Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin manganese (II)/Cu (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: 2020-11-17
ZHEJIANG UNIV OF TECH
View PDF7 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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 high reaction temperature, low conversion rate of substrate, poor selectivity of target product, especially the generation of aliphatic diacid 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin manganese (II)/Cu (II) salt
  • Method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin manganese (II)/Cu (II) salt
  • Method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin manganese (II)/Cu (II) salt

Examples

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 0.3996g (2.200mmol) copper 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), stirring at room temperature for 30 min to reduce the generated peroxide. Using acetone as solvent, the resulting reaction mixture was adjusted to 100 mL. Pipette 10mL of the resulting solution, and use toluene as an internal standard for gas chromatographic analysis; pipette 10mL of the resulting solution, and use benzoic acid as an internal standard for liquid chromatographic analysis. The conversion of cyclohexane was 7.23%, 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 0.3996g (2.200mmol) copper 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 ), stirring at room temperature for 30 min to reduce the generated peroxide. Using acetone as solvent, the resulting reaction mixture was adjusted to 100 mL. Pipette 10mL of the resulting solution, and use toluene as an internal standard for gas chromatographic analysis; pipette 10mL of the resulting solution, and use benzoic acid as an internal standard for liquid chromatographic analysis. The conversion rate of cyclohexane was 7.05%...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a method for synergistically catalyzing oxidization of cycloalkane by using confinement metalloporphyrin manganese (II) / Cu (II) salt. The method comprises the following steps:dispersing confinement metalloporphyrin manganese (II) (1*10<-4>-0.1%, mol / mol) and Cu (II) salt (0.01-10%, mol / mol) in cycloalkane, sealing a reaction system, heating the reaction system to 90-150 DEG C while stirring, introducing an oxidant, keeping the reaction system at a set temperature and a set pressure, carrying out stirring and reacting for 2.0-24.0 hours, and performing post-treatment on a reaction solution to obtain products, namely cycloalkyl alcohol and cycloalkyl ketone. The method disclosed by the invention has the advantages of high selectivity of cycloalkyl alcohol and cycloalkyl ketone, 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 cycloalkane oxidation to cycloalkane to synthesize cycloalkanol and cycloalkanone by localized metalloporphyrin manganese(II) / Cu(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 ) as an oxidizing agent, carried out at 150°C to 170°C, the main problems are high r...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/50C07C35/08C07C45/33C07C49/403B01J31/22B01J31/28B01J31/30C07C29/76C07C29/78C07C29/80C07C45/81C07C45/82
CPCC07C29/50C07C45/33B01J31/183B01J31/28B01J31/30C07C29/76C07C29/78C07C29/80C07C45/81C07C45/82C07C2601/14B01J2231/70B01J2531/025B01J2531/72C07C35/08C07C49/403
Inventor 沈海民倪家业
Owner ZHEJIANG UNIV OF TECH
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com