Phosphine-containing organic mixed polymer-metal heterogeneous catalyst and its preparation method and application

Abstract

The invention discloses a heterogeneous phosphine-containing organic polymer-metal catalyst with a hierarchical porous structure and its application in the production of butyraldehyde. One species and three species are used as the active components, and the multi-dentate organic phosphine ligands and monodentate organic phosphine ligands are copolymerized with multi-dentate organic phosphine ligands containing olefin groups, and the multi-dentate organic phosphine ligands are used as the carrier. . This coordination bond type heterogeneous catalyst is suitable for fixed bed, slurry bed, bubbling bed and trickle bed reactors. The heterogeneous catalyst provided by the invention has good performance in the production of butyraldehyde from propylene hydroformylation, and can produce butyraldehyde with a high isotropic ratio. The isotropic ratio can reach more than 25, and the propane content in the obtained product is lower than 0.1%, the heterogeneous catalyst has good stability, and the separation of the catalyst, reactants and products is simple and efficient.

Description

technical field [0001] The invention belongs to the field of heterogeneous catalysis and fine chemical industry, and specifically relates to a phosphine-containing organic mixed polymer-metal heterogeneous catalyst and its preparation method and its application in the reaction of propylene hydroformylation to produce butyraldehyde. Background technique [0002] In recent years, atomic economy reactions have become one of the hotspots in green chemistry research. The hydroformylation reaction of olefins is a typical atom-economic reaction, which refers to the reaction of olefins with CO and H 2 Under the action of a catalyst, aldehydes are generated, 100% of the atoms in the raw material molecules are converted into products, and the waste is zero discharged. [0003] The product of the olefin hydroformylation reaction is an aldehyde with one more carbon atom than the olefin, and the normal aldehyde has become the target product of most hydroformylation reactions because of ...

AI Technical Summary

Problems solved by technology

However, homogeneous catalysts are not easy to recycle and ligand synthesis is difficult

[0006] Patent CN1210514A reports the Rh complex catalyst for olefin hydroformylation reaction. The Rh complex uses a multi-dentate organic nitrogen compound as a ligand, and the ligand contains at least one tertiary nitrogen group that can be protonated in a weak acid , but the catalyst also faces the problem that it is not easy to recycle

[0007] In the patent CN102911021A, the composite catalytic system composed of Rh complex, biphenyl skeleton or binaphthyl skeleton diphosphine ligand, and triphenylphosphine or phosphite triphenyl ester monophosphine ligand is used as a catalyst. The normal aldehyde has higher selectivity in the formylation reaction, which reduces the amount of expensive bisphosphine ligands, but the catalytic system is still homogeneous

[0008] In the patent CN1986055A, bisphosphite and triphenylphosphine are also used to cooperate with Rh to form a composite catalytic system. In the hydroformylation reaction of propylene, the molar ratio of n-butyraldehyde and isobutyraldehyde is greater than 20, which significantly prolongs the bisphosphite The service life of the phosphate ligand significantly reduces the amount of triarylphosphine, but it is still a homogeneous reaction in nature, and it also faces the problem of difficulty in catalyst recycling

Images