DE4413405A1 - Process for synthesising polymeric catalyst supports based on silica gel and doping thereof with metal compounds - Google Patents

Process for synthesising polymeric catalyst supports based on silica gel and doping thereof with metal compounds

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Publication number
DE4413405A1
DE4413405A1 DE19944413405 DE4413405A DE4413405A1 DE 4413405 A1 DE4413405 A1 DE 4413405A1 DE 19944413405 DE19944413405 DE 19944413405 DE 4413405 A DE4413405 A DE 4413405A DE 4413405 A1 DE4413405 A1 DE 4413405A1
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DE
Germany
Prior art keywords
silica gel
compounds
doping
mixture
solvent
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.)
Granted
Application number
DE19944413405
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German (de)
Other versions
DE4413405C2 (en
Inventor
Joachim Daub
Thomas Dipl Chem Schlieper
Lutz-Steffen Dipl Che 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 DIPL CHE
DAUB JOACHIM DIPL GEOOEK
Original Assignee
BERGHOLD LUTZ STEFFEN DIPL CHE
DAUB JOACHIM DIPL GEOOEK
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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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    • 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

Abstract

Process for synthesising and doping a catalyst support based on silica gel, characterised in that a mixture of A) one or more nitrogen- or sulphure-containing aromatic or nonaromatic vinyl compounds and B) a silica gel derivatised by end groups active in polymerisation is reacted with addition of an initiator and is then doped with metals of groups 1 to 16 of the Periodic Table of the Elements.

Description

Die Erfindung betrifft ein Verfahren zur Darstellung ei­ nes mit organischen Polymeren derivatisierten Silicagels zur Verwendung als Katalysatorträger.The invention relates to a method for displaying egg silica gel derivatized with organic polymers for use as a catalyst support.

Ein Verfahren der gattungsgemäßen Art existiert zur Zeit nicht.A method of the generic type currently exists Not.

Ein Verfahren, das einen Katalysatorträger mit N-haltigen Endgruppen synthetisiert, ist durch das Patent Az. P 4,339,635 beschrieben. In diesem Verfahren wird ein Perl­ polymer, das aus 4-Vinylpyridin, Divinylbenzol und Methylmethacrylat besteht, synthetisiert und als Kataly­ satorträger eingesetzt.A process involving a catalyst support with N-containing End groups are synthesized by the patent Az. P 4,339,635. In this process, a pearl polymer consisting of 4-vinylpyridine, divinylbenzene and There is methyl methacrylate, synthesized and as Kataly sator carrier used.

Diese Erfindung betrifft ein Verfahren zur Synthese eines polymeren Katalysatorträgers auf Silicagelbasis und deren Dotierung mit Metallkomplexen.This invention relates to a method of synthesizing a polymeric catalyst carrier based on silica gel and their Doping with metal complexes.

Dabei werden zunächst Monomere mit polymerisationsaktiven Doppelbindungen wie z. B. 4-Vinylpyridin, mit einem Sili­ cagel, das polymerisationsaktive Endgruppen besitzt, un­ ter Zusatz eines Starters z. B. AIBN, in Chloroform bei einer Temperatur von 80-90°C polymerisiert.First, monomers with polymerization-active Double bonds such as B. 4-vinyl pyridine with a sili cagel, which has polymerization-active end groups, un ter addition of a starter z. B. AIBN, in chloroform polymerized at a temperature of 80-90 ° C.

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

Die Dotierung des Polymerträgers mit einer Metallverbin­ dung erfolgt in einem Lösungsmittel, indem der Polymerträ­ ger zunächst in diesem Lösungsmittel suspendiert wird und danach die Metallverbindung in fester oder gelöster Form zugegeben wird.Doping the polymer carrier with a metal compound is carried out in a solvent by the polymer carrier ger is initially suspended in this solvent and then the metal compound in solid or dissolved form is added.

Vorteile dieses Verfahrens der Darstellung von Katalysat­ orträgern gegenüber dem bekannten Verfahren (Patent Az. P 4,339,635):Advantages of this method of the preparation of catalyst against the known method (Patent Az. P 4,339,635):

  • - geringe Konten bei der Wahl der Monomere- small accounts 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 Silicagelkörner und somit Vergrößerung der Oberfläche (Durchmesser Perlpolymer 100 µm zu 5 µm beim Silicagel).- 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).

