EP3068533A1 - Composition catalytiquement active immobilisée avec des ligands phosphorés tridentés dans un liquide ionique pour l'hydroformylation de mélanges contenant des oléfines - Google Patents

Composition catalytiquement active immobilisée avec des ligands phosphorés tridentés dans un liquide ionique pour l'hydroformylation de mélanges contenant des oléfines

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Publication number
EP3068533A1
EP3068533A1 EP14796126.2A EP14796126A EP3068533A1 EP 3068533 A1 EP3068533 A1 EP 3068533A1 EP 14796126 A EP14796126 A EP 14796126A EP 3068533 A1 EP3068533 A1 EP 3068533A1
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EP
European Patent Office
Prior art keywords
composition
composition according
aromatic
substituted
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP14796126.2A
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German (de)
English (en)
Inventor
Katrin Marie DYBALLA
Hanna HAHN
Robert Franke
Dirk Fridag
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Publication of EP3068533A1 publication Critical patent/EP3068533A1/fr
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    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • 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
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • 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
    • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
    • B01J2531/002—Materials
    • B01J2531/007—Promoter-type Additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • 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
    • B01J2531/827—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • the present invention is directed to a composition
  • a composition comprising: a) at least one support material; b) at least one metal selected from subgroup VIII of the Periodic Table of the Elements and c) at least one compound comprising the structural element of the formula (I):
  • the invention further comprises a process for the preparation of such a composition, the use of the composition as a catalytically active composition and a process for hydroformylation in which the composition is used as the catalytically active composition.
  • the object of the present invention is to develop a process which enables both a favorable catalyst removal by omitting a catalytically active composition which has one or more catalyst complexes on a support material as well as the addition of further components and at the same time an improved catalyst lifetime compared to having the systems described in the prior art.
  • the catalyst life for this catalytically active composition should be significantly improved, since a multiple catalyst change in the course of a year of operation for the above reasons would be uneconomical and unprofitable.
  • Anthracentriol-based ligand systems have heretofore been used in homogeneously catalyzed hydroformylation and have high n-selectivity and improved resistance to inherent catalyst poisons, e.g. Water from an aldol condensation of the aldehyde formed in the hydroformylation, on (DE 10 201 1 085 883 A1). However, it is desirable to heterogenize this system and thus allow for catalyst separation.
  • the object of the present invention was to provide a catalyst system for the hydroformylation of unsaturated compounds which has one or more of the desired properties as described above.
  • an object of the present invention to provide a method which allows both a favorable catalyst separation, as well as isomerization unsaturated compounds to hydroformylate n-terminal aldehydes and preferably at the same time has an improved catalyst life compared to the systems described in the prior art.
  • composition according to claim 1 which has a catalyst complex dissolved in an ionic liquid on a support material, the so-called SILP phase, wherein the complex has a tridentate phosphorus ligands.
  • the phosphorus-containing organic compounds used in the composition according to the invention which contain the above-mentioned structural element of the formula (I) - an anthracenetriol substructure - have the disadvantages described in the prior art, such as. In rhodium-catalyzed hydroformylation, ed. By P.W. N. M. van Leeuwen et C. Claver, Kluwer Academic Publishers 2006, AA Dordrecht, NL, pages 45-46. In comparison to the phosphites mentioned in the prior art, the composition of the invention by far the best catalyst life and is characterized by high stability.
  • compositions according to the invention and their use are described below by way of example, without the invention being restricted to these exemplary embodiments. Given subsequent ranges, general formulas, or compound classes, these should include not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by extracting individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their content, in particular with regard to the facts in connection with which the document was cited, should be included in full in the disclosure of the present invention. Percentages are by weight unless otherwise indicated. If mean values are given below, the weight average is, unless stated otherwise. If subsequently parameters are specified which were determined by measurement, the measurements were carried out, unless otherwise stated, at a temperature of 25 ° C. and a pressure of 101,325 Pa.
  • inert is understood to mean the property of substances, components or mixtures which are distinguished by the fact that there are no adverse effects or adverse effects on the intended course of the reaction.
