EP2986376A1 - Composition catalytiquement active immobilisée, pour l'hydroformylation de mélanges contenant des oléfines - Google Patents

Composition catalytiquement active immobilisée, pour l'hydroformylation de mélanges contenant des oléfines

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Publication number
EP2986376A1
EP2986376A1 EP14721242.7A EP14721242A EP2986376A1 EP 2986376 A1 EP2986376 A1 EP 2986376A1 EP 14721242 A EP14721242 A EP 14721242A EP 2986376 A1 EP2986376 A1 EP 2986376A1
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EP
European Patent Office
Prior art keywords
hydroformylation
olefin
catalyst
aldol
reaction
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.)
Withdrawn
Application number
EP14721242.7A
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German (de)
English (en)
Inventor
Katrin Marie DYBALLA
Robert Franke
Hanna HAHN
Marc Becker
Andreas SCHÖNWEIZ
Jonas DEBUSCHEWITZ
Simon Walter
René WÖLFEL
Marco Haumann
Peter Wasserscheid
Andre KAFTAN
Mathias LAURIN
Jörg LIBUDA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
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Evonik Degussa GmbH
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Publication date
Priority claimed from PCT/EP2013/075833 external-priority patent/WO2014169975A1/fr
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Priority to EP14721242.7A priority Critical patent/EP2986376A1/fr
Publication of EP2986376A1 publication Critical patent/EP2986376A1/fr
Withdrawn legal-status Critical Current

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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
    • B01J31/1616—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
    • 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
    • B01J31/16—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
    • B01J31/2447—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 substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—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 substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B01J31/2457—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 substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • 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
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • 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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/30—Non-coordinating groups comprising sulfur
    • B01J2540/32—Sulfonic acid groups or their salts

