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Method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin cobalt (II)/Zn (II) salt

A technology of synergistic catalysis, porphyrin cobalt, applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problem of reducing the selection of cycloalkyl alcohols and cycloalkyl ketones In order to achieve high selectivity, inhibition of disordered diffusion, and small environmental impact

Pending Publication Date: 2020-11-17
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, the industrial catalytic oxidation of naphthenes is mainly based on homogeneous Co 2+ or Mn 2+ As a catalyst, oxygen (O 2 ) is an oxidizing agent, which is carried out at 150°C to 170°C. The main problems are that the reaction temperature is high, the conversion rate of the substrate is low, and the selectivity of the target product is poor, especially the formation of aliphatic diacids is difficult to suppress (Applied Catalysis A, General 2019,575:120-131; Catalysis Communications 2019,132:105809)
The main root causes of the above problems are: (1) O 2 Oxidation of cycloalkanes mainly undergoes a disordered free radical diffusion process; (2) the oxidation intermediate product, cycloalkyl hydroperoxide, converts to the target oxidation products cycloalkanol and cycloalkanone through a free radical thermal decomposition path, which increases the inability of the reaction system. controllability, reducing the selectivity of cycloalkyl alcohols and cycloalkyl ketones

Method used

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  • Method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin cobalt (II)/Zn (II) salt
  • Method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin cobalt (II)/Zn (II) salt
  • Method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin cobalt (II)/Zn (II) salt

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Experimental program
Comparison scheme
Effect test

Embodiment 47

[0024] Example 47 is an enlarged case of catalytic oxidation of naphthenes.

Embodiment 1

[0026] In a 100mL stainless steel autoclave with polytetrafluoroethylene liner, 0.0036g (0.0024mmol) 5,10,15,20-tetrakis(2-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin cobalt (II) and 0.4036g (2.200mmol) zinc acetate are dispersed in 16.8320g (200mmol) cyclohexane, seal the reaction vessel, stir and heat up to 120°C, and feed oxygen to 1.00MPa . Stir and react at 120°C, 1.0MPa oxygen pressure, 600rpm for 8.0h. After completion of the reaction, cool to room temperature with ice water, add 1.3115g (5.00mmol) triphenylphosphine (PPh 3), stirred at room temperature for 30min to reduce the generated peroxide. Using acetone as solvent, the resulting reaction mixture was adjusted to 100 mL. Pipette 10 mL of the resulting solution, and use toluene as an internal standard for gas chromatography analysis; pipette 10 mL of the resulting solution, and use benzoic acid as an internal standard for liquid chromatography analysis. The conversion rate of cyclohexane is 8.21%, the sel...

Embodiment 2

[0028] In a 100mL stainless steel autoclave with polytetrafluoroethylene liner, 0.0036g (0.0024mmol) 5,10,15,20-tetrakis(1-naphthyl)-2,3,7,8,12,13 , 17,18-octabromoporphyrin cobalt (II) and 0.4036g (2.200mmol) zinc acetate are dispersed in 16.8320g (200mmol) cyclohexane, seal the reaction vessel, stir and heat up to 120°C, and feed oxygen to 1.00MPa . Stir and react at 120°C, 1.0MPa oxygen pressure, 600rpm for 8.0h. After completion of the reaction, cool to room temperature with ice water, add 1.3115g (5.00mmol) triphenylphosphine (PPh 3 ), stirred at room temperature for 30min to reduce the generated peroxide. Using acetone as solvent, the resulting reaction mixture was adjusted to 100 mL. Pipette 10 mL of the resulting solution, and use toluene as an internal standard for gas chromatography analysis; pipette 10 mL of the resulting solution, and use benzoic acid as an internal standard for liquid chromatography analysis. The conversion rate of cyclohexane was 8.02%, the s...

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Abstract

The invention provides a method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin cobalt (II) / Zn (II) salt. The method comprises the following steps: dispersing confinement metalloporphyrin cobalt (II) (0.001%-5%, g / mol) and Zn (II) salt (0.01%-10%, mol / mol) into cycloalkane, sealing a reaction system, carrying out heating to 90-150 DEG C while stirring, introducing an oxidant, keeping the reaction system at a set temperature and aset pressure, conducting stirring and reacting for 2.0-24.0 hours, and carrying out aftertreatment on a reaction solution to obtain products, namely cycloalkyl alcohol and cycloalkyl ketone. The method provided by the invention has the advantages of high naphthenic alcohol and naphthenic ketone selectivity, low reaction temperature, few byproducts, small environmental influence and the like. In addition; the content of cycloalkyl hydroperoxide is low; and a safety coefficient is high. The invention provides the efficient; feasible and safe method for synthesizing cycloalkyl alcohol and cycloalkyl ketone through selective catalytic oxidation of cycloalkane.

Description

technical field [0001] The invention relates to a method for synergistically catalyzing and oxidizing cycloalkane to synthesize cycloalkanol and cycloalkanone by localized metalloporphyrin cobalt(II) / Zn(II) salt, which belongs to the field of industrial catalysis and fine organic synthesis. Background technique [0002] Catalytic oxidation of naphthenes is a very important conversion process in the chemical industry. The oxidation products cycloalkanol and cycloalkanone are not only important organic solvents, but also important fine chemical intermediates, widely used in pesticides, medicines, dyes, surface Synthesis of fine chemical products such as active agents and resins, especially the production of polyamide fibers nylon-6 and nylon-66. At present, the industrial catalytic oxidation of naphthenes is mainly based on homogeneous Co 2+ or Mn 2+ As a catalyst, oxygen (O 2 ) is an oxidizing agent, which is carried out at 150°C to 170°C. The main problems are that the re...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/50C07C35/08C07C45/33C07C49/403B01J31/22B01J31/26C07C29/76C07C29/78C07C29/80C07C45/81C07C45/82
CPCC07C29/50C07C45/33B01J31/183B01J31/26C07C29/76C07C29/78C07C29/80C07C45/81C07C45/82C07C2601/14B01J2231/70B01J2531/025B01J2531/845C07C35/08C07C49/403
Inventor 佘远斌倪家业宁磊沈海民
Owner ZHEJIANG UNIV OF TECH
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