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

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Problems solved by technology

The catalyst is separated from the reaction mixture by n

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

Examples

Experimental program
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Example Embodiment

[0050] Example 1: Preparation of organic ligand polymer

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

[0052]

[0053] The degree of polymerization n is 450-550, and it has a hierarchical pore structure including macropores, mesopores and micropores. The measured BET specific surface a...

Example Embodiment

[0054] Example 2: Preparation of organic ligand polymer

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

Example Embodiment

[0056] Example 3: Preparation of solid heterogeneous catalyst containing 2wt% Rh

[0057] Under 298K and nitrogen atmosphere, 50.10 mg of rhodium acetylacetonate dicarbonyl (I) was added to a three-necked flask containing 100.0 ml of tetrahydrofuran solvent, stirred to dissolve, and 1.0 g of the multistage hole prepared in Example 1 was added. Structure P-containing ligand polymer, the mixture is stirred at 298K and a nitrogen atmosphere for 24 hours, and then the solvent is vacuumed off at room temperature to obtain the polymerized P-containing ligand with a hierarchical pore structure It is a solid heterogeneous catalyst of supported metal Rh. The above-prepared solid heterogeneous catalyst composed of tris (4-vinylphenyl) phosphine polymer with hierarchical pore structure self-supporting metal components was packed into a fixed bed reactor, and a molar ratio of 1:2 Ethylene gas and CO / H as olefin raw materials 2 Mixed gas (where H 2 :CO volume ratio=1:1), under 393K, 1.0MPa, ...

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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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