Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin

A technology of air oxidation and metalloporphyrin, which is applied in the directions of oxidation reaction preparation, oxidation preparation of carbonyl compounds, hydrocarbon oxidation preparation of oxygen-containing compounds, etc. Problems such as reusability of linoline

Inactive Publication Date: 2003-03-26
HUNAN UNIV
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  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

Because the synthesis price of the polyhalogenated or perhalogenated metalloporphyrins used in the methods disclosed in these patents is extremely expensive, and

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0011] 3mg has the metalloporphyrin of general formula (I) structure, R 1 = R 2 = R 3 =CH 3 , M=Mn, and 10mg Cu 2 Cl 2 Add 400ml of cyclohexane, and pass through 6atm air. The reactant was stirred at 130° C. for 5 hours, the conversion rate of cyclohexane was 8.2%, and the yield of cyclohexanol and cyclohexanone in the reaction product was 95%.

Embodiment 2

[0013] 5mg has the metalloporphyrin of general formula (II) structure, R 1 = R 2 = R 3 =Cl,M 1 = M 2 = Fe, and 15 mg Cu 2 O was added to 500ml cyclohexane, and 5atm air was passed through. The reactant was stirred at 140° C. for 3 hours, the conversion rate of cyclohexane was 10.5%, and the yield of cyclohexanol and cyclohexanone in the reaction product was 96%.

Embodiment 3

[0015] 8mg has the metalloporphyrin of general formula (I) structure, R 1 = R 2 = R 3 = Cl, M = Fe, and 15 mg CoCl 2 Add in 500ml cyclohexane, and blow in 8atm air. The reactant was stirred at 135° C. for 3 hours, the conversion rate of cyclohexane was 12.5%, and the yield of cyclohexanol and cyclohexanone in the reaction product was 92%.

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Abstract

The invention relates to a new process in which under the catalytic action of metal porphyrin the cyclohexane can be selectively oxdated by air and made into cyclohexanol and cyclohexanone. Under the condition of 2-10 atm air, reaction temp. is 125-150 deg.C, it selects and uses micro-oxo double metal porphyrin and single metal porphyrin or their solid carrier as main catalyst, and uses transition metal salt or oxide as co-catalyst, the metal porphyrin can high-effectively and high-selectively catalyze oxidation of cyclohexane by using air in the biological concentratino as biological enzyme. The dose of metal porphyrin is small and said metal porphyrin can be repeatedly used, and said catalyst dose also is small, its catalystic effect is good, said catalyst can be used for making homogeneous catalysis, and after it is solid-carried, it also can be used for making heterogeneous catalysis.

Description

Technical field: [0001] The invention relates to a method for selectively oxidizing cyclohexane into cyclohexanol and cyclohexanone by air under metalloporphyrin catalysis. Background technique: [0002] Cyclohexane is an important petrochemical product. Oxidation of cyclohexane into cyclohexanol and cyclohexanone with air is an important method for converting cyclohexane into chemical raw material cyclohexanone. At present, the industrial method of producing cyclohexanone by oxidation of cyclohexane is the production technology of Stamica in the Netherlands. Specifically, cyclohexane is directly oxidized with air under high temperature and high pressure to produce peroxide, peroxide It decomposes under alkaline conditions to produce cyclohexanol and cyclohexanone. This process is currently an international general technology for producing cyclohexanone by oxidation of cyclohexane. Since the oxidation process needs to be carried out under high temperature and high pressure...

Claims

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Application Information

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IPC IPC(8): C07C27/12C07C29/48C07C35/08C07C45/28C07C49/403
Inventor 郭灿城刘强刘洋张晓兵
Owner HUNAN UNIV
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