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Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-222 (Co&Cu)

A bimetalloporphyrin, catalytic oxidation technology, applied in chemical instruments and methods, catalytic reaction, oxidation reaction preparation, etc., can solve the problem of reducing the selectivity of cycloalkyl alcohol and cycloalkyl ketone, increasing the uncontrollability of the reaction system, and the goal Problems such as poor product selectivity, to achieve the effect of high selectivity, inhibition of disordered diffusion, and small environmental impact

Pending Publication Date: 2020-12-18
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 catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-222 (Co&Cu)
  • Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-222 (Co&Cu)

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Synthesis of PCN-222(Co&Cu)-1: In a 35mL pressure-resistant reaction tube, T(4-COOH)PPCo(II)(0.0282g, 0.033mmol), T(4-COOH)PPCu(II)(0.0568 g, 0.067mmol), ZrCl 4 (0.1400g, 0.600mmol), benzoic acid (5.4000g, 44.3mmol) was dissolved in 16.0mL DMF, and ultrasonicated for 30min until all dissolved. The mixture was placed in an electric constant temperature blast drying oven at 120° C. for 48.0 hours of static reaction. After the reaction is complete, turn off the heating, cool to room temperature naturally, filter the crude product with suction and rinse with DMF and acetone successively, then transfer to a 10.0mL centrifuge tube, centrifuge for 5min in a low-speed centrifuge (3000rpm), pour out the upper layer, and dry the DMF Leach (3×8.0mL) until the upper layer is clear, dry acetone leaching (3×8.0mL) until the upper layer is clear, remove the solid in the lower layer, and dry at 90°C for 8.0h to obtain a brick red powder (0.0680g, 45.4% yield Rate).

Embodiment 2

[0029]Synthesis of PCN-222(Co&Cu)-2: In a 35mL pressure-resistant reaction tube, T(4-COOH)PPCo(II)(0.0424g, 0.05mmol), T(4-COOH)PPCu(II)(0.0425 g, 0.05mmol), ZrCl4 (0.1400g, 0.600mmol), benzoic acid (5.4000g, 44.3mmol) were dissolved in 16.0mL DMF, ultrasonic 30min until all dissolved. The mixture was placed in an electric constant temperature blast drying oven at 120° C. for 48.0 hours of static reaction. After the reaction is complete, turn off the heating, cool to room temperature naturally, filter the crude product with suction and rinse with DMF and acetone successively, then transfer to a 10.0mL centrifuge tube, centrifuge for 5min in a low-speed centrifuge (3000rpm), pour out the upper layer, and dry the DMF Leach (3×8.0mL) until the upper layer is clear, dry acetone leaching (3×8.0mL) until the upper layer is clear, remove the solid in the lower layer, and dry at 90°C for 8.0h to obtain a brick red powder (0.0687g, 45.2% yield Rate).

Embodiment 3

[0031] Synthesis of PCN-222(Co&Cu)-3: In a 35mL pressure-resistant reaction tube, T(4-COOH)PPCo(II)(0.0565g, 0.067mmol), T(4-COOH)PPCu(II)(0.0284 g, 0.033mmol), ZrCl 4 (0.1400g, 0.600mmol), benzoic acid (5.400g, 44.3mmol) was dissolved in 16.0mL DMF, ultrasonic 30min until all dissolved. The mixture was placed in an electric constant temperature blast drying oven at 120° C. for 48.0 hours of static reaction. After the reaction is complete, turn off the heating, cool to room temperature naturally, filter the crude product with suction and rinse with DMF and acetone successively, then transfer to a 10.0mL centrifuge tube, centrifuge for 5min in a low-speed centrifuge (3000rpm), pour out the upper layer, and dry the DMF Leach (3×8.0mL) until the upper layer is clear, dry acetone and leaching (3×8.0mL) until the upper layer is clear, remove the lower solid, and dry at 90°C for 8.0h to obtain a brick red powder (0.0697g, 45.8% yield Rate).

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Abstract

The invention relates to a method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-222 (Co&Cu), which comprises the following steps: dispersing bimetallic porphyrin MOFs PCN-222 (Co&Cu) in cycloalkane, the mass of which is 1-10% of the amount of a substance of cycloalkane, g / mol; and sealing the reaction system, heating to 90-150 DEG C while stirring, introducing anoxidant, keeping the set temperature and pressure, stirring to react for 2.0-24.0 hours, and carrying out after-treatment on the reaction solution to obtain the products naphthenic alcohol and naphthenic ketone. The method disclosed 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 the safety coefficient is high. The invention provides an efficient, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone through selective catalytic oxidation of cycloalkane.

Description

technical field [0001] The invention relates to a method for synthesizing cycloalkanol and cycloalkanone by catalytically oxidizing cycloalkane with double metal porphyrin MOFs PCN-222 (Co&Cu), 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 reaction temperature ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/33C07C29/50C07C49/403C07C49/413C07C35/08C07C35/20C07C35/205C07C49/395C07C35/06B01J31/22
CPCC07C45/33C07C29/50B01J31/183B01J31/1691C07C2601/08C07C2601/14C07C2601/20C07C2601/18B01J2231/70B01J2531/025B01J2531/16B01J2531/845C07C49/403C07C49/413C07C49/395C07C35/08C07C35/20C07C35/205C07C35/06
Inventor 沈海民郭阿兵
Owner ZHEJIANG UNIV OF TECH
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