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WO1999016547A1 - Alkylation selective de composes aromatiques avec des oxydes mixtes microporeux modifies en surface - Google Patents

Alkylation selective de composes aromatiques avec des oxydes mixtes microporeux modifies en surface Download PDF

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Publication number
WO1999016547A1
WO1999016547A1 PCT/EP1998/005835 EP9805835W WO9916547A1 WO 1999016547 A1 WO1999016547 A1 WO 1999016547A1 EP 9805835 W EP9805835 W EP 9805835W WO 9916547 A1 WO9916547 A1 WO 9916547A1
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WO
WIPO (PCT)
Prior art keywords
mixed oxides
aromatics
alkylation
modified
selective
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.)
Ceased
Application number
PCT/EP1998/005835
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German (de)
English (en)
Inventor
Wilhelm F. Maier
Stephan Neunerdt
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.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of WO1999016547A1 publication Critical patent/WO1999016547A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • 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
    • B01J21/12—Silica and alumina
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • 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
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • 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
    • 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
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm

Definitions

  • the invention relates to modified amorphous microporous mixed oxides and their use as catalysts with increased shape selectivity in chemical reactions.
  • the modification is carried out by targeted surface treatment with suitable reagents.
  • shape-selective catalysis can be described as a combination of molecular sieve effect and heterogeneous catalysis.
  • the starting materials, products or the intermediates and transition states occurring during the reaction are distinguished from one another on the basis of their shape and size.
  • the prerequisite here is that the reaction site, the catalytically active center, is in a spatially restricted environment.
  • This shape-selective effect ideally occurs in purely microporous pore systems with a narrow pore radius distribution if the molecules have a diameter similar to that of the pores.
  • zeolites have mainly been used as highly porous crystalline solids with a narrow microporous distribution.
  • the catalytic cracking, hydrocracking and dewaxing processes in the petrochemical industry, the MTG (methanol to gasoline) process or the gas phase ethylation of benzene to ethylbenzene according to the Mobil-Badger process are some examples in which the zeolites have found their industrial application.
  • the stable isomorphic replacement of elements other than aluminum in the silicate matrix of catalytically active zeolite structures is limited to a few elements and small proportions.
  • t-butyl ether can be prepared directly from n-alcohols and t-butyl alcohol or isobutene. No formation of t-butyl ether is observed under homogeneous conditions.
  • the epoxidation of olefins with 6 or fewer carbon atoms is much faster than the epoxidation of larger alkenes.
  • the product composition in the hydrogenating cracking test of decane is also comparable to the product distribution which is produced by catalysis with large-pore zeolites (PCT patent application WO96 / 26907, priority date February 28, 1995).
  • 4,4-Dialkylbiphenyls or 2,6-DialkyInaphtaline are important precursors for the production of liquid crystal polymers and other functional and structural materials.
  • a common synthetic route is the direct, acid-catalyzed alkylation of biphenyl or naphthalene on silica-alumina catalysts. The alkylation proceeds unselectively and the undesired isomers that arise have to be separated off at high cost.
  • H-mordenite Y. Sugi, M. Toba, Catal. Today 19 (1994) 187) and SAPO-11 (Matsuda, T. Kimura, E. Herawati, C. Kobayashi, E. Kikuchi, Appl. Catal.
  • Suitable modifying agents are reagents which form stable covalent bonds with existing surface hydroxyl groups and thus lead to a narrowing of the pore diameter.
  • Such reagents are, for example, pure or mixed halides, alkoxides or alkyl compounds of silicon, titanium, aluminum, zirconium, magnesium, calcium, barium, ytrium, lanthanum or cerium.
  • Such modified catalysts are suitable for increasing the selectivity of heterogeneously catalyzed alkylation, acylation, addition and pericyclic reactions, for cracking and hydrocracking reactions, oxidative dimerization reactions of small hydrocarbons (C- J -C ⁇ , and the conversion of methanol in hydrocarbons
  • the materials are also suitable as carrier materials for Fischer-Tropsch reactions and hydroformylations.
  • TEOS tetraethoxysilane
  • 80 mg of the catalyst to be modified is placed in a reaction tube and dried at 250 C for 1 h in an N2 stream of 4 ml / min.
  • 50 ml of tnisopropylsilyl chloride are evaporated in a carrier gas stream (4 ml of N 2 / min) and passed through the catalyst bed at 250 ° C.
  • the amount of catalyst reduces the excess of the silyating agent.
  • the catalyst is ready for use after this treatment.
  • reaction tube the reaction products are frozen out and examined by gas chromatography.
  • the 2,6-diisopropynaphthalene can be selected with a selectivity of 7.6% [sales 47%] can be obtained.
  • An unmodified mixed oxide shows a significantly lower selectivity with .3% [conversion 88%].

