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WO1999016547A1 - Selective alkylation of aromatics with surface-modified microporous mixed oxides - Google Patents

Selective alkylation of aromatics with surface-modified microporous mixed oxides 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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Prior art keywords
mixed oxides
aromatics
alkylation
modified
selective
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PCT/EP1998/005835
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German (de)
French (fr)
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Wilhelm F. Maier
Stephan Neunerdt
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Studiengesellschaft Kohle Mbh
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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
    • B01J31/0272—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%].

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to modified amorphous microporous mixed oxides and the use thereof as catalysts with increased form selectivity in chemical reactions. The inventive mixed oxides are modified by specific surface treatment using suitable reagents.

Description

Selektive Alkylierung von Aromaten mit oberflächenmodifizierten mikroporösen Mischoxiden. Selective alkylation of aromatics with surface-modified microporous mixed oxides.
Die Erfindung betrifft modifizierte amorphe mikroporöse Mischoxide und deren Einsatz als Katalysatoren mit erhöhter Formselektivität in chemischen Reaktionen. Die Modifizierung erfolgt durch gezielte Oberflächenbehandlung mit geeigneten Reagenzien.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.
Die Entwicklung neuer selektiver chemischer Produktionsprozesse vor dem Hintergrund steigender Entsorgungskosten und der wachsenden Umweltschutzauflagen ist ein wichtiges Ziel in der Katalyseforschung. Ein entscheidender Schritt hierbei ist die Entwicklung und der Einsatz formselektiver Katalysatoren. In vereinfachter Weise kann man die formselektive Katalyse als eine Kombination aus Molekularsiebeffekt und heterogener Katalyse beschreiben. Hierbei werden die Edukte, Produkte oder die während der Reaktion auftretenden Zwischenprodukte und Übergangszustände aufgrund ihrer Form und Größe voneinander unterschieden. Voraussetzung hierbei ist, daß der Reaktionsort, das katalytisch aktive Zentrum, in einer räumlich eingeschränkten Umgebung liegt. Dieser formselektive Effekt tritt idealerweise in rein mikroporösen Porensystemen mit enger Porenradienverteilung auf, wenn die Moleküle einen ähnlichen Durchmesser wie die Poren haben. Bisher kamen im wesentiichen Zeolithe als hochporöse kristalline Festkörper mit enger Mikroporenverteilung zum Einsatz. Die katalytischen Crack-, Hydrocrack und Dewaxing- Prozesse in der Petrochemie, der MTG (Methanol to Gasoline) Prozeß oder die Gasphasenethylierung von Benzol zum Ethylbenzol nach dem Mobil-Badger Prozeß sind einige Beispiele, in denen die Zeolithe ihre großtechnische Anwendung gefunden haben. Der Breite der Anwendbarkeit der Zeolithe sind aber grundsätzlich Grenzen gesetzt. So ist der stabile isomorphe Ersatz von anderen Elementen als Aluminium in der Silikatmatrix katalytisch aktiver Zeolithstrukturen auf wenige Elemente und geringe Anteile beschränkt.The development of new selective chemical production processes against the background of rising disposal costs and the growing environmental protection requirements is an important goal in catalysis research. A crucial step here is the development and use of shape-selective catalysts. In a simplified manner, 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. So far, 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. There are basically limits to the range of applicability of the zeolites. 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.
Mit einem speziell sauer katalysierten Sol-Gel Verfahren ohne Verwendung von Templatmolekülen kann die Synthese von amorphen mikroporösen Silicium, Titan-, Zirkon- und Aluminiumoxiden mit enger Porenradienverteilung durchgeführt werden (Maier, W.F.; Tilgner, l.-C.;, Wiedom, M.; Ko, H.-C, Advanced Materials. 10 (1993) 726). Der zusätzlichen Dotierung solcher Materialien mit weiteren Metallen ist prinzipiell keine Grenze gesetzt (S. Klein, J. Martens, R. Parton, K. Vercuysse, P.A. Jacobs, W.F. Maier, Catal. Lett.. 38 (1996) 209). Alle Gläser zeigen die charakteristische Typ-I-Isotherme für rein mikroporöse Gläser und haben eine hohe spezifische Oberfläche. Diese mikroporösen Mischoxide zeigen analog den Zeolithen formselektive katalytische Eigenschaften (W.F. Maier, S. Klein, J. Martens, J. Heilmann, R. Parton, K. Vercuysse, P.A. Jacobs, Angew. Chemie. 