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

Abstract

The invention discloses a phosphine-containing organic mixed polymer-metal heterogeneous catalyst and its use in butyraldehyde production. The heterogeneous catalyst comprises one, two or three of Rh, Co and Ir as active ingredients and utilizes a multistage pore-structure phosphine-containing organic mixed polymer as a carrier. The phosphine-containing organic mixed polymer is prepared from an alkylene-containing polydentate organic phosphine ligand and a single dentate organic phosphine ligand through copolymerization. The coordination bond-type heterogeneous catalyst is suitable for a fixed bed reactor, a slurry bed reactor, a bubbling bed reactor and a trickle-bed reactor. The heterogeneous catalyst has good effects in hydrogen-propene formylation preparation of butyraldehyde, can produce high-normal / isomeric ratio butyraldehyde with a normal / isomeric ratio of 25 or more and realizes product propane content less than 0.1%. The heterogeneous catalyst has good stability and can be simply and efficiently separated from reactants and products.

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 ...

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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

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