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Heterogeneous catalyst adopting phosphine-containing organic mixed polymer-metal as well as preparation and application of heterogeneous catalyst

A heterogeneous catalyst, catalyst technology, applied in the direction of organic compound/hydride/coordination complex catalyst, carbon monoxide reaction preparation, physical/chemical process catalyst, etc., can solve the problem of rapid catalyst deactivation and no catalyst recycling. , to achieve the effect of long catalyst life, improved metal utilization efficiency, and improved utilization efficiency

Active Publication Date: 2016-11-23
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

However, the problem of heterogeneity of homogeneous catalysts has not been fundamentally solved, the catalyst deactivation is very fast, and the recycling of catalysts has not been realized.
[0009] The hydroformylation of internal olefins has always been a difficult and hot topic in research. Chemists have devoted a lot of effort to the synthesis of homogeneous multidentate ligands applied to the hydroformylation of internal olefins, but there is no specific target for Emergence of heterogeneous catalysts and processes for internal olefin hydroformylation

Method used

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  • Heterogeneous catalyst adopting phosphine-containing organic mixed polymer-metal as well as preparation and application of heterogeneous catalyst
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  • Heterogeneous catalyst adopting phosphine-containing organic mixed polymer-metal as well as preparation and application of heterogeneous catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Under 298K and an inert gas protection atmosphere, 10.0 grams of Vinyl Biphephos monomer (attached figure 1 ) was dissolved in 100.0ml tetrahydrofuran solvent, and 2.5g comonomer tris (4-vinylphenyl) phosphine (L1) was added simultaneously; Hour. The stirred solution was moved to an autoclave, and polymerized by solvothermal polymerization at 373K and an inert gas atmosphere for 24 hours. After the above polymerized solution is cooled to room temperature, the solvent is removed under vacuum at room temperature to obtain an organophosphine mixed polymer carrier copolymerized with Vinyl Biphephos and tris(4-vinylphenyl)phosphine organic monomer. figure 2 It is a schematic diagram of Vinyl Biphephos organic mixed polymer carrier polymerization technology route. Take by weighing 3.13 milligrams of tricarbonyl rhodium acetylacetonate and be dissolved in 10.0 ml of tetrahydrofuran solvent, add 1.0 gram of organic mixed polymer carriers obtained by copolymerization of Vinyl...

Embodiment 2

[0044] In Example 2, except taking 10.0 grams of comonomer tris (4-vinylphenyl) phosphine (L1), replacing 2.5 grams of comonomer tris (4-vinylphenyl) phosphine (L1), the remaining The catalyst synthesis process is the same as in Example 1.

Embodiment 3

[0046] In Example 3, except that 0.1 gram of free radical initiator azobisisobutyronitrile was weighed instead of 1.0 gram of free radical initiator azobisisobutyronitrile, the rest of the catalyst synthesis process was the same as that of Example 1.

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Abstract

The invention discloses a heterogeneous catalyst adopting a hierarchical pore structure and adopting phosphine-containing organic mixed polymer-metal as well as preparation and an application of the heterogeneous catalyst in production of aldehyde with a high normal / isomeric ratio through internal olefin hydroformylation. In the heterogeneous catalyst, one, two or three of metal Rh, Co and Ir are taken as active components, and a phosphine-containing organic mixed polymer adopting the hierarchical pore structure is taken as a carrier and is prepared from multidentate organic phosphine ligands containing alkylene and monodentate organic phosphine ligands through copolymerization. The coordinate bond type heterogeneous catalyst is applicable to a fixed bed reactor, a slurry bed reactor, a bubble column reactor, a trickle-bed reactor and other reactors. The provided heterogeneous catalyst has good presentation in the internal olefin hydroformylation reaction, internal olefins are firstly isomerized to be terminal-group olefins under the action of the catalyst, a hydroformylation reaction is performed, corresponding normal aldehyde is selectively generated, accordingly, the normal / isomeric ratio of the product aldehyde is high and can be higher than 15, and the content of alkane in the obtained product is lower than 1%.

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, a preparation method thereof, and an application thereof in the production of high isocyanide by hydroformylation of internal olefins. Background technique [0002] Olefin hydroformylation (Hydroformylation, also known as OXO-Synthesis) refers to the olefin and synthesis gas (CO / H 2 ) to generate an aldehyde with one carbon higher than the raw material olefin, which is the first homogeneous complexation catalytic process to realize industrial production. The continuous development of olefin hydroformylation is mainly due to the impetus of the petrochemical industry. The petroleum cracking process and the Fischer-Tropsch synthesis process produce a large amount of olefins, which provide cheap synthetic raw materials for the hydroformylation reaction and make it in...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C47/02C07C45/50
CPCB01J31/06B01J31/24C07C45/49C07C47/02Y02P20/50
Inventor 丁云杰李存耀严丽
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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