  • composition according to the invention is characterized in that it comprises: a) at least one support material, which is preferably porous; at least one ionic liquid; at least one metal selected from the VIII. Subgroup of the Periodic Table of the Elements; at least one phosphorus-containing organic compound which has the structural element of the formula (I)
  • the compound having at least two OP bonds which may start from the same P 1 "or different P 1 "; in the case where the structural element (I) occurs twice in the compound, these are linked to one another via a C 10 -C 10 'carbon bond or via the following X 1 -G 1 -X 2 unit:
  • X 1 and X 2 may be independently selected; wherein Y 1 , Y 2 , Y 3 is selected from: hydrogen, unsubstituted or substituted aliphatic, unsubstituted or substituted aromatic hydrocarbon group;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are selected from: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group; F, Cl, Br, I, -OR 8 , -C (O) R 9 , -CO 2 R 1 °, -C0 2 M 1 , -SR 11 , -SOR 12 , -S0 2 R 13 , -S0 3 R 14 , -S0 3 M 2 ,
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are selected from: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic or heteroaromatic or condensed aromatic or condensed aromatic-heteroaromatic hydrocarbon group; -OR 17 ; wherein R 17 is selected from: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group; wherein two or more of R 1 to R 17 may be covalently linked together; wherein M 1 and M 2 are selected from: alkali metal, alkaline earth metal, ammonium, phosphonium, and wherein the meaning for M 1 and M 2 may be independently selected, e) optionally one or more organic amines.
  • carrier materials it is possible to use all known carrier materials, preferably porous carrier materials.
  • porous support materials are those which are inert with respect to the further constituents of the composition and the reaction partners and products of the reactions in which the compositions are used.
  • Preferred support materials are inorganic, preferably oxidic support materials. Particularly suitable as support materials are oxides of aluminum, silicon, titanium, zirconium or activated carbon or mixtures thereof, which may optionally have further elements.
  • Preferred support materials are for. As aluminosilicates, zeolites, Al 2 0 3 or silicon dioxide.
  • the support material particularly preferably comprises or consists of silicon dioxide.
  • the porous support material preferably has one or more of the following texture properties: i) mean pore diameter in a range from 1 to 423 nm; ii) pore volume in a range of 0.1 to 2 ml / g; iii) BET surface area in a range from 10 to 2050 m 2 / g, the determination of these values being carried out according to the Hg method according to DIN 66133 and the N 2 adsorption according to DIN 66131 and DIN 66135.
  • Preferred porous support materials have all of the surface parameters mentioned.
  • the porous carrier material has one or more of the following texture properties: i) average pore diameter in a range of 8 to 14 nm; ii) pore volume in a range of 0.9 to 1.1 ml / g; iii) BET surface area in a range of 300 to 400 m 2 / g
  • ionic liquids are liquids which are at a pressure of 101,325 Pa and a temperature of less than 100 ° C., preferably less than 50 ° C. and more preferably less than or equal to 25 ° C. in the liquid state present and have almost no measurable vapor pressure, as in Angew. Chem. Int. Ed. 2000, 39, 3772-3789. They are to be distinguished from inert solvents as used for the preparation of the composition according to the invention. As IL all ionic liquids can be used, which have the aforementioned properties.
  • Preferred ionic liquids used are those in which the anion is selected from the group comprising: tetrafluoroborate ([BF 4 ] “ ), hexafluorophosphate ([PF 6 ] “ ), dicyanamide ([N (CN) 2 ] “ ), bis (trifluoromethylsulfonyl) imide ([NTf 2 ] “ ), tricyanomethide ([C (CN) 3 ] " ), tetracyano borate ([B (CN) 4 ] “ ), halides (CI “ , Br “ , F “ ,), hexafluoroantimonate ([SbF 6 ] “ ), hexafluoroarsenate ([AsF 6 ] “ ), sulfate ([S0 4 ] 2 “ ), tosylate ([C 7 H 7 S0 3 ] “ ), triflate (CF 3 S0 3 " ), nonafiat ([C 4 F 9 S0
  • pyridine nucleus may be substituted with at least one group R na with n 2, which is selected from -C 6 alkyl, -C 6 alkoxy, CrC 6 - substituted aminoalkyl substituted aryl or C5-C12- substituted aryl-C 1 -C 6 -alkyl groups;
  • pyrazole nucleus may be substituted with at least one group R na with n
  • CrC 6 is selected from CrC - substituted aminoalkyl substituted aryl or C5-C12 aryl-substituted -C 6 alkyl groups;
  • the ionic liquid is particularly preferably selected from the group consisting of the following: a) 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, b) 1-butyl-3-methylimidazolium hexafluorophosphate, c) 1-butyl 3-methylimidazolium tetrafluoroborate.