Definitions

  • the present invention provides a composition and the use of this composition as a catalytically active composition in processes for the synthesis of chemical compounds, in particular the hydroformylation of olefinically unsaturated hydrocarbon mixtures.
  • Aldehydes in particular linear aldehydes such as butyraldehyde, valeraldehyde, hexanal or octanal have technical significance as starting materials for plasticizer alcohols, surfactants, and fine chemicals.
  • Catalysts which are generally used in the hydroformylation reaction are, in particular, rhodium and cobalt compounds in the presence of ligand. the. Homogeneously dissolved rhodium-based organometallic catalysts are nowadays used in the hydroformylation processes since, in contrast to the cobalt-based processes, significantly milder reaction conditions can be chosen (see: H.-W. Bohnen, B. Cornils, Adv. Catal , 47, 1).
  • hydroformylation of olefins using rhodium-containing catalyst systems is carried out essentially according to two basic variants.
  • the Ruhrchemie / Rhone-Poulenc process the catalyst system consisting of rhodium and a water-soluble ligand, usually alkali metal salts of sulfonated phosphines, dissolved in an aqueous phase.
  • the educt-product mixture forms a second liquid phase.
  • the two phases are mixed by stirring and by synthesis gas and olefin, if gaseous, flows through.
  • the separation of the educt product mixture from the catalyst system is carried out by phase separation.
  • the separated organic phase is worked up by distillation (see: C.W. Kohlpaintner, R.W. Fischer, B. Cornils, Appl. Catal. A Chem. 2001, 221, 219).
  • the rhodium-containing catalyst system is homogeneously dissolved in an organic phase. Synthesis gas and feed olefin are introduced into this phase.
  • the reaction mixture withdrawn from the reactor is separated by, for example, distillation or membrane separation into a product-starting phase and a high-boiling phase containing the rhodium-containing catalyst system dissolved.
  • the rhodium catalyst system containing phase is recycled to the reactor, the other phase is worked up by distillation (see: K.-D. Wiese, D. fruit, Hydroformylation in: Catalytic Carbonylation Reactions; M. Beller (Ed.), Topics in Organometallic Chemistry 18, Springer, Heidelberg, Germany, 2006, 1).
  • Hydroformylation produces high boilers. For the most part, these are aldol addition or aldol condensation products from the aldehydes formed. To ensure that the high-boiling point concentration in the reactor remains limited, it is necessary to discharge a partial flow, if possible one, in which the high boilers are concentrated.
  • This substream contains rhodium compounds. To keep the rhodium losses small, rhodium must be recovered from this effluent stream. The rhodium separation from such streams is not complete and expensive. Further rhodium losses occur through clustering of rhodium. These rhodium clusters are deposited on device walls and possibly form alloys with the device materials. These amounts of rhodium are no longer catalytically active and can be recovered only after the shutdown of the plant very expensive and only partially.
  • Supported Aqueous Phase (SAP) concept see H. Delmas, U. Jaeuregui-Haza, A.-M. Wilhelm, Supported Aqueous Phase Catalysis as the Alternative Method in: Multiphase Homogeneous Catalysis, B. Cornils, WA Herrmann, IT Horväth, W. Leitner, S. Mecking, H. Olivier-Bourbigou, D.
  • Supported Liquid phase (SLP) concept is another concept for the heterogenization of homogeneous catalyst complexes:
  • SLP Supported Liquid phase
  • TPP Triphenylphosphine
  • a problem with a very large ligand excess in the case of the catalyst systems considered is the formation of various transition metal complexes, which may result in suppression of the catalytic activity.
  • SILP catalyst systems The most promising development so far is the hydroformylation of olefins to aldehydes by means of so-called supported-ionic-liquid-phase, in short called SILP catalyst systems.
  • catalytically active compositions in a multiphase system consisting of a solid, inert, porous support material that is ionic Liquid is enveloped - the so-called SILP phase - in which the transition metal, in particular rhodium containing catalyst is included.
  • Catalyst recycling in particular - combined with product separation - and ligand stability play a crucial role - not only in view of the high rhodium and ligand prices, but also of only slightly known ones Influence of Impurities from Ligand Degradation Processes on Activity and Product Spectrum.
  • a disadvantage of the described SILP process here is the use of the ionic liquid, called IL for short; the long-term toxicity of these ionic liquids is z.T. still unclear or it has been found that some possible cations and anions are ecotoxic. For example, longer alkyl chains exhibit aquatoxicity. Two further problems are the still high production costs and the lack of resistance to higher temperatures in many ionic liquids.
  • Ionic liquids consist exclusively of ions (anions and cations).
  • ionic liquids are salt melts with low melting points. In general, not only the liquid compounds which are liquid at ambient temperature but also all salt compounds melting below 100 ° C. are included.
  • inorganic salts such as common salt (melting point 808 ° C) are reduced in ionic liquids by charge delocalization, lattice energy and symmetry, which can lead to solidification points below -80 ° C. (Römpp Chemie Lexikon)
  • molten salts is that ionic liquids normally contain organic cations instead of inorganic cations.
  • Ligand deactivation and degradation result in less active ligand being present in the system, which may adversely affect the performance of the catalyst (conversion, yield, selectivity).