108 (1996) 222; Int. Ed. 35 (1996) 180). So kann beispielsweise t-Butylether direkt aus n-Alkoholen und t- Butylalkohol oder Isobuten hergestellt werden. Unter homogenen Bedingungen wird keine t-Butyletherbildung beobachtet. Die Epoxidierung von Olefinen mit 6 oder weniger Kohlenstoffatomen läuft viel schneller als die Epoxidierung größerer Alkene. Ebenfalls ist die Produktzusammensetzung beim hydrierenden Cracktest von Decan vergleichbar mit der Produktverteilung, die durch Katalyse mit großporigen Zeolithen entsteht (PCT-Patentanmeldung WO96/26907, Prioritätsdatum 28.2.95).With a specially acid-catalyzed sol-gel process without the use of template molecules, the synthesis of amorphous microporous silicon, titanium, zirconium and aluminum oxides with a narrow pore radius distribution can be carried out (Maier, WF; Tilgner, l.-C.;, Wiedom, M .; Ko, H.-C, Advanced materials. 10 (1993) 726). In principle, there is no limit to the additional doping of such materials with other metals (S. Klein, J. Martens, R. Parton, K. Vercuysse, PA Jacobs, WF Maier, Catal. Lett .. 38 (1996) 209). All glasses show the characteristic Type I isotherm for purely microporous glasses and have a high specific surface. Analogously to the zeolites, these microporous mixed oxides show shape-selective catalytic properties (WF Maier, S. Klein, J. Martens, J. Heilmann, R. Parton, K. Vercuysse, PA Jacobs, Angew. Chemie. 108 (1996) 222; Int. Ed 35 (1996) 180). For example, 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).
Von Nachteil ist bisher, daß sich die Selektivität dieser Materialien nicht gezielt auf die gewünschten Produkte einstellen läßt. Dies wird am Beispiel der Alkylierung der Biphenyle und Naphthaline deutlich:It has been a disadvantage so far that the selectivity of these materials cannot be specifically adjusted to the desired products. This becomes clear from the example of the alkylation of biphenyls and naphthalenes:
4,4 -Dialkylbiphenyle bzw. 2,6-DialkyInaphtaline sind wichtige Vorstufen zur Herstellung von Flüssigkristallpolymeren und weiteren Funktions- und Strukturmaterialien. Ein gängiger Syntheseweg besteht in der direkten, sauer katalysierten Alkylierung von Biphenyl bzw. Naphtalin an Silica-Alumina Katalysatoren. Die Alkylierung verläuft unselektiv und die entstehenden ungewünschten Isomere müssen kostenintensiv abgetrennt werden. Der H- Mordenit (Y. Sugi, M. Toba, Catal. Today 19 (1994) 187) und der SAPO-11 (Matsuda, T. Kimura, E. Herawati, C. Kobayashi, E. Kikuchi, Appl. Catal. A: 136 (1996) 19) sind bisher die einzigen Zeolithe die formselektiv diese Reaktion zu katalysieren vermögen. Hierbei nutzt man die Tatsache, daß die 4,4'- Dialkylbiphenyle wie auch die 2,6-Dialkylnaphtaline von allen möglichen Isomeren die sterisch anspruchslosesten sind. Diese Isomere werden daher bevorzugt in den engen Poren des H-Mordeniten bzw. SAPO-11 gebildet bzw. können schneller aus den Poren diffundieren. Unmodifizierte amorphe mikroporöse Mischoxide zeigen in solchen Alkylierungsreaktionen hohe Alkylierungsaktivität bei geringer Selektivität.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. A: 136 (1996) 19) are so far the only zeolites that are able to catalyze this reaction in a form-selective manner. Here, the fact is used that the 4,4'-dialkylbiphenyls as well as the 2,6-dialkylnaphtalines are the most sterically undemanding of all possible isomers. These isomers are therefore preferably formed in the narrow pores of the H-mordenite or SAPO-11 or can diffuse out of the pores more quickly. Unmodified amorphous Microporous mixed oxides show high alkylation activity with low selectivity in such alkylation reactions.
Wir haben nun gefunden, daß dieses unselektive Verhalten überraschenderweise durch nachträgliche Modifizierung der Materialien mit Silylierungs- und Alkylierungsreagenzien gezielt verbesserbar ist. Die nachträgliche Modifizierung von Katalysatoren ist durchaus bekannt und wird gezielt zur Verbesserung von katalytischen Eigenschaften eingesetzt (Offenlegungsschrift 2311822 DE). Dies wurde zum Beispiel zu Verbesserungen von Katalysatoren zur Herstellung von Epoxiden genutzt (DE 21 48 637 B2). Unbekannt war bisher, daß mit solchen Verfahren die Formselektivität von amorphen Mischoxiden mit enger Porenverteilung verbessert werden kann. Beliebige amorphe Mischoxide mit einer engen Porenverteilung lassen sich durch solch einen nachträglichen Modifizierungsschritt auf die gewünschte Reaktionsselektivität einstellen. Als Modifizieragenzien eignen sich Reagenzien, die mit vorhandenen Oberflächenhydroxylgruppen stabile kovalente Bindungen eingehen und damit zu einer Verengung der Porendurchmesser führen. Solche Reagenzien sind z.B. reine oder gemischte Halogenide, Alkoxide oder Alkyl- verbindungen von Silizium, Titan, Aluminium, Zirkon, Magnesium, Calzium, Barium, Ytrium, Lanthan oder Cer. Solchermassen modifizierte Katalysatoren sind geeignet für die Erhöhung der Selektivität von heterogen katalysierten Alkylierungs-, Acylierungs-, Additions- und Pericyclischen Reaktionen, für Crack- und Hydrocracking-Reaktionen, oxidative Dimerisierungsreaktionen kleiner Kohlenwasserstoffe (C-j-C^, und die Umwandlung von Methanol in Kohlenwasserstoffe. Die Materialien eignen sich auch als Trägermaterialien für Fischer-Tropsch Reaktionen und Hydroformylierungen.We have now found that this unselective behavior can surprisingly be improved in a targeted manner by subsequent modification of the materials with silylation and alkylation reagents. The subsequent modification of catalysts is well known and is used specifically to improve catalytic properties (published specification 2311822 DE). This was used, for example, to improve catalysts for the production of epoxides (DE 21 48 637 B2). It was previously unknown that the shape selectivity of amorphous mixed oxides with a narrow pore distribution can be improved with such processes. Any amorphous mixed oxides with a narrow pore distribution can be adjusted to the desired reaction selectivity by such a subsequent modification step. 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.
