Molecular sieve encapsulated rhodium heterogeneous core-shell catalyst for olefin hydroformylation, and catalytic method thereof

A heterogeneous catalyst, catalyst technology, applied in molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve problems such as difficult industrial production, achieve easy recycling, improve sintering resistance and catalytic activity, High temperature sintering stability and easy effect

Active Publication Date: 2019-06-14
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, it is difficult to achieve industrial production of single-atom catalysts, and such catalysts are currently limited to the laboratory research stage

Method used

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  • Molecular sieve encapsulated rhodium heterogeneous core-shell catalyst for olefin hydroformylation, and catalytic method thereof
  • Molecular sieve encapsulated rhodium heterogeneous core-shell catalyst for olefin hydroformylation, and catalytic method thereof
  • Molecular sieve encapsulated rhodium heterogeneous core-shell catalyst for olefin hydroformylation, and catalytic method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] (1) Thiolation treatment of S-1 seed crystal

[0030] Take 0.2 g of self-made S-1 seed crystals with a size of about 150 nm, disperse them into 20 mL of ethanol, and add 2.86 mmol of 3-mercaptopropyltrimethoxysilane dropwise. The seed crystal suspension was stirred at 60° C. for 6 h to obtain S-1 seed crystals that had undergone mercaptolation treatment. The self-made S-1 seed crystal in this step can be prepared by any method known in the art, such as the preparation of the S-1 seed crystal mentioned in Chinese invention patent application CN107442155A.

[0031] (2) Loading of rhodium precursor solution

[0032] Disperse the mercapto-treated S-1 seed crystals obtained in step (1) into 15 mL of deionized water to obtain mixture A; take 0.005 g of RhCl 3 The powder was dissolved in 5mL deionized water to obtain solution B. Add B into A, stir at room temperature for 4h, and obtain S-1 seed crystals supported by rhodium ions (Rh 3+ / S-1).

[0033] (3) Rh 3+ / S-1 epit...

Embodiment 2

[0038] (1) The thiolation treatment of the S-1 seed crystal is the same as that in Example 1.

[0039] (2) The loading of the rhodium precursor solution is the same as in Example 1.

[0040] (3) Rh 3+ / S-1 epitaxial growth of S-1 shell

[0041] According to TEOS:TPAOH:H 2 The molar ratio of O=40:10:20000 is used to prepare the S-1 shell layer synthesis solution, and the Rh obtained in step (2) 3+ / S-1 seed crystals were added to the synthesis solution and aged for 2 hours at room temperature. After the aging, the synthetic solution was put into a synthesis kettle with a polytetrafluoroethylene liner, and hydrothermally synthesized at 170° C. for 24 hours in a rotary oven at a speed of 3 r / min. After the synthesis is completed, the mixed liquid in the polytetrafluoroethylene lining is centrifuged in a high-speed centrifuge, and the solid product is taken for drying, and roasted in a muffle furnace at 550 ° C for 6 hours, and finally the S-1 zeolite molecular sieve encapsula...

Embodiment 3

[0045] (1) The thiolation treatment of the S-1 seed crystal is the same as that in Example 1.

[0046] (2) The loading of the rhodium precursor solution is the same as in Example 1.

[0047] (3) Rh 3+ The / S-1 epitaxially grown S-1 shell is the same as in Example 2.

[0048] (4) Application of Rh@S-1 core-shell catalyst in hydroformylation process

[0049] Weigh the Rh@S-1 catalyst and reactants with a molar ratio of metal rhodium and 1-hexene of 1:6400, and disperse them in 8 mL of toluene solvent. CO and H in a 1:1 volume ratio 2 As a reaction gas, after purging the reaction device 4 times, the reaction was carried out at 80° C. for 12 hours under a pressure of 5 MPa. After the reaction, the catalyst and feed liquid are centrifuged, and the solid catalyst is dried and recovered, and the liquid product is detected by gas chromatography (chromatographic column: SE-30, FID).

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Abstract

The invention discloses a molecular sieve encapsulated rhodium heterogeneous core-shell catalyst for olefin hydroformylation, and a catalytic method thereof, and belongs to the field of novel catalysis materials. Submicron Silicalite-1 (S-1) zeolite molecular sieve grain supported rhodium ions are used as a crystal seed to induce epitaxial growth of an S-1 shell, a ruthenium catalytically active species is encapsulated in the S-1 zeolite molecular sieve to form the core-shell Rh@S-1 catalyst, and the catalyst is used in a heterogeneous hydroformylation reaction to synthesize normal aldehydes.The olefin conversion rate and the aldehyde yield are respectively more than 95%, a normal-to-iso ratio of the hydroformylation products is 1.1-2.0, and the catalyst can be recycled. Compared with homogeneous catalyst system industrially applied at present, the catalyst in the invention solves the problem of high energy consumption needed by separation of the catalyst and the hydroformylation products, and avoids the degradation abuse of the catalytically active component due to the high temperature rectification process during separation of the catalyst, so the recycling of the catalyst is benefited, and the catalyst has a broad application prospect.

Description

technical field [0001] The invention belongs to the field of novel catalytic materials, and in particular relates to a novel heterogeneous core-shell catalyst applied in olefin hydroformylation reaction. The catalyst is formed by encapsulating rhodium nanoparticles in Silicalite-1 zeolite. Background technique [0002] As the world's largest industrial catalytic reaction, CO and H 2 Homogeneous rhodium complexes containing phosphine ligands are often used as catalysts for the hydroformylation of olefins to aldehydes in ambient atmosphere. This type of homogeneous catalyst has the advantages of high catalytic activity and high product regioselectivity (the molar ratio of normal aldehyde and isomeric aldehyde in the aldehyde product, that is, the normal / iso ratio). However, separating the homogeneous rhodium catalyst from the reaction products by processes such as rectification consumes a lot of energy. In addition, the high temperature conditions in the separation process w...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/035C07C45/50C07C47/02
CPCY02P20/584
Inventor 张雄福刘存刘嵩刘海鸥
Owner DALIAN UNIV OF TECH
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