  • 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 heterogeneous support, as well as the addition of further components.
  • the addition of an IL should become superfluous. This can, on the one hand, save costs for the synthesis of the IL or its procurement. the; on the other hand, the introduction of catalyst poisons such as water via the IL can be avoided.
  • a further object was to develop a method which allows both a favorable catalyst separation, as well as a shortening of the dynamic process of pore filling and the adjustment of the stationary equilibrium state between condensation and evaporation.
  • Composition comprising:
  • thermodynamic model In process development, simulation tools based on a thermodynamic model are used.
  • the substance data method NRTL-RK is used.
  • This is an activity coefficient model (g E model) for the description of the liquid phase.
  • the vapor phase is described by a state equation; in this case with the Redlich-Kwong state equation, which describes the vapor phase well up to medium pressures.
  • the behavior of multicomponent systems is predicted from information from the binary systems in the NRTL model.
  • the vapor pressure curves of the pure substances are calculated using the extended Antoine equation.
  • the parameters, which were adapted to measurement data, were taken from AspenPlus ⁇ Version 7.3.
  • the inert porous support material has the texture properties:
  • the phosphorus-containing organic compounds are selected from phosphines, phosphites, phosphoramidites.
  • the phosphines are selected from:
  • the high boiling liquid is formed in-situ during use in a chemical synthesis process.
  • the high boiling liquid is formed in-situ during the hydroformylation of olefin-containing hydrocarbon mixtures.
  • the aldol compound in process step e) is selected from:
  • 2-Propyl-hept-2-enal (secondary product of butene hydroformylation, CAS 34880-43-8).
  • the phosphorus-containing organic compound from process step d) is selected from:
  • the inert, porous carrier material in method step b) is selected from:
  • Silicon dioxide aluminum oxide, titanium dioxide, zirconium dioxide, silicon carbide, coal, mixtures of these components.
  • the inert, porous carrier material in process step b) has the texture-poor properties:
  • pore volume in a range of 0.1 to 2 ml / g; iii) BET surface area in a range of 10 to 2050 m2 / g.
  • the olefin-containing hydrocarbon mixture is selected from the group comprising:
  • the reaction mixture is free of ionic liquids.
  • the metal, the phosphorus-containing organic compound and the aldol compound are first mixed in a separate vessel before they are introduced into the reaction vessel.
  • reaction vessel is meant the vessel in which the hydroformylation takes place. This may be, for example, a reactor.
  • the inert, porous carrier material is added to the mixture before the mixture is introduced into the reaction vessel.
  • the Kelvin equation describes the change in the vapor pressure of a pure substance at a curved gas / liquid interface versus a saturated vapor pressure of a non-curved surface, as defined by an incompressible liquid and an ideal gas as the gas phase.
  • Equation 1 describes the saturation vapor pressure over a curved surface, p s the saturation vapor pressure over a non-curved surface, ⁇ the interfacial tension, M the molar mass, R the universal gas constant, T the temperature, 5 / the density of the liquid and r Pore den Radius of the pore.
  • the interfacial tension ⁇ can be determined using an empirically determined Brock and Bird formula (BE Poling, JM Prausnitz, JP O'Connell, Surface Tension: The Properties of Gases and Liquids, McGraw-Hill, USA, 2001, 691) based on the critical parameters of the liquid are calculated (see Equation 2 and 3). Equation 2
  • Equation 3 p c or T c describe the critical pressure or temperature, T S p describes the boiling point of the liquid phase.
  • FIG. 1 Time-resolved operando DRIFTS spectra of CO vibration regions at selected times between 30 minutes and 96 hours: (a) Range between 1950-2200 cm -1 ; (b) Range between 1600-1800 cm -1 ; and (c) time course of the signal intensities from (a); and (d) time course of the signal intensities from (b).
  • IR signals were recorded daily for approximately 16 hours over a total experimental run time of 1 to 10 hours. In the empty regions of (c) and (d), the catalytic reaction continues to take place but could not be measured continuously due to equipment limitations.
  • FIG. 2 is a diagrammatic representation of FIG. 1
  • DRIFTS spectra obtained (i) operando after 96 h reaction; (ii) for silica 100 impregnated with pure aldol (E) -2-ethylhex-2-enal; (iii) for silica 100 impregnated with pure iso-butanal; and (iv) for silica 100 impregnated with pure n-butanal.
  • FIG. 3 is a diagrammatic representation of FIG. 3
  • FIG. 4 is a diagrammatic representation of FIG. 4
  • FIG. 5 is a diagrammatic representation of FIG. 5
  • FIG. 6 is a diagrammatic representation of FIG. 6
  • FIG. 7 is a diagrammatic representation of FIG. 7
  • thermodynamic model In process development, simulation tools based on a thermodynamic model are used.
  • the substance data method NRTL-RK is used.
  • This is an activity coefficient model (g E model) for the description of the liquid phase.
  • the vapor phase is described by a state equation; in this case with the Redlich-Kwong state equation, which describes the vapor phase well up to medium pressures.
  • the behavior of multicomponent systems is predicted from information from the binary systems in the NRTL model.
  • the vapor pressure curves of the pure substances are calculated using the extended Antoine equation.
