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Method for fixing homogeneous catalyst and catalyst material

A technology of homogeneous catalysts and catalytic materials, applied in the direction of catalyst carriers, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problems of limited separation, fine crystals are not stable enough, and hinder

Inactive Publication Date: 2006-09-27
HALDOR TOPSOE AS
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the use of such small crystals would hinder or severely limit the possibility of isolating the catalyst from the reaction mixture by filtration.
At the same time, fine crystals may not be sufficiently stable under the relevant reaction conditions

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 3

[0035] 2.0g of mesoporous MFI type zeolite was mixed with 1.0g of Mn(CH 3 COO) 2 4H 2 The aqueous solution of O was ion-exchanged at room temperature for 24 h. After filtration and drying, the zeolitic material was suspended in CH 2 Cl 2 / methanol (1:1). To this slurry was added 0.10 ml of diaminocyclohexane. The mixture was stirred for 24h. After addition of 200 mg of 3,5-bis(tert-butyl)salicylaldehyde and 100 mg of LiCl, the mixture was stirred in air for another 48 h.

[0036] The resulting light brown material, Jacobsen's catalyst immobilized in a mesoporous MFI type zeolite, was filtered and washed with CH 2 Cl 2 Wash several times and dry in air at 50°C.

Embodiment 4

[0038] 2.0g of mesoporous MFI type zeolite was mixed with 0.50g of Co(CH 3 COO) 2 4H 2 O and 0.98gMn(CH 3 COO) 2 4H 2 An aqueous solution of O (molar ratio Co:Mn 1:2) was ion-exchanged at 65°C for 4h. After filtration and drying, the zeolitic material was suspended in glacial acetic acid (18 ml). To the slurry was added pyridine (3.6ml), NaBr (0.60g) and H 2 o 2 (35%, 7.7ml). The mixture was stirred at room temperature while passing air flow through the solution for 2h.

[0039] In the product, the catalyst of Chavan et al. immobilized in a mesoporous MFI type zeolite, after filtration, with CH 3 COOH washed and dried in vacuo.

[0040] The catalyst of Comparative Example 1 had a metal loading of 1315 ppm Mn. The catalyst of Example 3 had a metal loading of 5970 ppm Mn.

[0041] The IR spectra of the two catalysts were indistinguishable from each other and compared with the unsupported Jacobsen catalyst N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexane-diami...

Embodiment 5

[0046] Sodium hypochlorite aqueous solution and Na 2 HPO 4 The solution was mixed and the pH was adjusted to 11.3. The catalyst from Comparative Example 1 (908 mg) or from Example 3 (200 mg, providing the same amount of Mn for both catalysts) was added to the cooled solution (0°C). A solution of 10 mmoles of styrene in 10 ml of dichloromethane was then added with stirring. The biphasic mixture was stirred at room temperature for a total of 5 h. Stir intermittently every 20min, and take samples from the separated organic phase, wash with water, in Na 2 SO 4 dried and analyzed by GC-MS. The mesoporous catalyst from Example 3 shows faster conversion of styrene to styrene oxide than the non-mesoporous catalyst from Comparative Example 1 .

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Abstract

The invention concerns a process for the immobilisation of a homogeneous catalyst comprising immobilising the homogeneous catalyst in zeotype crystals with a non-crystallographic mesopore system and a mesopore volume of the zeotype crystals above 0.25 ml / g. The invention also concerns a catalytic material prepared by the immobilisation process.

Description

technical field [0001] The present invention relates to the use of zeolite crystals as substrates for homogeneous catalysts, so-called "ship-in-the-bottle" catalysts, and to catalytic materials and methods for their preparation. [0002] In the present invention, the zeolite matrix is ​​a mesoporous zeolite, wherein the morphological structural modification of the zeolite leading to mesoporosity is introduced into individual zeolite single crystals primarily during the crystallization of the zeolite and not by post-treatment of the normally crystallized zeolitic material. Background technique [0003] For the transformation of many organic functional groups, homogeneous catalysts with high activity and selectivity have been developed. Homogeneously catalyzed reactions are usually carried out in suitable solvents under mild reaction conditions, in which not only the starting materials and metal catalysts are dissolved, but also the reaction products. From these complex mixtu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/06B01J29/40B01J31/22B01J29/03B01J29/076B01J29/48B01J32/00B01J35/10C07C51/265C07D301/03C07D301/12C07D303/04
CPCC07D301/14B01J29/061B01J29/076B01J29/48B01J35/10B01J2229/60C07D301/12C07D303/04Y02P20/50B01J35/633
Inventor K·赫布斯特M·布鲁尔森I·施密特C·J·H·雅各布森
Owner HALDOR TOPSOE AS