Method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin manganese (II)/Zn (II) salt

A technology of synergistic catalysis and manganese porphyrin, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of reducing the selection of cycloalkyl alcohols and cycloalkyl ketones Problems such as non-resistance, increasing the uncontrollability of the reaction system, and poor selectivity of the target product can achieve the effects of high selectivity, inhibition of disordered diffusion, and low environmental impact

Pending Publication Date: 2020-11-27
ZHEJIANG UNIV OF TECH
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  • 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 and oxidizing cycloparaffin through confined metalloporphyrin manganese (II)/Zn (II) salt
  • Method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin manganese (II)/Zn (II) salt
  • Method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin manganese (II)/Zn (II) salt

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Experimental program
Comparison scheme
Effect test

Embodiment 47

[0024] Example 47 is a scale-up experiment 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 manganese (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 7.06%, the...

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 manganese (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 6.88%, the ...

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Abstract

The invention discloses a method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin manganese (II)/Zn (II) salt. The preparation method comprises the following steps: dispersing confined metalloporphyrin manganese (II) (1*10<-4>%-0.1%, mol/mol) and Zn (II) salt (0.01%-10%, mol/mol) into cycloparaffin; and sealing the reaction system, heating to 90-150 DEGC while stirring, introducing an oxidant, keeping the set temperature and pressure, carrying out stirring to react for 2.0-24.0 hours, and carrying out after-treatment on the reaction solution to obtain the products cycloalkyl alcohol and cycloalkyl ketone. The method disclosed by the invention has the advantages of high cycloalkyl alcohol and cycloalkyl ketone selectivity, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of cycloalkyl hydroperoxide is low, and the safety coefficient is high. The invention provides an efficient, feasible and safe method for synthesizing cycloalkyl alcohol and cycloalkyl ketone through selective catalytic oxidation of cycloparaffin.

Description

technical field [0001] The invention relates to a method for synergistically catalyzing and oxidizing cycloalkane to synthesize cycloalkanol and cycloalkanone by localized metalloporphyrin manganese(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...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/33C07C29/50C07C49/403C07C49/413C07C35/08C07C35/20C07C35/205C07C49/395C07C35/06C07C27/12B01J31/22
CPCC07C45/33C07C29/50B01J31/183C07C2601/08C07C2601/14C07C2601/20C07C2601/18B01J2231/70B01J2531/025B01J2531/72B01J2531/26C07C49/403C07C49/413C07C35/08C07C35/20C07C35/205C07C49/395C07C35/06
Inventor 沈海民倪家业
Owner ZHEJIANG UNIV OF TECH
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