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Catalyst containing covalent organic framework polymer material, preparation method and application of catalyst and method for catalytically oxidizing alkane

A technology of covalent organic frameworks and polymer materials, applied in the preparation of organic compounds, organic compound/hydride/coordination complex catalysts, carbon compound catalysts, etc., can solve high cyclohexanone selectivity and poor catalyst stability , reduce economic value and other issues, and achieve the effect of high ketone-alcohol ratio, high selectivity, and high activity selectivity

Pending Publication Date: 2021-12-10
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The generation of highly synergistic peroxidation products affects the overall selectivity of cyclohexanone and cyclohexanol, reducing the economic value of the entire reaction
At present, a number of technologies have disclosed the method of metalloporphyrin or phthalocyanine to catalyze the oxidation of cyclohexane. US280115 and US5120882 disclose the method of metalloporphyrin catalytic oxidation of cyclohexane under the system of benzene, acetic acid, etc., and US4917784 discloses the method of iron porphyrin oxidation. The method of catalyzing the oxidation of cyclohexane under the coexistence of phyllin and manganese porphyrin and photosensitizer, the catalysts used in these technologies are basically homogeneous catalysts such as metalloporphyrin or phthalocyanine, and metalloporphyrin or metalphthalocyanine are used as catalysts to catalyze Although the method for oxidizing cyclohexane can obtain higher cyclohexane conversion rate and KA oil selectivity, it cannot obtain higher cyclohexanone selectivity, and the cyclohexanone selectivity of porphyrin catalyzed oxidation cyclohexane is 40% Left and right, the product KA oil still contains more cyclohexanol, and the stability of the catalyst is poor, so it is difficult to separate from the product

Method used

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  • Catalyst containing covalent organic framework polymer material, preparation method and application of catalyst and method for catalytically oxidizing alkane
  • Catalyst containing covalent organic framework polymer material, preparation method and application of catalyst and method for catalytically oxidizing alkane
  • Catalyst containing covalent organic framework polymer material, preparation method and application of catalyst and method for catalytically oxidizing alkane

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preparation example Construction

[0032] The preparation method of the covalent organic framework polymer material described in the present invention can use 1,2,4,5-benzenetetracarbonitrile as a structural synthesis monomer, metal M n+ (M is iron, copper, cobalt, nickel, manganese, zinc, platinum, palladium, n is the valence) as the active center, with 1,8-diazabicycloundec-7-ene (DBU) as the catalyst The polymerization reaction to obtain a covalent organic framework polymer material, for example, comprises the following steps:

[0033] Take monomer 1,2,4,5-benzene tetracarbonitrile and metal source M n+ Dissolve in a solvent, M is selected from iron, copper, cobalt, nickel, manganese, zinc, platinum, palladium, etc. After adding a catalyst such as 1,8-diazabicycloundec-7-ene (DBU), mix Uniform; heat up to 70°C-220°C for reaction, cool down after reaction, wash and separate.

Embodiment approach

[0034] According to a preferred embodiment of the present invention, the mass ratio of the covalent organic framework polymer material to the carrier is (1-10):100, thereby improving the oxidation activity of the catalyst and the selectivity of the target product.

[0035] According to the present invention, the type of the carrier has no special requirements, such as one or more of molecular sieves, alumina, sepiolite, reduced graphene oxide, carbon nanotubes, carbon black and carbon fibers, according to one of the present invention In a preferred embodiment, the preferred carrier is reduced graphene oxide.

[0036] In the present invention, reduced graphene oxide refers to single-layer graphene obtained by reducing graphene oxide, for example, single-layer graphene obtained by reduction with hydrazine hydrate. Preferably the specific surface area of ​​reduced graphene oxide is 50-2000m 2 / g.

[0037] The present invention provides a method for preparing a catalytic oxidati...

preparation Embodiment 1

[0075] Prepare according to the method disclosed in CN108409976A, adopt the method of CN108409976A embodiment to prepare the covalent organic polymer material of the present invention, specifically as follows:

[0076] Covalent organic framework polymers (COFs) BTC ) Synthesis of materials

[0077]

[0078] Take monomer 1,2,4,5-pyrene tetracarbonitrile and excess metal chloride MCl x (M is iron) is dissolved in a solvent, and after adding a catalyst 1,8-diazabicycloundec-7-ene (DBU) of 5% of the total volume of the catalyst in the solution, the mixture is uniformly mixed. After raising the temperature to 70° C. for 15 minutes and reacting for 15 minutes, the temperature was raised to 220° C. and stirred for 4 hours. Gradually lower to room temperature, the color of the solution becomes dark green or black, the reaction is stopped, and the dark green product is obtained after the solvent is spin-dried, and the final product COF is obtained by centrifugation after washing w...

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Abstract

The invention provides a catalyst containing a covalent organic framework polymer material, a preparation method and application of the catalyst and a method for catalytically oxidizing alkane. The catalyst contains a carrier and a covalent organic framework polymer material which is loaded on the carrier and has a repetitive structure unit as shown in a formula (I), wherein M is one or more metal atoms of iron, copper, cobalt, nickel, manganese, zinc, palladium and platinum. The catalytic oxidation catalyst contains the covalent organic framework polymer material, has the remarkable advantages of high activity and high selectivity when being used for a catalytic oxidation reaction, and has the remarkable advantage of high ketone-alcohol ratio when being used for an alkane oxidation reaction, particularly a cyclohexane oxidation reaction.

Description

technical field [0001] The invention relates to a catalyst containing a covalent organic framework polymer material, a preparation method and application thereof, and a method for catalytically oxidizing alkanes. Background technique [0002] The selective oxidation of cyclohexane to cyclohexanone and cyclohexanol (KA oil) is one of the important reactions in petrochemical industry, and it is also a research hotspot of many researchers. This is because most of caprolactam and adipic acid (monomers of nylon 6 and nylon 66) are produced by oxidation of cyclohexane, and the market demand for these two substances is large, and cyclohexanone has a higher industrial value. However, the efficiency of cyclohexane oxidation in the traditional industry is low, the environment is seriously polluted, and it is difficult to meet the needs of the market. In the traditional industrial cyclohexane radical oxidation, cyclohexane reacts to produce cyclohexyl hydroperoxide as an intermediate...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/06B01J31/26B01J37/02B01J37/08C07C35/08C07C29/50C07C49/403C07C45/33
CPCB01J31/06B01J31/26B01J37/0213B01J37/0203B01J37/08C07C29/50C07C45/33C07C2601/14C07C2531/06B01J2231/70C07C35/08C07C49/403
Inventor 向中华夏辉赵云
Owner BEIJING UNIV OF CHEM TECH