung von Pentanderivaten und Derivaten alpha, beta-ungesättigter Decenale aus Propylen
DE102013113719A1 (de) 2013-12-09 2015-06-11 Oxea Gmbh Verfahren zur Herstellung von Pentanderivaten und Derivaten α,β-ungesättigter Decenale
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CN105749969A (zh) * 2014-12-18 2016-07-13 中国科学院大连化学物理研究所 一种氢甲酰化固体催化剂的制备方法及催化剂和应用
CN105749969B (zh) * 2014-12-18 2017-12-05 中国科学院大连化学物理研究所 一种氢甲酰化固体催化剂的制备方法及催化剂和应用

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