  • composition according to the invention preferably comprises phosphorus-containing organic compounds having the structural element (II): where W is selected from:
  • G 2 and G 3 are each selected from: hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic or condensed aromatic or fused aromatic-heteroaromatic hydrocarbon group with any further substitution; F, Cl, Br, I, or -OR 18 , -C (O) R 19 , -CO 2 R 2 °, -CO 2 M 1 , -SR 21 , -SOR 22 , -SO 2 R 23 , -SO 3 R 24 , -S0 3 M 2 , -NR 25 R 26 ; wherein R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 are selected from: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group; -OR 27 ; wherein R 27 is selected from: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group; F,
  • R 28 , R 29 and R 30 may be independently selected and wherein R 28 and R 29 may be covalently linked together.
  • further preferred phosphorus-containing organic compounds have the structural element (III):
  • Z is G 4 or an X 1 -G 1 -X 2 unit, and G 4 is selected from: hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic or condensed aromatic or fused aromatic-heteroaromatic hydrocarbon group with any further substitution; F, Cl, Br, I, or -OR 31 , -C (O) R 32 , -CO 2 R 33 , -C0 2 M 1 , -SR 34 , -SOR 35 , -S0 2 R 36 , -S0 3 R 37 , -S0 3 M 2 , -NR 38 R 39 , wherein R, R, R, R, R ib, R, R, R, R are selected d9 of: hydrogen, the unsubstituted or substituted te, linear or branched, aliphatic or aromatic hydrocarbon group; -OR 40 ; wherein R 40 is selected from: hydrogen, unsubstituted or substituted, linear or branched, ali
  • composition according to the invention further preferred phosphorus-containing organic compounds have the structural element (IV):
  • G 5 and G is selected from: hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic or condensed aromatic or fused aromatic-heteroaromatic hydrocarbon group with any further substitution; F, Cl, Br, I, or -OR 41 , -C (O) R 42 , -C0 2 R 43 , -C0 2 M 1 , -SR 44 , -SOR 45 , -S0 2 R 46 , -S0 3 R 47 , -S0 3 M 2 , -NR 48 R 49 ,
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 are selected from: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group; -OR 50 ; wherein R is selected from: hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group; wherein M 1 and M 2 is selected from: alkali metal, alkaline earth metal, ammonium, phosphonium, and wherein the meaning for M 1 and M 2 may be independently selected, wherein the meaning of G 5 and G 6 may be independently selected, and G 5 and G 6 may be covalently linked together.
  • W stands for a P '"(G 2 ) (G 3 ) group.
  • X 1 , X 2 O.
  • G 1 comprises a bisarylene group with any further substitution.
  • G 1 comprises the structural element (V):
  • G 2 and G 3 are preferably covalently linked to one another.
  • linkages G 2 -G 3 have the following structural element (VI):
  • linkage G 5 -G 6 has the following structural element (VII):
  • the P '''(G 2 ) (G 3 ) group corresponds to the structural formula of the P m (G 5 ) (G 6 ) group.
  • the phosphorus-containing organic compound is:
  • the composition of the invention comprises an organic amine.
  • the organic amine used comprises at least one residue with a 2,2,6,6- etramethylpipendinmaschine according to formula
  • the organic amine in the composition according to the invention is particularly preferably selected from the compounds of the formulas (Ea) - (Eh):
  • the metal is preferably selected from: cobalt, rhodium, iridium, ruthenium, in particular rhodium.
  • composition of the invention may be prepared in any known manner by mixing the components.
  • the composition according to the invention is preferably prepared by the process according to the invention described below or can be obtained thereby.
  • the process according to the invention for the preparation of the composition according to the invention is characterized in that it comprises the steps of: i) preparing a precursor of at least one compound of a metal from subgroup VIII of the Periodic Table of the Elements; ii) contacting at least one compound of a metal from subgroup VIII of the Periodic Table of the Elements with a molar excess of at least
  • steps i) to iv) are carried out in any desired sequence and wherein preferably in step i) at least one compound of a metal from subgroup VIII can be initially charged in an inert solvent.
  • the composition of the invention can be used as a catalytically active composition.
  • the composition of the invention is used as a catalytically active composition in a process for the hydroformylation of unsaturated compounds or mixtures thereof.