  • the parameters, which were adapted to measurement data, were taken from AspenPlus ⁇ Version 7.3.
  • Table 1 Vapor pressure as a function of the temperature of aldol compound in process step e).
  • Table 2 shows the physicochemical data for n-pentanal (hydroformylation product of a C4-olefin).
  • the inert, porous support material and the substrate to be hydroformylated such as olefins or olefin-containing hydrocarbon mixtures varies.
  • High-boiling compounds can be characterized by the fact that they are estimated according to Equation 1 (considering that Equation 1 by definition does not apply to complex mixtures) or via a substance data model (Substance Data Method NRTL-RK, AspenPlus ⁇ Version 7.3), a lower vapor pressure relative to the having average pore diameter of the support material, as the product formed in the reaction aldehyde.
  • a substance data model Subjectstance Data Method NRTL-RK, AspenPlus ⁇ Version 7.3
  • FIG. 1 b shows a significant adsorption band at 1723 cm -1 and another at 1670 cm -1 .
  • the Intensity of the band at 1723 cm “1 increases rapidly and reaches a stationary state after 6 h, whereas the band at 1670 cm “ 1 can only be observed after a reaction time of 6 h and its intensity increases over the entire duration of the experiment (see FIG. FIG. 1 d).
  • the CH and CO stretching ranges are compared for the following systems: (i) A selected spectrum from the above-mentioned Operando experiment, and (ii-iv) the pure aldehyde and aldol products immobilized on calcined silica 100.
  • the operando spectrum shows the greatest similarity with the spectrum of pure n-butanal (iv).
  • the spectra of 2-ethylhex-2-enal (ii) and / ' so-butanal (iii) show no particular features that would allow a concrete distinction.
  • the catalyst performance shown can be divided into 3 phases: within the first 6 hours the catalyst shows a distinct behavior activation (Phase 1), wherein the change revenues and n // 'so selectivity time strong. Between 6 h and 30 h run time (Phase 2), the changes are much less pronounced and the regioselectivity reaches a stable level, although the catalyst activity is still slightly increasing. A constant level is reached after 30 h both for the propene and for the n // 'selectivity so that continually does not change significantly (Phase 3).
  • the macroporous silicon dioxide is in each case as Trisopor® 423 (particle size 100 to 200 ⁇ , BET surface area in the range of 10 - 30 m 2 / g, average pore diameter 423 nm) of VitroBio GmbH or as silica 100, as for example for preparative column chromatography is used, commercially available.
  • the activated carbon used is commercially available (particle size 500 ⁇ , BET surface area in the range of 2000 - 2010 m 2 / g) and comes from Blücher GmbH.
  • the macroporous silica - Trispor® 423 - as well as silica 100 was each calcined at 873.15 K for 18 hours prior to use to prepare the catalytically active composition.
  • Ethene (99.95%), propene (99.8%), carbon monoxide (99.97%) and hydrogen (99.999%) were purchased from Linde AG.
  • 2-Methyl-2-pentenal (97%) was purchased from Sigma Aldrich.
  • 2-Propyl-2-heptenal was prepared according to a literature procedure by base catalyzed aldol reaction of freshly purified n-pentanal. The formed aldol products were separated by subsequent distillation to obtain a high purity of 2-propyl-2-heptenal.
  • the reactor was made of stainless steel (diameter 12 mm, length 500 mm) and had on the exit side a porous frit for the positioning of the catalyst material. Through an internal thermocouple, the temperature could be recorded in the catalyst bed. A 7 ⁇ filter after the reactor additionally prevented unwanted discharge of catalyst material.
  • 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 stream was divided using a needle valve, so that only a small portion of the total flow to the on-line gas chromatograph (source Agilent, Model 7890A) was passed. The larger proportion was passed directly into the exhaust air. Through a 6-port valve with a 1 ml sample loop, samples of the product gas stream were injected into the gas chromatograph 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 GS GasPro capillary column (Agilent Technologies, length 30 m, internal diameter 0.32 mm) and a flame ionization detector (FID).
  • Set measurement parameters injector temperature 523.15 K, split ratio 10: 1, constant column flow helium 4.5 ml min "1 , detector temperature 533.15 K, heating ramp: initial temperature 533.15 K, holding time 2.5 min, heating to 473 , 15 K with 20 K min "1 , holding time 4 min, total time per measurement 10 min.
  • Headspace GC / MS analyzes were performed on a Varian 450 gas chromatograph combined with Varian 220-MS mass spectrometer.
  • a Combi PAL GC autosampler (source: Fa. CTC Analytics) with heatable, gas-tight syringe and heatable shaker was used.
  • 0.5 g of the catalyst material to be examined was placed in a headspace vial and heated to 403.15 K for 15 min.
  • 500 ⁇ gas samples were injected into the GC.
  • a Fac- torFour VF-5 ms capillary column source Fa. Varian, length 30 m, internal diameter 0.25 mm
  • the ionization of the separated components was carried out by means of electron impact ionization.
  • Set measurement parameters injector temperature 523.15 K, split ratio 10: 1, constant column flow helium 1, 0 ml min "1.
  • Heating ramp initial tempera- heating 313.15 K, holding time 3.0 min, heating to 373.15 K with 5 K min -1 , holding time 10.5 min, heating to 473.15 K at 10 K min -1 , holding time 0.5 min, Total time per measurement 36 min.
  • a defined amount of corresponding high-boiling liquids such as aldol products, are already added; so-called aldol doping.
