Method for catalyzing oxygen-oxidized cyclohexane by using cross-linked polystyrene immobilized metalloporphyrin

Abstract

The invention belongs to the technical field of cyclohexane oxidation, and particularly relates to a method for catalyzing oxygen-oxidized cyclohexane by using cross-linked polystyrene immobilized metalloporphyrin, which solves the problems of low transformation ratio and low product selectivity existing in the conventional cyclohexane oxidation method. The method comprises the following steps of: continuously introducing oxygen under normal pressure; and carrying out reaction by taking the cross-linked polystyrene immobilized metalloporphyrin as a catalyst at the temperature of between 30 DEG C and 50 DEG C for 5-8 hours, wherein the concentration of the catalyst is between 0.5 mu mol / ml and 2 mu mol / ml. The method has the advantages that: the cross-linked polystyrene immobilized metalloporphyrin catalyst has high catalytic performance in a reaction for oxidizing cyclohexane into cyclohexanol by using oxygen. Along with the changes of the dosage of the immobilized metalloporphyrin and the reaction temperature, the transformation ratio of cyclohexane is between 12 percent and 45 percent. The reaction temperature is between 30 DEG C and 50 DEG C, so that advanced oxidation of the cyclohexane is effectively controlled and the selectivity of the cyclohexanol is over 90 percent.

Description

technical field

[0001] The invention belongs to the technical field of cyclohexane oxidation, and in particular relates to a method for catalyzing oxygen oxidation of cyclohexane by crosslinked polystyrene immobilized metalloporphyrin. Background technique

[0002] The oxidation of cyclohexane to prepare cyclohexanol and cyclohexanone is an important reaction in industry. The oxidation products cyclohexanol and cyclohexanone are important organic chemical raw materials, and they are intermediates for the production of adipic acid and caprolactam, respectively. At present, the production technology of Stamica in the Netherlands is widely used in industry, that is, cyclohexane is oxidized directly under high temperature and high pressure to produce peroxide, and peroxide is decomposed under alkaline conditions to produce cyclohexanol and cyclohexanone. However, this process not only has a low conversion rate of cyclohexane (4% to 5%), low selectivity of alcohol and ketone (abo...

Examples

Embodiment 1

[0011] 0.37g of cross-linked polystyrene immobilized metalloporphyrin with the structure of general formula (I), R=NO 3 , M=Co, X=acetic acid, add 20 mL of cyclohexane, continuously feed O under normal pressure 2 , The reaction was carried out at a constant temperature of 40°C for 7 hours, the conversion rate of cyclohexane was 40.07%, and the selectivity of cyclohexanol was 90.7%. After the reaction is over, the immobilized metalloporphyrin is soaked and washed with cyclohexane and ethanol for several times until the filtrate is free of oxidation products, then recovered and reused, and reused 8 times. The conversion rate of cyclohexane and the selectivity of cyclohexanol are basically constant.

Embodiment 2

[0013] Add 0.74g of cross-linked polystyrene immobilized metalloporphyrin with the structure of general formula (I), R=Cl, M=Co, X=acetic acid, into 20 mL of cyclohexane, and continuously inject o 2 , The reaction was carried out at a constant temperature of 40°C for 7 hours, the conversion rate of cyclohexane was 35.6%, and the selectivity of cyclohexanol was 90%. After the reaction is over, the immobilized metalloporphyrin is soaked and washed with cyclohexane and ethanol for several times until the filtrate is free of oxidation products, then recovered and reused, and reused 8 times. The conversion rate of cyclohexane and the selectivity of cyclohexanol are basically constant.

Embodiment 3

[0015] Add 0.37g of cross-linked polystyrene immobilized metalloporphyrin with the structure of general formula (I), R=H, M=Co, X=acetic acid, into 20 mL of cyclohexane, and continuously pass it under normal pressure o 2 , The reaction was carried out at a constant temperature of 40°C for 7 hours, the conversion rate of cyclohexane was 13%, and the selectivity of cyclohexanol was 90%. After the reaction is over, the immobilized metalloporphyrin is soaked and washed with cyclohexane and ethanol for several times until the filtrate is free of oxidation products, then recovered and reused, and reused 8 times. The conversion rate of cyclohexane and the selectivity of cyclohexanol are basically constant.

technical field

[0001] The invention belongs to the technical field of cyclohexane oxidation, and in particular relates to a method for catalyzing oxygen oxidation of cyclohexane by crosslinked polystyrene immobilized metalloporphyrin. Background technique

[0002] The oxidation of cyclohexane to prepare cyclohexanol and cyclohexanone is an important reaction in industry. The oxidation products cyclohexanol and cyclohexanone are important organic chemical raw materials, and they are intermediates for the production of adipic acid and caprolactam, respectively. At present, the production technology of Stamica in the Netherlands is widely used in industry, that is, cyclohexane is oxidized directly under high temperature and high pressure to produce peroxide, and peroxide is decomposed under alkaline conditions to produce cyclohexanol and cyclohexanone. However, this process not only has a low conversion rate of cyclohexane (4% to 5%), low selectivity of alcohol and ketone (abo...

Examples

Embodiment 1

[0011] 0.37g of cross-linked polystyrene immobilized metalloporphyrin with the structure of general formula (I), R=NO 3 , M=Co, X=acetic acid, add 20 mL of cyclohexane, continuously feed O under normal pressure 2 , The reaction was carried out at a constant temperature of 40°C for 7 hours, the conversion rate of cyclohexane was 40.07%, and the selectivity of cyclohexanol was 90.7%. After the reaction is over, the immobilized metalloporphyrin is soaked and washed with cyclohexane and ethanol for several times until the filtrate is free of oxidation products, then recovered and reused, and reused 8 times. The conversion rate of cyclohexane and the selectivity of cyclohexanol are basically constant.

Embodiment 2

[0013] Add 0.74g of cross-linked polystyrene immobilized metalloporphyrin with the structure of general formula (I), R=Cl, M=Co, X=acetic acid, into 20 mL of cyclohexane, and continuously inject o 2 , The reaction was carried out at a constant temperature of 40°C for 7 hours, the conversion rate of cyclohexane was 35.6%, and the selectivity of cyclohexanol was 90%. After the reaction is over, the immobilized metalloporphyrin is soaked and washed with cyclohexane and ethanol for several times until the filtrate is free of oxidation products, then recovered and reused, and reused 8 times. The conversion rate of cyclohexane and the selectivity of cyclohexanol are basically constant.

Embodiment 3

[0015] Add 0.37g of cross-linked polystyrene immobilized metalloporphyrin with the structure of general formula (I), R=H, M=Co, X=acetic acid, into 20 mL of cyclohexane, and continuously pass it under normal pressure o 2 , The reaction was carried out at a constant temperature of 40°C for 7 hours, the conversion rate of cyclohexane was 13%, and the selectivity of cyclohexanol was 90%. After the reaction is over, the immobilized metalloporphyrin is soaked and washed with cyclohexane and ethanol for several times until the filtrate is free of oxidation products, then recovered and reused, and reused 8 times. The conversion rate of cyclohexane and the selectivity of cyclohexanol are basically constant.