Beispiele:Examples:
Beispiel 1 :Example 1 :
Herstellung eines amorphen mikroporösen Aluminium-Silicium-MischoxidesProduction of an amorphous microporous aluminum-silicon mixed oxide
20 ml Tetraethoxysilan (TEOS) werden in 14 ml Ethanol gelöst und mit 2,9 ml20 ml of tetraethoxysilane (TEOS) are dissolved in 14 ml of ethanol and 2.9 ml
H2O und 2,3 ml konz. HCI versetzt. Die Lösung wird für 12 h gerührt und anschließen mit 1 ,1 g Aluminium-sec-butoxid versetzt. Nach erfolgter Gelierung wird das Material auf 65 C mit einer Heizrate von 0,5 C aufgeheizt, 3 h bei 65 C gehalten, mit einer Heizrate von 0,2 C auf 250 C aufgeheizt und weitere 3 h bei dieser Temperatur kalziniert. Die Ad-/Desorptionisothermen zeigen eine monomodale Mikroporenverteilung, eine berechnete Oberfläche nach BET von 530m2/g und ein Porendurchmesser von 0,67 nm. Festkörper-NMR- Untersuchungen an dem so hergestellten Katalysator zeigen, daß das Aluminium tetraedisch koordiniert in der Matrix vorliegt.H2O and 2.3 ml conc. HCI added. The solution is stirred for 12 h and then 1.1 g of aluminum sec-butoxide are added. After gelation, the material is heated to 65 C with a heating rate of 0.5 C, 3 h at 65 C kept, heated at a heating rate of 0.2 C to 250 C and calcined at this temperature for a further 3 h. The adsorption / desorption isotherms show a monomodal micropore distribution, a calculated BET surface area of 530 m 2 / g and a pore diameter of 0.67 nm. Solid-state NMR investigations on the catalyst prepared in this way show that the aluminum is present in a tetrahedron coordinated manner in the matrix .
Beispiel 2:Example 2:
Silylierung des KatalysatorsSilylation of the catalyst
80 mg des zu modifizierenden Katalysators wird in ein Reaktionsrohr gefüllt und bei 250 C für 1 h in einem N2 Strom von 4 ml/min getrocknet. Zur Silylierung werden 50 ml Tnisopropylsilylchlorid im Trägergastrom (4 ml N2/min) verdampft und durch die Katalysatorschüttung bei 250 C geleitet. Bei gößeren80 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. For silylation, 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. With larger ones
Katalysatormengen reduziert sich der Überschuß des Silyiierungsmittels. DerThe amount of catalyst reduces the excess of the silyating agent. The
Katalysator ist nach dieser Behandlung einsatzbereit.The catalyst is ready for use after this treatment.
Beispiel 3:Example 3:
Selektive Propylierung von BiphenylSelective propylation of biphenyl
In einem Trägergasstrom von Propen (7 ml/min) wird 2,5 mmol/h Biphenyl verdampft und durch die Katalysatorschüttung (80 mg modifizierte Katalysator aus Beispiel 2 bei 250 C geleitet. Am Ende des Reaktionsrohres werden die2.5 mmol / h of biphenyl is evaporated in a carrier gas stream of propene (7 ml / min) and passed through the catalyst bed (80 mg of modified catalyst from Example 2 at 250 ° C. At the end of the reaction tube, the
Reaktionsprodukte ausgefroren und gaschromatographisch untersucht. Am modifizierten aluminiumhaltigen amorphen Mischoxid kann das 4,4'-Diisopropyl- biphenyl mit einer Selektivität von 11 ,4 % [Umsatz 42%] erhalten werden. Ein unmodifiziertes Mischoxid zeigt mit 5,1% [Umsatz 45 %] eine deutlich geringereReaction products frozen out and examined by gas chromatography. The 4,4'-diisopropylbiphenyl can be obtained with a selectivity of 11.4% [conversion 42%] on the modified aluminum-containing amorphous mixed oxide. An unmodified mixed oxide shows a significantly lower rate of 5.1% [conversion 45%]
Selektivität.Selectivity.
Beispiel 4:Example 4:
Selektive Propylierung von NaphtalinSelective propylation of naphthalene
In einem Trägergasstrom von Propen (7 ml/min) wird 2,5 mmol/h Naphtalin verdampft und durch die Katalysatorschüttung bei 250 C geleitet. Am Ende des2.5 mmol / h of naphthalene is evaporated in a propene carrier gas stream (7 ml / min) and passed through the catalyst bed at 250.degree. At the end of
Reaktionsrohres werden die Reaktionsprodukte ausgefroren und gaschromatographisch untersucht. Am modifizierten aluminiumhaltigen amorphen Mischoxid kann das 2,6-Diisopropynaphtalin mit einer Selektivität von 7,6 % [Umsatz 47 %] erhalten werden. Ein unmodifiziertes Mischoxid zeigt mit ,3 % [Umsatz 88 %] eine deutlich geringere Selektivität. Reaction tube, the reaction products are frozen out and examined by gas chromatography. On the modified aluminum-containing amorphous mixed oxide, 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%].

