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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
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
• • 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
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
  • B01J31/124—Silicones or siloxanes or comprising such units
  • B01J31/125—Cyclic siloxanes
• • 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
  • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
  • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
  • B01J31/1683—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins the linkage being to a soluble polymer, e.g. PEG or dendrimer, i.e. molecular weight enlarged complexes
• • 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
• • 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
  • B01J31/40—Regeneration or reactivation
  • B01J31/4015—Regeneration or reactivation of catalysts containing metals
  • B01J31/4061—Regeneration or reactivation of catalysts containing metals involving membrane separation
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
  • C07F15/0073—Rhodium compounds
  • C07F15/008—Rhodium compounds without a metal-carbon linkage
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/584—Recycling of catalysts

Definitions

• the hydroformylation of olefins and olefin-containing mixtures is a research topic of the chemical industry.
• a permanent problem in the case of catalytic hydroformylation is the maintenance of the activity and the selectivity of the catalytically active compositions used in each case in comparison with the olefins to be hydroformylated and olefin-containing mixtures under the reaction conditions.
• transition metal-containing, catalytically active compositions it is an object of research to at least significantly limit the inhibition of the catalytic activity, the formation of transition metal clusters and the failure of the transition metal itself.
• the present invention provides a contribution to this problem by providing a way in which, while avoiding thermal stress on the reaction mixture, the desired target products can be easily separated from the catalytically active composition while retaining its catalytic activity.
• An object of the present invention are POSS-modified ligands, wherein POSS are understood as meaning polyhedral oligomers silsesquioxane derivatives.
• the polyhedral oligomers silsesquioxane derivatives used are reacted with per se known ligand precursors.
• the resulting POSS-modified ligands have dramatically increased molecular weight compared to unmodified ligands.
• triphenylphosphine for example, alkylphenyl-substituted, in particular an ethylphenyl-substituted, POSS-substituted triphenylphosphine derivative are prepared: Si 8
• Another object of the present invention in the hydroformylation of olefins and olefin-containing mixtures catalytically active, transition metal-containing compositions obtainable by reacting the POSS-modified ligands with suitable transition metal precursors.
• Characteristic of these novel transition-metal complexes prepared in the catalytically active compositions with POSS-modified ligands is that the activity and selectivity for the non-POSS-modified transition metal complexes are maintained.
• the catalytically active compositions according to the invention are completely separable from the reaction mixture by means of organic nanofiltration and can be recycled to the hydroformylation reaction.
• the previously described POSS-substituted triphenylphosphine is reacted with a rhodium-containing, suitable transition metal precursor, such as e.g. B. [Rh (acac) (CO) 2], converted to the catalytically active composition.
• a rhodium-containing, suitable transition metal precursor such as e.g. B. [Rh (acac) (CO) 2]
• Another object of the present invention is the use of POSS-modified ligands in catalytically active compositions in the hydroformylation of olefins and olefin-containing mixtures.
• the above-described POSS-substituted triphenylphosphine is reacted with a rhodium-containing, suitable transition metal precursor, such as e.g. [Rh (acac) (CO) 2], converted to the catalytically active composition which in the hydroformylation of olefins, such.
• a rhodium-containing, suitable transition metal precursor such as e.g. [Rh (acac) (CO) 2]
• Example 1 Hydroformylation of 1-octene in a continuously operated membrane reactor
• the hydroformylation experiments were carried out in a continuously operated pilot plant; s. Plant sketch.
• This pilot plant consisted of a reaction part and a membrane part.
• the reaction section comprised a 100 mL autoclave b with a circulation pump c.
• the autoclave b was equipped with a pressure hold A for the synthesis gas. By this pressure A During the reaction, the synthesis gas pressure was kept constant throughout the system.
• the synthesis gas uptake of the system was determined by a flow measurement C.
