Method for synergistic catalytic oxidation of cycloalkane by metalloporphyrin MOFs PCN-222 (Co)/Cu (II) salt

A technology of metalloporphyrin and synergistic catalysis, 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 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: 2020-12-15
ZHEJIANG UNIV OF TECH
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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, 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 problems mentioned above 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 synergistic catalytic oxidation of cycloalkane by metalloporphyrin MOFs PCN-222 (Co)/Cu (II) salt
  • Method for synergistic catalytic oxidation of cycloalkane by metalloporphyrin MOFs PCN-222 (Co)/Cu (II) salt
  • Method for synergistic catalytic oxidation of cycloalkane by metalloporphyrin MOFs PCN-222 (Co)/Cu (II) salt

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Synthesis of PCN-222(Co)-m: In a 35mL pressure-resistant reaction tube, T(3-COOH)PPCo(II) (0.0847g, 0.1mmol), ZrCl 4 (0.1400g, 0.6mmol), benzoic acid (5.4000g, 44.3mmol) was dissolved in 16.0mL DMF, ultrasonic 30min until completely dissolved. The mixture was placed in an electric constant temperature blast drying oven at 120 °C for 48.0 h. 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 Static extraction (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, 44.7% yield Rate).

Embodiment 2

[0032] Synthesis of PCN-222(Co)-p: In a 35mL pressure-resistant reaction tube, T(4-COOH)PPCo(II) (0.0847g, 0.1mmol), ZrCl 4(0.1400g, 0.6mmol), benzoic acid (5.4000g, 44.3mmol) was dissolved in 16.0mL DMF, ultrasonic 30min until completely dissolved. The mixture was placed in an electric constant temperature blast drying oven at 120 °C for 48.0 h. 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 Static extraction (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 (0.0690g, 45.3% yield Rate).

Embodiment 3

[0034] Synthesis of PCN-222(Co)-d: In a 35mL pressure-resistant reaction tube, [T(4-(4-COOH)P)PPCo(II)] (0.1152g, 0.1mmol), ZrCl 4 (0.1400g, 0.6mmol), benzoic acid (5.4000g, 44.3mmol) was dissolved in 16.0 mLDMF, and ultrasonicated for 30min until all dissolved. The mixture was put into an electric constant temperature blast drying oven at 120°C and left to react for 48.0h. 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 in a low-speed centrifuge for 5min (3000rpm), pour out the upper layer, and dry the DMF Static extraction (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 (0.0660g, 43.4% yield Rate).

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Abstract

The invention relates to a method for synergistic catalytic oxidation of cycloalkane by a metalloporphyrin MOFs PCN-222 (Co) / Cu (II) salt. The method comprises the following steps of: dispersing PCN-222 (Co) (1%-10%, g / mol) and a Cu (II) salt (0.01%-10%, mol / mol) into cycloalkane, sealing a reaction system, performing heating to 90-150DEG C while stirring, introducing an oxidant (0.10-2.0MPa), keeping the set temperature and pressure, carrying out stirring reaction for 2.0-24.0h to obtain a reaction solution, and conducting post-treatment to obtain the products cycloalkyl alcohol and cycloalkyl ketone. The method 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 cycloalkyl hydroperoxide content 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 cycloalkane.

Description

technical field [0001] The invention relates to a method for synergistically catalyzing the oxidation of naphthenes to synthesize cycloalkanol and cycloalkanone by metalloporphyrin MOFs PCN-222(Co) / 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 ) is an oxidizing agent, carried out at 150°C to 170°C, the main problems are high reaction temperat...

Claims

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Application Information

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IPC IPC(8): B01J31/22B01J31/04C07C29/48C07C35/08C07C35/06C07C35/20C07C35/205C07C45/27C07C49/403C07C49/395C07C49/413
CPCB01J31/1691B01J31/04C07C29/48C07C45/27B01J2531/845B01J2531/025B01J2231/70C07C35/08C07C35/06C07C35/20C07C35/205C07C49/403C07C49/395C07C49/413
Inventor 沈海民郭阿兵佘远斌
Owner ZHEJIANG UNIV OF TECH
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