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des oxydes mixtes microporeux amorphes modifiés et leur utilisation comme catalyseurs présentant une sélectivité de forme accrue dans des réactions chimiques. Ces oxydes mixtes sont modifiés par traitement de surface spécifique à l'aide de réactifs appropriés.
PCT/EP1998/005835 1997-09-30 1998-09-15 Alkylation selective de composes aromatiques avec des oxydes mixtes microporeux modifies en surface Ceased WO1999016547A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19743165.8 1997-09-30
DE19743165A DE19743165A1 (de) 1997-09-30 1997-09-30 Selektive Alkylierung von Aromaten mit oberflächenmodifizierten mikroporösen Mischoxiden

Publications (1)

Publication Number Publication Date
WO1999016547A1 true WO1999016547A1 (fr) 1999-04-08

Family

ID=7844131

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/005835 Ceased WO1999016547A1 (fr) 1997-09-30 1998-09-15 Alkylation selective de composes aromatiques avec des oxydes mixtes microporeux modifies en surface

Country Status (2)

Country Link
DE (1) DE19743165A1 (fr)
WO (1) WO1999016547A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008529784A (ja) * 2005-02-17 2008-08-07 ビーピー エクスプロレーション オペレーティング カンパニー リミテッド 改質触媒および合成ガスから炭化水素への変換のための前記触媒の使用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2691380A1 (fr) * 1992-05-25 1993-11-26 Inst Francais Du Petrole Composition catalytique à base de silice et son utilisation pour la polymérisation de composés hétérocycliques.
WO1994027934A1 (fr) * 1993-05-28 1994-12-08 Mobil Oil Corporation Procede pour modifier la selectivite de forme d'un catalyseur a la zeolite et utilisation du catalyseur ainsi modifie
WO1995011753A1 (fr) * 1993-10-26 1995-05-04 Shell Internationale Research Maatschappij B.V. Procede et catalysateur d'hydrotraitement
DE19506843A1 (de) * 1995-02-28 1996-08-29 Studiengesellschaft Kohle Mbh Mikroporöse amorphe Mischmetalloxide für formselektive Katalyse
DE19545042A1 (de) * 1995-12-02 1997-06-05 Studiengesellschaft Kohle Mbh Amorphe mikroporöse Mischoxidkatalysatoren mit kontrollierter Oberflächenpolarität für die selektive heterogene Katalyse Adsorption und Stofftrennung
EP0841092A2 (fr) * 1996-11-12 1998-05-13 Phillips Petroleum Company Matériel zéolitique et son application dans la conversion d'hydrocarbures non aromatiques en aromates et oléfines légères

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1002056A (en) * 1970-10-01 1976-12-21 Harald P. Wulff Catalyst for producing oxirane compounds by epoxidizing olefins with hydroperoxides
DE3042410C2 (de) * 1980-11-11 1983-10-20 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Herstellung von Liganden aufweisenden Trägern und diesen entsprechenden Komplexkatalysatoren
ES2007545A6 (es) * 1988-08-03 1989-06-16 Petroquimica Espanola S A Petr Proceso de alquilacion catalitica en lecho fijo de hidrocarburos aromaticos.
EP0504541B1 (fr) * 1991-03-21 1998-07-22 Solutia Europe N.V./S.A. Procédé catalytique amélioré pour l'alcoylation sélective d'hydrocarbures aromatiques
US5382733A (en) * 1992-03-27 1995-01-17 Mitsubishi Kasei Corporation Process for preparing naphthalene or derivative thereof
DE4309660A1 (de) * 1993-03-25 1994-09-29 Studiengesellschaft Kohle Mbh Selektive anorganische Katalysatoren in Form von molekularen Abdrücken in Hohlräumen
DE4311028A1 (de) * 1993-03-30 1994-10-06 Schering Ag Methylierungs- bzw. Ethylierungsmittel und Verfahren zur 1,4-Addition einer Methyl- bzw. Ethylgruppe an eine alpha,beta-ungesättigte Keto-Verbindung

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2691380A1 (fr) * 1992-05-25 1993-11-26 Inst Francais Du Petrole Composition catalytique à base de silice et son utilisation pour la polymérisation de composés hétérocycliques.
WO1994027934A1 (fr) * 1993-05-28 1994-12-08 Mobil Oil Corporation Procede pour modifier la selectivite de forme d'un catalyseur a la zeolite et utilisation du catalyseur ainsi modifie
WO1995011753A1 (fr) * 1993-10-26 1995-05-04 Shell Internationale Research Maatschappij B.V. Procede et catalysateur d'hydrotraitement
DE19506843A1 (de) * 1995-02-28 1996-08-29 Studiengesellschaft Kohle Mbh Mikroporöse amorphe Mischmetalloxide für formselektive Katalyse
DE19545042A1 (de) * 1995-12-02 1997-06-05 Studiengesellschaft Kohle Mbh Amorphe mikroporöse Mischoxidkatalysatoren mit kontrollierter Oberflächenpolarität für die selektive heterogene Katalyse Adsorption und Stofftrennung
EP0841092A2 (fr) * 1996-11-12 1998-05-13 Phillips Petroleum Company Matériel zéolitique et son application dans la conversion d'hydrocarbures non aromatiques en aromates et oléfines légères

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008529784A (ja) * 2005-02-17 2008-08-07 ビーピー エクスプロレーション オペレーティング カンパニー リミテッド 改質触媒および合成ガスから炭化水素への変換のための前記触媒の使用

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