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DE4413405C2 - Process for the preparation of polymeric catalyst supports based on silica gel and their doping with metal compounds - Google Patents

Process for the preparation of polymeric catalyst supports based on silica gel and their doping with metal compounds

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Publication number
DE4413405C2
DE4413405C2 DE19944413405 DE4413405A DE4413405C2 DE 4413405 C2 DE4413405 C2 DE 4413405C2 DE 19944413405 DE19944413405 DE 19944413405 DE 4413405 A DE4413405 A DE 4413405A DE 4413405 C2 DE4413405 C2 DE 4413405C2
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Germany
Prior art keywords
compounds
silica gel
doping
mixture
aromatic
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.)
Expired - Fee Related
Application number
DE19944413405
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German (de)
Other versions
DE4413405A1 (en
Inventor
Joachim Daub
Thomas Schlieper
Lutz-Steffen Berghold
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.)
BERGHOLD LUTZ STEFFEN
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BERGHOLD LUTZ STEFFEN
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Priority to DE19944413405 priority Critical patent/DE4413405C2/en
Publication of DE4413405A1 publication Critical patent/DE4413405A1/en
Application granted granted Critical
Publication of DE4413405C2 publication Critical patent/DE4413405C2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • 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
    • 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
    • B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
    • 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
    • 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
    • B01J31/1805—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 nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • 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
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • 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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • 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
    • B01J2531/842—Iron

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Darstellung eines mit organischen Polymeren derivatisierten Kieselgels zur Verwendung als Katalysator.The invention relates to a method for display one derivatized with organic polymers Silica gel for use as a catalyst.

Ein Verfahren, das einen Katalysatorträger mit N-haltigen Endgruppen synthetisiert, ist aus der US-PS 4,339,635 bekannt. Nach diesem bekannten Verfahren wird ein Perlpolymer, das aus 4-Vinylpyridin, Divinylbenzol und Methylmethacrylat besteht, synthetisiert und als Katalysatorträger eingesetzt.A process involving a catalyst support with N-containing End groups synthesized is from US Pat. No. 4,339,635 known. According to this known method, a Bead polymer consisting of 4-vinylpyridine, divinylbenzene and Methyl methacrylate consists, synthesized and as Catalyst carrier used.

Die US-PS 5,213,895 beschreibt ein Verfahren, das kolloidale Partikel aus Metallen oder Metallverbindungen stabil auf einem festen, mit Polymeren beschichteten Träger aufbringt. Der polymere Träger ist derart gestaltet, daß keine kovalenten Bindungen zwischen Träger und umhüllender Kunststoffschicht entstehen. Im wesentlichen werden hierbei Metallchloride mit (Poly-)N- vinyl-2-pyrrolidon (durchschnittliches Molekulargewicht: 10.000) in eine Organometallsuspension überführt, welche anschließend auf einem festen Träger, z. B. Aktivkohle getrocknet wird. U.S. Patent 5,213,895 describes a method that colloidal particles of metals or metal compounds stable on a solid, coated with polymers Applies carrier. The polymeric carrier is such designed that no covalent bonds between supports and enveloping plastic layer. in the Metal chlorides with (poly) N- vinyl-2-pyrrolidone (average molecular weight: 10,000) in an organometallic suspension, which then on a solid support, e.g. B. activated carbon is dried.  

In der WO 98/08500 A sind organische Beschichtungen von Kieselgel mit Hilfe von Naturstoffen wie Stärke, Zellulose, Agar, Albumin, u. a. beschrieben.WO 98/08500 A describes organic coatings from Silica gel with the help of natural substances such as starch, Cellulose, agar, albumin and the like. a. described.

Die vorliegende Erfindung betrifft ein Verfahren zur Synthese eines polymeren Katalysatorträgers auf Kieselgelbasis und deren Dotierung mit Metallkomplexen. Sie ist im Anspruch 1 angegeben, vorteilhafte weitere Verfahrensschritte in den Ansprüchen 2 bis 5.The present invention relates to a method for Synthesis of a polymeric catalyst support Silica gel base and its doping with metal complexes. It is specified in claim 1, advantageous others Process steps in claims 2 to 5.

Bevorzugte Verwendungen sind in den Ansprüchen 6 und 7 angegeben.Preferred uses are in claims 6 and 7 specified.

Gemäß der Erfindung werden zunächst Monomere mit polymerisationsaktiven Doppelbindungen, wie z. B. 4- Vinylpyridin, mit einem Kieselgel, das polymerisationsaktive Endgruppen besitzt, unter Zusatz eines Starters z. B. AIBN, in Chloroform bei einer Temperatur von 80-90°C polymerisiert.According to the invention, monomers are first used polymerization-active double bonds, such as. B. 4- Vinyl pyridine, with a silica gel that has polymerization-active end groups, with addition a starter z. B. AIBN, in chloroform at a Polymerized temperature of 80-90 ° C.

