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Solid heterogeneous catalyst for hydroformylation of olefins, preparation method and application thereof

A heterogeneous catalyst, olefin hydroformyl technology, applied in the direction of carbon monoxide reaction preparation, organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, etc., can solve the problem of unsatisfactory reaction results and achieve high Stability, broad industrial prospects, simple preparation method

Active Publication Date: 2015-06-17
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst is separated from the reaction mixture by nanofiltration and the reaction result is not satisfactory

Method used

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  • Solid heterogeneous catalyst for hydroformylation of olefins, preparation method and application thereof
  • Solid heterogeneous catalyst for hydroformylation of olefins, preparation method and application thereof
  • Solid heterogeneous catalyst for hydroformylation of olefins, preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Embodiment 1: Preparation of organic ligand polymer

[0051] Under 298K and a nitrogen gas protection atmosphere, 10.0 grams of tris (4-vinylphenyl) phosphine was dissolved in 100.0 ml of tetrahydrofuran solvent, and 1.0 grams of free radical initiator azobisisobutyronitrile was added to the above solution, and stirred for 2 hours . The stirred solution was allowed to stand at 373K under a nitrogen atmosphere for 24h. After the above-mentioned standing solution is cooled to room temperature, the solvent is vacuumed off at room temperature (about 298K), and the tris(4-vinylphenyl)ylphosphine is polymerized by solvothermal method to obtain a compound containing P ligand polymer. The three (4-vinylphenyl) phosphine ligand polymer carrier polymerization technical route in the present embodiment is as follows:

[0052]

[0053] Among them, the degree of polymerization n is 450-550, with a hierarchical pore structure including macropores, mesopores and micropores, and t...

Embodiment 2

[0054] Embodiment 2: Preparation of organic ligand polymer

[0055] The preparation process is the same as in Example 1, except that bis(4-vinylphenyl)-2-pyridylphosphine monomer is used instead of tris(4-vinylphenyl)phosphine monomer.

Embodiment 3

[0056] Embodiment 3: preparation of solid heterogeneous catalyst containing 2wt%Rh

[0057] Under 298K and a nitrogen gas protection atmosphere, 50.10 mg of rhodium acetylacetonate dicarbonyl (I) was added to a three-necked flask filled with 100.0 ml of tetrahydrofuran solvent, stirred and dissolved, and 1.0 gram of the multi-level pore compound prepared in Example 1 was added. structure of the P ligand-containing polymer, the mixture was stirred at 298K and nitrogen gas protection atmosphere for 24 hours, and then the solvent was vacuumed off at room temperature, and the P-ligand-containing polymer with a hierarchical porous structure was obtained. Solid Heterogeneous Catalysts from Supported Metal Rh. The above prepared solid heterogeneous catalyst consisting of tri(4-vinylphenyl) phosphine polymer self-supporting metal component with hierarchical pore structure is loaded into a fixed bed reactor, and the molar ratio of 1:2 is passed through Ethylene gas and CO / H as olefin ...

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Abstract

The invention relates to a novel solid heterogeneous catalyst for hydroformylation of olefins, a preparation method and an application thereof and relates to a solid heterogeneous catalyst applied in hydroformylation of olefins. The solid heterogeneous catalyst is composed of a metal component and an organic ligand polymer, wherein the metal component is one or more selected from metallic Rh, Ir or Co; the organic ligand polymer is a polymer which is generated by polymerization of an organic ligand monomer containing P and alkylene and optional N by a solvothermal polymerization method and has large specific surface area and hierarchical porous structure; and the metal component reacts with P atom or N in the organic ligand polymer skeleton to form a coordinate bond and the coordinate bond exists in the state of single atomic dispersion. In hydroformylation of olefins, an intermediate active species which is similar to a homogeneous catalyst is generated in situ due to coordination between the metal component and P and / or N atom. The catalyst provided by the invention has excellent catalytic performance, is easy to separate and has high stability.

Description

technical field [0001] The invention relates to a solid heterogeneous catalyst for olefin hydroformylation reaction and its preparation method and application, belonging to the technical field of heterogeneous catalysis. Background technique [0002] Olefin hydroformylation is one of the important methods for the industrial synthesis of organic compounds such as aldehydes and alcohols. At present, more than 10 million tons of aldehydes and alcohols are produced by olefin hydroformylation technology every year in the world. This reaction can generate aldehydes from raw material olefins under less severe conditions, and the product aldehydes can be further converted into alcohols by hydrogenation. The homogeneous catalytic system has higher catalytic activity and selectivity of the target product under milder reaction conditions, but it is difficult to separate the catalyst from the reaction materials. Compared with homogeneous catalysis, the biggest advantage of heterogeneou...

Claims

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Application Information

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IPC IPC(8): B01J31/24B01J35/10C07C47/02C07C45/50
CPCY02P20/50
Inventor 丁云杰姜淼严丽林荣和
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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