  • the process according to the invention for the hydroformylation of unsaturated compounds is accordingly distinguished by the fact that a composition according to the invention is used as the catalytically active composition.
  • the process according to the invention for the hydroformylation of unsaturated compounds preferably uses a fixed bed reactor.
  • the unsaturated compounds are preferably selected from C 2 -C 4 -olefins and their technical mixtures, such as, for example, as raffinate streams-raffinate I, II, or III-in the preparation and further processing in the petrochemical industry, in particular ethene, propene, Butenes or mixtures containing these compounds.
  • the final subject of the present invention is a multiphase reaction mixture comprising:
  • Synthesis gas consisting of a mixture with a volume fraction of 1 to 1 of hydrogen and carbon monoxide (> 99.97%).
  • the technical C4 blends have the following compositions: Table 1
  • butane [a] GC area in% (Agilent Technologies column length 50 m, inside diameter 0.32 mm, film thickness 0.5 ⁇ , carrier gas helium, detector: FID, evaporator temperature 473.15 K, split ratio 33.5: 1, constant column flow helium 91, 6 ml min "1 , detector temperature 523.15 K, heating ramp: initial temperature 323.15 K, holding time 15 min, heating to 473.15 K at 25 K min " 1 , holding time 40 min, total time per Measurement 61 min)
  • a degree of loading ⁇ is set such that it has a Value of 0.1 or 10 vol .-% assumes.
  • a degree of loading ⁇ is the ratio of the volume under normal conditions of the ionic liquid IL used in each case to the pore volume of the carrier material used in each case.
  • the reactant gas stream was homogenized before it flowed through the tube reactor and catalyst bed from above.
  • the reactor was made of stainless steel (diameter 12 mm, length 390 mm) and had on the output side a grid for the positioning of the catalyst material. Through an internal thermocouple, the temperature could be recorded in the catalyst bed.
  • the total pressure in the pilot plant was regulated by means of an electronic pressure maintenance valve (source: Samson). On the low-pressure side of the product gas flow was divided using a valve, so that only a small portion of the total flow to the on-line gas chromatograph (source Agilent, model 6890) was passed. The larger portion was passed directly into a product barrel. Samples of the product gas stream were injected into the gas chromatograph through a valve at regular intervals. The data analysis was carried out by the ChemStation software from Agilent.
  • the product gas composition during the experimental run was analyzed on an online gas chromatograph.
  • the gas chromatograph was equipped with a dimethyl polysiloxane-coated column (Agilent Technologies, length 50 m, inner diameter 0.2 mm, film thickness 0.5 ⁇ m) and a flame ionization detector (FID).
  • Set measurement parameters injector temperature 423.15 K, split ratio 33.5: 1, constant column flow helium 74 ml min "1 , detector temperature 523.15 K, heating ramp: initial temperature 323.15 K, holding time 15 min, heating to 473.15 K with 25 K min "1 , holding time 40 min, total time per measurement 61 min.
  • the catalytically active composition Rh- (17) shows n / iso selectivities of on average> 85% (see Figure 1) with a conversion of> 12%.
  • n / iso selectivities of on average> 85% see Figure 1
  • a significantly longer catalyst life of over 2000 h can be observed at 120 ° C. than for other SILP catalyst systems.
  • the course of the reaction of the catalytically active composition Rh- (17) shows only a creeping decline in the conversion from about 650 h experimental period.
  • the catalytically active composition based on Rh- (17) was modified by the optional addition of at least one organic amine.
  • organic amine commercially available sebacic acid di-4 (2,2,6,6-tetramethylpiperidinyl) ester was used.
  • FIG. 2 shows that the conversion was increased over an average reaction time of more than 1300 h to 36% by adding sebacic acid di-4 (2,2,6,6-tetramethylpiperidinyl) ester; In comparison, the conversion without this optional addition is only 12%, as shown in Figure 1. Also, by the optional addition of at least one organic amine, preferably sebacic di-4 (2,2,6,6-tetramethylpiperidinyl) ester, the yield of target product of the same order of magnitude can be improved. This is all the more surprising because the composition of the invention without the addition of the organic amine contains a lower proportion of rhodium: As usual in heterogeneous catalysis, the proportion of catalytically active metal is given in relation to the support mass.