Der auf diese Weise synthetisierte Katalysatorträger wird zur Reinigung mit Toluol und danach mit 2-Propanol gewaschen.The catalyst support synthesized in this way becomes for cleaning with toluene and then with 2-propanol washed.

Die Dotierung des Polymerträgers mit einer Metallverbindung erfolgt in einem Lösungsmittel, indem der Polymerträger zunächst in diesem Lösungsmittel suspendiert wird und danach die Metallverbindung in fester oder gelöster Form zugegeben wird.The doping of the polymer carrier with a Metal compound is made in a solvent by the polymer carrier first in this solvent is suspended and then the metal compound in solid or dissolved form is added.

Vorteile dieses Verfahrens der Darstellung von Katalysatorträgern gegenüber dem bekannten Verfahren (US- PS 4,339,635):
Advantages of this method of producing catalyst supports compared to the known method (US Pat. No. 4,339,635):

  • - geringe Kosten bei der Wahl der Monomere- Low cost in the choice of monomers
  • - höhere Reaktivität des erfindungsgemäßen trägergebundenen Katalysators unter gleichen Bedingungen- Higher reactivity of the invention supported catalyst under the same conditions
  • - kleinere erreichbare Teilchengröße durch Wahl der Kieselgelkörner und somit Vergrößerung der Oberfläche (Durchmesser Perlpolymer 100 µm zu 5 µm beim Kieselgel)- Smaller achievable particle size by choosing the Grains of silica gel and thus enlargement of the surface (Diameter pearl polymer 100 µm to 5 µm for silica gel)

Speziell der Kostenvorteil ist auch gegenüber dem Verfahren nach der US-PS 5,213,895 gegeben.The cost advantage is also special compared to that Given method according to US Patent 5,213,895.

Zur Erläuterung der Erfindung sind nachfolgend mehrere Versuche aufgeführt:To explain the invention, there are several below Trials listed:

Beispiel 1example 1 Darstellung eines KatalysatorträgersRepresentation of a catalyst carrier

10 g Acrylkieselgel (Kieselgel mit Acryloylendgruppen), 5 µm Durchmesser wurden mit 8 ml (75,3 mmol) 4-Vinylpyridin in 60 ml CHCl3 3 h unter Argon auf 80-90°C erhitzt. Danach wurde abgekühlt und der Rückstand in (50 + 50) ml Toluol und danach in (50 + 50 + 50) ml 2-Propanol gewaschen.10 g of acrylic silica gel (silica gel with acryloyl end groups), 5 μm in diameter, were heated with 8 ml (75.3 mmol) of 4-vinylpyridine in 60 ml of CHCl 3 at 80-90 ° C. for 3 hours under argon. It was then cooled and the residue was washed in (50 + 50) ml toluene and then in (50 + 50 + 50) ml 2-propanol.

Beispiel 2Example 2 Dotierung des erfindungsgemäßen Katalysatorträgers mit TiCl4 Doping the catalyst support according to the invention with TiCl 4

In 50 ml Heptan wurden in einem Schienkrohr 3 g Träger­ material suspendiert und 2 ml (18 mmol) TiCl4 zugesetzt. Es wurde 1 h bei Raumtemperatur geschüttelt, danach die überstehende Lösung abdekantiert, der Kontakt mit Heptan gewaschen und bei 50°C im Vakuum getrocknet. In 50 ml of heptane, 3 g of carrier material were suspended in a Schienk tube and 2 ml (18 mmol) of TiCl 4 were added. The mixture was shaken at room temperature for 1 h, then the supernatant solution was decanted off, the contact was washed with heptane and dried at 50 ° C. in vacuo.

Beispiel 3Example 3 Dotierung des erfindungsgemäßen Katalysatorträgers mit FeCl3 Doping the catalyst support according to the invention with FeCl 3

In 50 ml Heptan wurden in einem Schlenkrohr 2,5 g Trägermaterial suspendiert und 1 g (6,2 mmol) FeCl3 zugesetzt. Es wurde 1 h bei Raumtemperatur geschüttelt, danach die überstehende Lösung abdekantiert, der Kontakt mit Heptan gewaschen und bei 50°C im Vakuum getrocknet.2.5 g of carrier material were suspended in 50 ml of heptane in a Schlenk tube and 1 g (6.2 mmol) of FeCl 3 was added. The mixture was shaken at room temperature for 1 h, then the supernatant solution was decanted off, the contact was washed with heptane and dried at 50 ° C. in vacuo.

