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Olefin hydroformylation heterogeneous Co-based catalyst and preparation method thereof

A heterogeneous catalyst, olefin hydroformyl technology, applied in the direction of carbon monoxide reaction preparation, metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, etc., can solve the problem of low yield of the target product, Achieve good recycling performance, not easy to lose, high activity effect

Active Publication Date: 2019-05-31
NINGXIA UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In order to overcome the separation technical problems of homogeneous catalysts and solve the problem of low yield of target products of existing heterogeneous catalysts, the present invention proposes a heterogeneous Co-based catalyst for olefin hydroformylation and a preparation method thereof, in which the Co element is supported On a carrier with a high specific surface area and modified to form an active component of M1 x M2 y CoAs z The Co-based supported heterogeneous catalyst changes the electronic state of Co atoms, which can not only make the active sites uniformly dispersed, but also improve its activity, and has high stability in the air

Method used

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  • Olefin hydroformylation heterogeneous Co-based catalyst and preparation method thereof

Examples

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Effect test

Embodiment 1

[0045] Prepare 0.1mol / L cobalt chloride solution. Weigh 1.6g of NiCl 2 ﹒ 6H 2 O, dissolve in 68mL of 0.1mol / L cobalt chloride solution, add 2g of carrier SBA-15, stir for 24h, and sonicate for 2h. Evaporate to dryness in a stirrer, dry in a vacuum oven at 80 °C for 10 h; in a nitrogen atmosphere, roast at 350 °C for 5 h, transfer the obtained powder to a three-necked flask, add 68 mL of deionized water, N 2 Stir evenly under the ice-water bath under the atmosphere, prepare 0.1mol / L sodium borohydride solution, measure 28mL of the solution and add it dropwise to the three-necked flask, and react for 0.5h after the addition is completed; wash the obtained suspension until neutral Then use water and ethanol to wash 3 times to obtain the desired catalyst Na-Ni-Co-B / SBA-15. 1-hexene hydroformylation activity evaluation: feed gas composition CO: H 2 = 1:1, the reaction temperature is 120 o C, the rotation speed is 1200 r.p.m, the reaction pressure is 5MPa, and the reaction time...

Embodiment 2

[0047] Prepare 0.1mol / L cobalt chloride solution. Weigh 0.8g of FeCl 3 ﹒ 6H 2 O, dissolve in 68mL of 0.1mol / L cobalt chloride solution, add 2g of carrier MCM-41, stir for 24h, and sonicate for 2h. Evaporate to dryness in a stirrer, dry in a vacuum oven at 80 °C for 10 h; in a nitrogen atmosphere, roast at 350 °C for 5 h, transfer the obtained powder to a three-necked flask, add 68 mL of deionized water, N 2 Stir evenly under the ice-water bath under the atmosphere, prepare 0.1mol / L potassium borohydride solution, measure 24mL of the solution and add it dropwise to the three-necked flask, and react for 0.5h after the addition is completed; wash the obtained suspension until neutral Then wash with water and ethanol for 3 times to obtain the required catalyst K-Fe-Co-B / MCM-41. 1-octene hydroformylation activity evaluation: feed gas composition H 2 : CO= 1:1, the reaction temperature is 120 o C, the rotation speed is 1200 r.p.m, the reaction pressure is 5MPa, and the reaction...

Embodiment 3

[0049] Prepare 0.1mol / L cobalt chloride solution. Weigh 0.5g of RhCl 2 ﹒ 6H 2 O, dissolve in 68mL of 0.1mol / L cobalt chloride solution, add 2g carrier ZSM-5, stir for 24h, and sonicate for 2h. Evaporate to dryness in a stirrer, dry in a vacuum oven at 80 °C for 10 h; in a nitrogen atmosphere, roast at 350 °C for 5 h, transfer the obtained powder to a three-necked flask, add 68 mL of deionized water, N 2 Stir evenly under the ice-water bath under the atmosphere, prepare 0.1mol / L calcium borohydride solution, measure 20mL of the solution and add it dropwise to the three-necked flask, and react for 0.5h after the addition is completed; wash the obtained suspension until neutral It is then washed with water and ethanol for 3 times to obtain the desired catalyst Ca-Rh-Co-B / ZSM-5. Evaluation of 1-octene hydroformylation activity: feed gas composition H 2 : CO= 1:1, the reaction temperature is 120 o C, the rotation speed is 1200 r.p.m, the reaction pressure is 5MPa, and the reac...

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Abstract

The invention relates to an olefin hydroformylation heterogeneous Co-based catalyst and a preparation method thereof. The technology problem of homogenous phase catalyst separation is solved, and theproblem that an existing heterogenous catalyst is low in target product yield is solved. A Co element is loaded on a carrier with the high specific surface area, modification is performed, a Co-basedload type heterogenous catalyst with M1xM2yCoAx being the active ingredient is formed, the Co atom electron state is changed, active loci can be evenly dispersed, the activity can be improved, and thehigh stability in air is achieved. The preparation method of the catalyst is simple and easy to store, and the obtained target product aldehyde yield is high.

Description

technical field [0001] The invention belongs to the technical field of catalyst preparation, and relates to a heterogeneous Co-based catalyst for olefin hydroformylation and a preparation method thereof. Background technique [0002] The product of olefin hydroformylation is an aldehyde or alcohol with one carbon more than the raw material olefin. It is an important organic chemical raw material for the production of plasticizers, surfactants, additives, solvents, intermediates and fragrances. Homogeneous metal rhodium ligand catalysts are currently mainly used in olefin hydroformylation reactions. Homogeneous catalysts have excellent catalytic activity, showing outstanding conversion and selectivity, and play an important role in industrial applications. However, the homogeneous catalyzed hydroformylation reaction has disadvantages such as high catalyst cost, difficult separation and recovery, and high separation cost, which largely limits its development. Therefore, in rec...

Claims

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Application Information

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IPC IPC(8): B01J29/03B01J29/46B01J27/185B01J23/78C07C45/50C07C47/02
Inventor 范素兵王启馨戎静雅郭靖赵天生张建利马清祥高新华
Owner NINGXIA UNIVERSITY
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