Claims

Patentansprüche: Claims:
1. Amorphe mikroporöse Mischoxide, die eine hohe Porosität von 10-50% und für mindestens 80% der Poren einen Porendurchmesser kleiner als 1 ,2 nm mit einer engen Porenverteilung aufweisen, dadurch gekennzeichnet, daß die Mischoxide durch Reaktion mit einer oder mehreren der Verbindungen vom Typ RχMXy oder ROxMR'y mit R= Me, Et, n-Pr, i-Pr, n-Bu, i-Bu„ i-Bu, Phenyl, Tolyl; M=Si, Ti, Zr, AI, Ce, La; X=CI, Br, MeO, EtO, i-PrO, n-PrO, n-Bu; x=1- 5, y=1-5 in der Flüssigphase oder der Gasphase modifiziert sind.1. Amorphous microporous mixed oxides which have a high porosity of 10-50% and for at least 80% of the pores have a pore diameter of less than 1.2 nm with a narrow pore distribution, characterized in that the mixed oxides by reaction with one or more of the compounds of the type R χ MX y or RO x MR ' y with R = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu „i-Bu, phenyl, tolyl; M = Si, Ti, Zr, Al, Ce, La; X = CI, Br, MeO, EtO, i-PrO, n-PrO, n-Bu; x = 1- 5, y = 1-5 in the liquid phase or the gas phase are modified.
2. Verfahren zur formselektiven Durchführung von heterogen katalysierten Reaktionen, dadurch gekennzeichnet, daß amorphe mikroporöse Mischoxide gemäß Anspruch 1 als Katalysatoren eingesetzt werden.2. Process for the form-selective implementation of heterogeneously catalyzed reactions, characterized in that amorphous microporous mixed oxides according to claim 1 are used as catalysts.
3. Verfahren gemäß Anspruch 2 zur Durchführung von heterogen katalysierten Alkylierungs-, Acylierungs-, Additions-, und Cycloadditionsreaktionen3. The method according to claim 2 for carrying out heterogeneously catalyzed alkylation, acylation, addition, and cycloaddition reactions
4. Verfahren nach Anspruch 3 zur Herstellung von Dialkylaromaten durch Alkylierung oder Acylierung der entspechenden unalkylierten, unacylierten oder monoalkylierten bzw. monoacylierten Aromaten. 4. The method according to claim 3 for the preparation of dialkyl aromatics by alkylation or acylation of the corresponding unalkylated, unacylated or monoalkylated or monoacylated aromatics.
PCT/EP1998/005835 1997-09-30 1998-09-15 Selective alkylation of aromatics with surface-modified microporous mixed oxides WO1999016547A1 (en)

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JP2008529784A (en) * 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 Use of said catalysts for reforming catalysts and synthesis gas to hydrocarbon conversion

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JP2008529784A (en) * 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 Use of said catalysts for reforming catalysts and synthesis gas to hydrocarbon conversion

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