Claims (7)

1. Verfahren zur Darstellung und Dotierung eines Katalysators auf Kieselgelbasis, dadurch gekennzeichnet, daß ein Gemisch aus
  • A) einer oder mehreren stickstoff- oder schwefelhaltigen aromatischen oder nichtaromatischen Vinylverbindungen und
  • B) einem mit polymerisationsaktiven Endgruppen derivatisierten Kieselgel
unter Zusatz eines Initiators in einem Lösungsmittel oder einem Gemisch aus mehreren Lösungsmitteln umgesetzt wird, gegebenenfalls gereinigt und anschließend mit einem oder mehreren Metallen der Gruppen 1 bis 16 des Periodensystems oder Metallverbindungen der Metalle der Gruppen 1 bis 16 des Periodensystems ohne Lösungsmittel oder in einem oder einem Gemisch mehrerer Lösungsmittel umgesetzt wird, wobei die Verfahrensschritte bei einer Temperatur zwischen -90°C und 180°C und einem Druck zwischen 10 mbar und 10 kbar durchgeführt werden.1. A process for the preparation and doping of a catalyst based on silica gel, characterized in that a mixture of
  • A) one or more nitrogenous or sulfur-containing aromatic or non-aromatic vinyl compounds and
  • B) a silica gel derivatized with polymerization-active end groups
with the addition of an initiator in a solvent or a mixture of several solvents, optionally purified and then with one or more metals from groups 1 to 16 of the periodic table or metal compounds of metals from groups 1 to 16 of the periodic table without solvent or in one or A mixture of several solvents is reacted, the process steps being carried out at a temperature between -90.degree. C. and 180.degree. C. and a pressure between 10 mbar and 10 kbar. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als stickstoffhaltige aromatische Vinylverbindung 4-Vinylpyridin eingesetzt wird. 2. The method according to claim 1, characterized characterized that as nitrogenous aromatic vinyl compound 4-vinylpyridine is used.   3. Verfahren nach einem oder mehreren der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß als Starter Azodiisobutyronitril (AIBN) eingesetzt wird.3. The method according to one or more of claims 1 to 2, characterized in that as a starter Azodiisobutyronitrile (AIBN) is used. 4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als Lösungsmittel Chloroform eingesetzt wird.4. The method according to one or more of claims 1 to 3, characterized in that as Chloroform solvent is used. 5. Verfahren nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Träger in Heptan mit FeCl3 dotiert wird.5. The method according to one or more of the preceding claims, characterized in that the carrier is doped with FeCl 3 in heptane. 6. Verwendung der nach einem der Ansprüche 1-5 hergestellten Katalysatoren für die chromatographische Trennung von Stoffgemischen (Ligandenaustauschchromatographie).6. Use of the produced according to one of claims 1-5 Catalysts for the chromatographic separation of Mixtures of substances (ligand exchange chromatography). 7. Verwendung der nach einem der Ansprüche 1-5 hergestellten Katalysatoren zur Hydrierung von ungesättigten Verbindungen, zur Kernhydrierung von aromatischen Verbindungen, zur Polymerisation von ungesättigten Kohlenwasserstoffen, zur Halogenierung von ungesättigten oder gesättigten Verbindungen, zur Kernhalogenierung von aromatischen Verbindungen, zu Abbaureaktionen von organischen Stoffen, insbesondere von organischen Abfällen oder Schadstoffen, mit oder ohne Einwirkung von künstlicher oder natürlicher Strahlung.7. Use of the manufactured according to one of claims 1-5 Catalysts for the hydrogenation of unsaturated compounds, for the nuclear hydrogenation of aromatic compounds, for Polymerization of unsaturated hydrocarbons Halogenation of unsaturated or saturated Compounds for the nuclear halogenation of aromatic Compounds, for decomposition reactions of organic substances, especially of organic waste or pollutants or without the influence of artificial or natural Radiation.
DE19944413405 1994-04-18 1994-04-18 Process for the preparation of polymeric catalyst supports based on silica gel and their doping with metal compounds Expired - Fee Related DE4413405C2 (en)

Priority Applications (1)

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DE19944413405 DE4413405C2 (en) 1994-04-18 1994-04-18 Process for the preparation of polymeric catalyst supports based on silica gel and their doping with metal compounds

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DE19944413405 DE4413405C2 (en) 1994-04-18 1994-04-18 Process for the preparation of polymeric catalyst supports based on silica gel and their doping with metal compounds

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DE4413405A1 DE4413405A1 (en) 1994-10-27
DE4413405C2 true DE4413405C2 (en) 2000-06-08

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989008500A1 (en) * 1988-03-19 1989-09-21 Eric Robinson Composite adsorbents
US5213895A (en) * 1990-09-11 1993-05-25 Daiso Co., Ltd. Particle-bearing composite and a method for producing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989008500A1 (en) * 1988-03-19 1989-09-21 Eric Robinson Composite adsorbents
US5213895A (en) * 1990-09-11 1993-05-25 Daiso Co., Ltd. Particle-bearing composite and a method for producing the same

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