• the reactor was equipped with a pressure burette a, which could be charged with syngas and thus allowed a dosage of the educt and catalyst solutions under reaction conditions.
• the autoclave b was also equipped with a level control B.
• the Eduktpumpe e was controlled, which then pumped from a template h Edukthus comprising the olefin-containing mixture, optionally solvent, in the autoclave b, so as to keep the state constant in the autoclave.
• This educt template h was covered with argon to avoid contact with air.
• the necessary turbulence in the autoclave was generated by the circulation pump c, which was specially designed for this application.
• the pump c built a loop of the reaction solution through a nozzle in the head of the autoclave b and thus provided for a corresponding gas / liquid exchange.
• the synthesis gas and the educt were also metered into the nozzle.
• a cross-flow chamber f was also installed.
• the cross flow chamber f separates the reaction part from the membrane part of the plant.
• the cross-flow chamber f ensures the mixing of the membrane circulation with the reactor discharge and ensured that the free gas fraction in the outlet of the reactor could not get into the membrane part, but was returned to the reaction cycle.
• the membrane part consisted of a pressure tube containing a ceramic membrane j of 200mm length with a specific filter area of 0.0217m2 / m and a cut-off of 450D, and a circulation pump g which created a loop across the membrane.
• the connection to the reaction part was realized via the already described cross flow chamber f.
• the permeate flow through the membrane j was realized by a pressure maintenance F on the permeate side.
• a pressure maintenance F on the permeate side.
• the preparation of the catalyst solution was carried out under an argon atmosphere. Subsequently, a differential pressure TMP of 0.35 MPa was set on the membrane j via the permeate pressure control F in order to remove the generated product i, aldehydes, from the system.
• Example 2 Hydroformylation of 1-Butene in a Continuously Operated Membrane Reactor The hydroformylation experiments were carried out in a continuously operated pilot plant; s. Plant sketch. This pilot plant consisted of a reaction part and a membrane part.
• the reaction section comprised a 1 00 mL autoclave b with a circulation pump c.
• the autoclave b was with a Pressure maintenance A equipped for the synthesis gas. Through this pressure A, the synthesis gas pressure was kept constant during the reaction throughout the system.
• the synthesis gas uptake of the system was determined by a flow measurement C.
• the reactor was equipped with a pressure burette a, which could be charged with syngas and thus allowed a dosage of the educt and catalyst solutions under reaction conditions.
• the autoclave b was also equipped with a level control B.
• the Eduktpumpe e was controlled, which then pumped from a template h Eduktsignificant comprising the olefin-containing mixture, optionally solvent, in the autoclave b, so as to keep the state constant in the autoclave.
• This educt template h was covered with argon to avoid contact with air.
• the necessary turbulence in the autoclave was generated by the circulation pump c, which was specially designed for this application.
• the pump c built a loop of the reaction solution through a nozzle in the head of the autoclave b and thus provided for a corresponding gas / liquid exchange.
• the synthesis gas and the educt were also metered into the nozzle.
• a cross-flow chamber f was also installed.
• the cross flow chamber f separates the reaction part from the membrane part of the plant.
• the cross-flow chamber f ensures the mixing of the membrane circulation with the reactor discharge and ensured that the free gas fraction in the outlet of the reactor could not get into the membrane part, but was returned to the reaction cycle.
• the membrane part consisted of a pressure tube which contained a ceramic membrane j of 200 mm length with a specific filter area of 0.0217 m 2 / m and a cut-off of 450 D, and a circulation pump g which generated a circulation across the membrane.
• the connection to the reaction part was realized via the already described cross flow chamber f.
• the permeate flow through the membrane j was realized by a pressure maintenance F on the permeate side.
• a pressure maintenance F on the permeate side.
• the preparation of the catalyst solution was carried out under an argon atmosphere. Subsequently, a differential pressure of 0.30 MPa was set on the membrane j via the permeate pressure control F in order to remove the generated product i, aldehydes, from the system.
• Raffinates such as. As raffinate I, raffinate II, but also mixtures containing olefins having 3 to 20 carbon atoms used.

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• 2010
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