  • the amount of added aldol product corresponded to the weight gain measured on a previously tested catalyst with purely physisorbed rhodium-ligand species after a 70 hour experimental run.
  • the "aldol-doped" added high-boiling liquids during the preparation of the catalytically active composition
  • catalysts are more active and selective in terms of the spectrum of high-boiling compounds formed compared to materials without an initial addition of aldol these were the Rh-Sulfoxantphos (SX, 1) systems on the SiO2 carrier Trisopor 423 (Rh-1 / Trisopor423) and Rh-Xantphos (X, 2) on an activated charcoal carrier (Rh). 2 / activated carbon).
  • Integration of the peak areas provides a ratio of propanal / 2-methyl-2-pentenal and 2-methyl-2-pentanal / 2-methyl-2-pentenal of 9.7 and 0.1, respectively.
  • the ratios are 0.3 and 0.14, respectively.
  • the secondary component Ce ketone was not detected at all.Thus, it can be said that a targeted aldol doping on the one hand increase the activity of the supported catalyst and on the other hand can positively influence byproduct formation.
  • Table 3 Overview Characteristics of the catalyst systems tested: (1) maximum conversion during hydroformylation experiment, (2) mass change of the catalyst material used after complete test run time, (3 and 4) ratio of propanal / 2-methyl-2-pentenal or 2-methyl-2 pentanal (NK) / 2-methyl-2-pentenal according to GC / MS peak areas.
  • Rh-2 / activated carbon 1 -butene 0.9 5.2 n.b. n.d.
  • nb not determined
  • the high boilers thus formed condense to a certain degree in the interior of the pores.
  • the micropores and subsequently the larger pores are filled.
  • the originally physisorbed Hgand-modified rhodium complex then dissolves in this condensed aldol phase, thus providing a liquid phase for catalysis (immobilization of the ligand-modified rhodium complex) (see FIG. 7b).
  • the resulting reaction behaves like a classic reaction in organic solvents and has comparable n / iso selectivities. Since the proportion of the dissolved catalyst at the beginning of a long-term experiment is initially low, and the turnover is low when using macroporous supports. As the reaction progresses, it gradually forms more products, ie aldehydes, and due to subsequent reactions more aldol products, which in turn condense in the pores until an equilibrium between condensation and evaporation occurs under the given reaction conditions.
  • the degree of pore filling remains at a constant level that is characteristic of a given set of reaction parameters.
  • the characterization of the catalyst material was carried out with a Bruker Vertex 80v IR spectrometer equipped with an additional aluminum chamber in front of the sample chamber with the necessary feedthroughs to guide the optical path during the To be able to evacuate measurements.
  • DRIFTS diffuse Reflectance Fourier Transform Infrared Spectroscopy
  • Measurements were taken using Harrick's "Praying Mantis” accessories and HVC-DRP-4 high-temperature reaction chamber Modified with a type K thermocouple to measure the temperature directly in the powder during the reaction, Bronkhorst mass flow and pressure regulators were used to adjust the mass flow rates and pressures
  • the catalyst powder was removed under argon (5 mL min-1 2 bar) at 80 ° C for 3 h to remove water and solvent residues IR spectra were measured with a spectral resolution of 2 cm-1, 151 measurements per spectrum and a detection rate of 40 kHz, which corresponds to one measurement period 60 s per spectrum Simultaneously, online GC
  • the catalytic analysis in the tubular reactor was carried out in the structure previously described under catalysis experiments. The analysis used was taken over unchanged.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention a pour objet une composition et l'utilisation de cette composition, en tant que composition catalytiquement active, dans des procédés de synthèse de composés chimiques, en particulier pour l'hydroformylation de mélanges d'hydrocarbures oléfiniquement insaturés. De préférence, la composition renferme un complexe métallique, en particulier un complexe Rh, renfermant un ligand phosphane ou phosphite, sur un support poreux inerte, et elle est chargée, dans le but de l'hydroformylation, avec le produit secondaire aldol de l'aldéhyde souhaité, dans le sens d'une utilisation du concept « phase liquide supportée » (SLP).
EP14721242.7A 2013-04-19 2014-04-16 Composition catalytiquement active immobilisée, pour l'hydroformylation de mélanges contenant des oléfines Withdrawn EP2986376A1 (fr)

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EP14721242.7A EP2986376A1 (fr) 2013-04-19 2014-04-16 Composition catalytiquement active immobilisée, pour l'hydroformylation de mélanges contenant des oléfines

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DE102013207104 2013-04-19
PCT/EP2013/075833 WO2014169975A1 (fr) 2013-04-19 2013-12-06 Composition catalytiquement active immobilisée pour l'hydroformylation de mélanges contenant des oléfines
DE102014207246.8A DE102014207246A1 (de) 2013-04-19 2014-04-15 Immobilisierte katalytisch aktive Zusammensetzung zur Hydroformylierung von olefinhaltigen Gemischen
EP14721242.7A EP2986376A1 (fr) 2013-04-19 2014-04-16 Composition catalytiquement active immobilisée, pour l'hydroformylation de mélanges contenant des oléfines
PCT/EP2014/057793 WO2014170392A1 (fr) 2013-04-19 2014-04-16 Composition catalytiquement active immobilisée, pour l'hydroformylation de mélanges contenant des oléfines

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EP2986376A1 true EP2986376A1 (fr) 2016-02-24

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Non-Patent Citations (1)

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