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

Beispiel 1: Darstellung eines KatalysatorträgersExample 1: Representation of a catalyst carrier

10 g Acrylsilicagel (Silicagel mit Acryloylendgruppen), 5 µm 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 da­ nach in (50+50+50) ml 2-Propanol gewaschen. 10 g of acrylic silica gel (silica gel with acryloyl end groups), 5 µm were mixed with 8 ml (75.3 mmol) of 4-vinylpyridine in 60 ml CHCl₃ heated to 80-90 ° C for 3 h under argon. After that was cooled and the residue in (50 + 50) ml of toluene and there after washed in (50 + 50 + 50) ml of 2-propanol.  

Beispiel 2: Dotierung des erfindungsgemäßen Katalysator­ trägers mit TiCl₄Example 2: Doping of the catalyst according to the invention carrier with TiCl₄

In 50 ml Heptan wurden in einem Schlenkrohr 3 g Trägerma­ terial 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 in a Schlenk tube 3 g vehicle suspended material and 2 ml (18 mmol) TiCl₄ added. It was shaken for 1 h at room temperature, then the decanting the supernatant solution, contact with heptane washed and dried at 50 ° C in a vacuum.

Beispiel 3: Dotierung des erfindungsgemäßen Katalysator­ trägers mit FeCl₃Example 3: Doping of the catalyst according to the invention carrier with FeCl₃

In 50 ml Heptan wurden in einem Schlenkrohr 2,5 g Träger­ material 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 support were placed in 50 ml of heptane in a Schlenk tube suspended material and 1 g (6.2 mmol) FeCl₃ added. It was shaken for 1 h at room temperature, then the decanting the supernatant solution, contact with heptane washed and dried at 50 ° C in a vacuum.

Claims (7)

1. Verfahren zur Darstellung und Dotierung eines Kataly­ satorträgers auf Silicagelbasis, dadurch gekennzeichnet, daß ein Gemisch aus
  • A) einer oder mehreren stickstoff- oder schwefel­ haltigen aromatischen oder nichtaromatischen Vinylverbindungen und
  • B) einem mit polymerisationsaktiven Endgruppen derivatisierten Silicagel
1. A process for the preparation and doping of a catalyst carrier 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
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 Perioden­ systems oder Metallverbindungen der Metalle der Gruppen 1 bis 16 des Periodensystems ohne Lösungsmittel oder in ei­ nem 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.with the addition of an initiator in a solvent or a mixture of several solvents is implemented, cleaned if necessary and then with an or several metals from groups 1 to 16 of the period systems or metal compounds of the metals of group 1 to 16 of the periodic table without solvent or in egg nem or a mixture of several solvents being, the process steps at a temperature between -90 ° C and 180 ° C and a pressure between 10 mbar and 10 kbar. 2. Verfahren nach Anspruch 1, dadurch ge­ kennzeichnet, daß als stickstoffhaltige aroma­ tische Vinylverbindung 4-Vinylpyridin eingesetzt wird. 2. The method according to claim 1, characterized ge indicates that as a nitrogenous aroma table vinyl compound 4-vinylpyridine is used.   3. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß als Starter Azodiisobutyronitril (AIBN) eingesetzt wird.3. The method according to one or more of claims 1 to 4, characterized in that as 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. Method according to one or more of the preceding Claims, characterized, that the carrier is doped in FeCl₃ with heptane. 6. Verfahren nach einem oder mehreren der vorhergehenden Ansprüche, gekennzeichnet zur Synthese hoch­ reaktiver dotierter Metallträgerkatalysatoren zur Verwen­ dung für die chromatographische Trennung von Stoffgemi­ schen (Ligandenaustauschchromatographie) oder der Verwen­ dung für katalytische Reaktionen wie Hydrierung von unge­ sättigten Verbindungen, zur Kernhydrierung von aromati­ schen Verbindungen, zur Polymerisation von ungesättigten Kohlenwasserstoffen, zur Halogenierung von ungesättigten oder gesättigten Verbindungen sowie zur Kernhalogenierung von aromatischen Verbindungen, zu Abbaureaktionen von or­ ganischen Stoffen, speziell organischen Abfällen oder Schadstoffen, mit oder ohne Einwirkung von künstlicher oder natürlicher Strahlung.6. Method according to one or more of the preceding Claims characterized for high synthesis reactive doped metal supported catalysts for use for the chromatographic separation of material mixtures (ligand exchange chromatography) or use for catalytic reactions such as hydrogenation of unsaturated saturated compounds, for the core hydrogenation of aromati compounds, for the polymerization of unsaturated Hydrocarbons, for the halogenation of unsaturated or saturated compounds and for nuclear halogenation of aromatic compounds, to degradation reactions of or ganic substances, especially organic waste or Pollutants, with 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)

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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 true DE4413405A1 (en) 1994-10-27
DE4413405C2 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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