Preparation method of ferromagnetic nanoparticle supported rhodium complex hydroformylation catalyst

Abstract

The invention provides a preparation method of a ferromagnetic nanoparticle supported rhodium complex hydroformylation catalyst. The method comprises the following step: bonding a rhodium complex to the surface of the superparamagnetic Fe3O4 nanoparticles by a bridging ligand to obtain the ferromagnetic nanoparticle supported rhodium complex hydroformylation catalyst. The invention provides a catalyst prepared by the method and application of the catalyst in hydroformylation reaction. According to the SPION-Rh catalyst, the nanoparticles with huge surface area are combined with rhodium to construct the nano catalytic cluster, thereby being beneficial to enhancing the catalytic efficiency. The catalyst has favorable activity in hydroformylation reaction. After introducing the magnetic particles, the metal rhodium can be simply recovered by applying an external magnetic field, thereby easily solving the problem of difficulty in recovery of rhodium in the homogeneous catalysis in industry.

Description

technical field [0001] The invention relates to a preparation method of a hydroformylation catalyst with rhodium complex supported by ferromagnetic nanoparticles, belonging to the field of fine petrochemical industry. Background technique [0002] The hydroformylation reaction is olefin and synthesis gas (CO / H 2 ) under catalyst conditions to prepare an aldehyde with one carbon more than the raw material olefin, which is the earliest industrialized process in the homogeneous complexation catalysis process. Hydroformylation produces cheap and easily available olefins into high value-added aldehydes, providing a new route for the high-value conversion of olefins. Aldehydes have active carbonyl groups and are important organic chemicals that can be used as intermediates in organic synthesis. Alcohols can be used as solvents, wetting agents, surfactants and the main raw materials for the production of plasticizers. [0003] Since the German Otto Roelen invented the hydroformy...

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Problems solved by technology

[0004] The second generation is a cobalt catalyst modified by tertiary phosphine, such as the modified cobalt method (cobalt phosphine catalyst, US Pat.3239566) of Shell (Shell), although it has a higher ratio of positive and negative, the catalyst cost is higher, and the activity lower

[0005] The third generation is an oil-soluble rhodium ligand complex catalyst, and is also the most widely used hydroformylation catalyst in industry, such as the rhodium-tertiary phosphine method (US Pat.3527809, US Pat.3527809, US Pat. Pat.4247486, US Pat.5105018) etc., the catalyst has higher activity, selectivity and milder reaction conditions, but the product aldehyde and the catalyst are in a uniform liquid phase, the separation of the product and the catalyst and the separation of the catalyst Recovery usually adopts the method of distillation or vacuum distillation (as U.S. Patent No. 4,528,403), which is not suitable for catalyzers that are easily decomposed by heat, especially for the hydroformylation of higher carbon olefins, the boiling point of product aldehyde is higher, The method of separating the catalyst by distillation often leads to problems such as product polymerization, catalyst decomposition and deactivation

[0006] The fourth generation is a water-soluble rhodium-phosphine composite catalyst, such as US Pat.4248802. The catalyst and the product are easily separated, and the process flow is simple. However, due to the low mass transfer efficiency of the two-phase reaction, the addition of a phase transfer agent will cause separation problems. May even cause emulsification and increase the difficulty of phase separation

[0008] The disclosed technical scheme of CN10144475A adopts haloalkyltrimethylsilane and diphenylphosphine lithium as coupling agent, and rhodium complex is immobilized on mesoporous molecular sieve or nano silicon dioxide, and the catalyst active group prepared by this method is solid The load is firm, not easy to lose, and the catalyst and the product can be separated well, but the catalyst activity is low, resulting in low olefin conversion

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