  • the rhodium composition per support material is identical (0.2% by weight) in both compositions according to the invention (with and without stabilizer), but the proportion of rhodium per composition according to the invention is 30% lower in the case of the added amine.
  • Table 2 discloses that, for example, the space-time yield of n-pentanal is increased by an average of 139.5 kg m "3 h " 1 compared to a space-time yield of only 52.2 kg m "3 h " 1 without this optional addition of an amine can.
  • the space-time yield (RZA) is calculated as the ratio of the mass flow of the aldehydes formed and the bulk volume of the composition according to the invention. Especially for large-scale continuously operated processes, a high space-time yield is desirable.
  • a composition according to the invention with a high space-time yield is equivalent to a higher production capacity, ie smaller reaction vessel size and thus better heat removal and additionally lower bound capital due to reduced catalyst volume and cost compared to a composition with a lower space-time yield.
  • the present invention now shows a way in which a hydroformylation reaction using the composition according to the invention, which is based on tridentate, anthracene triol-based ligands, can be carried out with long-term stability by the optional addition of at least one organic amine in the process according to the invention for i 5 hydroformylation ,
  • long-term stable reaction times in the order of 900 to 2200 h are to be regarded.
  • DE 10 201 1085883 A1 it was therefore surprising that, in contrast to a homogeneously conducted hydroformylation, the optional addition of at least one organic amine is now possible in a SILP catalyst system as part of a heterogeneously carried out hydroformylation
  • the in the Table 2 shows an increase by a factor of 2.7 in a hydroformylation of technical C4 mixtures compared to a composition of a SILP catalyst system without corresponding addition.
  • the use of the composition according to the invention in the process according to the invention for the hydroformylation has a reduced rhodium requirement compared to the process procedure without optional addition of at least one organic amine.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne une composition comprenant : a) au moins un matériau de support; b) au moins un liquide ionique, c) au moins un métal sélectionné dans le VIIIe sous-groupe du tableau périodique des éléments; d) au moins un composé organique contenant du phosphore, lequel présente l'élément de structure de la formule (I), et e) en option, une ou plusieurs amines organiques. L'invention concerne en outre un procédé de fabrication d'une telle composition, l'utilisation de la composition comme composition catalytiquement active ainsi qu'un procédé d'hydroformylation dans lequel la composition est utilisée comme composition catalytiquement active.
EP14796126.2A 2013-11-14 2014-11-11 Composition catalytiquement active immobilisée avec des ligands phosphorés tridentés dans un liquide ionique pour l'hydroformylation de mélanges contenant des oléfines Withdrawn EP3068533A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013223228.4A DE102013223228A1 (de) 2013-11-14 2013-11-14 Immobilisierte katalytisch aktive Zusammensetzung mit tridentaten Phosphorliganden in einer ionischen Flüssigkeit zur Hydroformylierung von olefinhaltigen Gemischen
PCT/EP2014/074281 WO2015071266A1 (fr) 2013-11-14 2014-11-11 Composition catalytiquement active immobilisée avec des ligands phosphorés tridentés dans un liquide ionique pour l'hydroformylation de mélanges contenant des oléfines

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DE102013217174A1 (de) 2013-08-28 2015-03-05 Evonik Industries Ag Zusammensetzung und deren Verwendung in Verfahren zur Hydroformylierung von ungesättigten Verbindungen
DE102013225883A1 (de) 2013-12-13 2015-06-18 Evonik Industries Ag Zweistufige Hydroformylierung mit Kreisgas- und SILP-Technologie
CN113385234B (zh) * 2021-01-12 2022-05-24 杭州师范大学 一种催化剂体系及其制备己二胺的方法
CN113694969B (zh) * 2021-04-26 2022-12-16 河南平煤神马尼龙工程技术有限公司 一种催化剂体系及其催化合成1，6-己二胺的方法

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US4789753A (en) 1984-02-17 1988-12-06 Union Carbide Corporation Phosphite ligands
CN1163463C (zh) 1998-12-10 2004-08-25 三菱化学株式会社 醛的制备方法
DE102006058682A1 (de) 2006-12-13 2008-06-19 Evonik Oxeno Gmbh Bisphosphitliganden für die übergangsmetallkatalysierte Hydroformylierung
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
DE102011085883A1 (de) 2011-11-08 2013-05-08 Evonik Oxeno Gmbh Neue Organophosphorverbindungen auf Basis von Anthracentriol

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