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A method for selective oxidation of cyclohexane to generate cyclohexanol and cyclohexanone

A technology for cyclohexane and cyclohexanol, which is applied in the field of selective catalytic oxidation of cyclohexane to generate cyclohexanol and cyclohexanone, can solve the problems of low conversion rate of cyclohexane, poor selectivity of alkanols and ketones, complicated processes, etc. High conversion rate, low cost, good selectivity

Active Publication Date: 2016-04-06
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The traditional process of producing cyclohexanol and cyclohexanone has low conversion rate of cyclohexane, poor selectivity of alcohol and ketone, complex process, serious pollution, and needs to be improved. Therefore, the research and development of new catalysts has become a focus

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0026] The preparation method of porphyrin MOF catalyst of the present invention comprises the following steps:

[0027] (1) Prepare porphyrin or porphyrin derivatives by reacting pyrrole with corresponding aldehyde.

[0028] The aldehyde is p-carboxybenzaldehyde, m-carboxybenzaldehyde, p-phosphonate benzaldehyde, m-phosphonate benzaldehyde, p-sulfonate benzaldehyde, m-sulfonate benzaldehyde.

[0029] (2) Using the corresponding metal salt and porphyrin or porphyrin derivative to obtain the corresponding metalloporphyrin or metalloporphyrin derivative by reflux reaction in DMF solvent.

[0030] The metal salts are nitrates, acetates, perchlorates, halides, and sulfates corresponding to Mn, Fe, V, Pd, Pt, and Ru.

[0031] (3) Preparation of polypyridine analog auxiliary carrier by reaction of acid anhydride and p-aminopyridine.

[0032] The acid anhydride is 1,4,5,8-naphthalene tetracarboxylic anhydride or pyromellitic anhydride.

[0033] (4) In a mixed solvent, react metall...

Embodiment 1

[0038] In a mixed solvent of DMF, EtOH and nitric acid, the benzoic acid derivatives of manganese porphyrin, the polypyridine analogs prepared by the reaction of 1,4,5,8-naphthalene tetracarboxylic anhydride and aminopyridine, and zinc nitrate were placed at 80oC for one day Afterwards, dark brown crystals were obtained, which were then filtered, washed with solvents such as DMF, ethanol, and ether, and finally dried in air. The MOF material is a porous zeolite compound through single crystal X-ray diffraction, PLATON calculation and BET specific surface area calculation. The MOF material was further characterized by powder X-ray diffraction, thermogravimetric and IR.

[0039] Example 1

[0040] Catalyst activity evaluation was carried out in a simple reaction glass reactor with magnetic stirring. 1.1 mL of cyclohexane, 3.3 g of PhIO, 15 mL of acetonitrile and 1 g of catalyst were successively added into the glass reactor. After the reaction time at room temperature was 20 ...

Embodiment 2

[0042] Catalyst activity evaluation was carried out in a simple reaction glass reactor with magnetic stirring. 1.1 mL of cyclohexane, 3.3 g of PhIO, 15 mL of acetone, and 1 g of catalyst were successively added into the glass reactor. After the reaction time at room temperature was 20 hours, the reaction product was centrifuged and filtered, and the conversion rate of cyclohexane was analyzed by gas chromatography to be 41%. The products were cyclohexanol and cyclohexanone, and cyclohexanol / cyclohexanone=65 / 35 .

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Abstract

The invention relates to a method for generating cyclohexanol and cyclohexanone through selective oxidation of cyclohexane. The method comprises the steps: successively adding 1.1 mL of cyclohexane, 3.3 g of PhIO, 15 mL of acetonitrile and 1 g of a catalyst into a glass reactor; after carrying out a reaction for 20 hours at the room temperature, centrifuging and filtering the reaction product, and thus obtaining cyclohexanol and cyclohexanone. The catalyst comprises porphyrin or a porphyrin derivative as a basic carrier, a polypyridine analogue as an auxiliary carrier, a transition metal ion as an active component, and a metal ion as a node; the transition metal ion active component is Mn, Fe, V, Pd, Pt or Ru; the porphyrin or porphyrin derivative basic carrier is porphyrin, or a carboxylic acid derivative, a phosphonic acid derivative or a sulfonic acid derivative thereof; the pyridine analogue auxiliary carrier is 4,4'-bipyridine or an analogue having pyridyls at two ends; and the metal ion node is Fe, Co, Ni, Cu, Zn, Mn or Cd. The method allows the cyclohexane conversion rate to be up to 94%.

Description

technical field [0001] The invention relates to a method for selectively catalyzing and oxidizing cyclohexane to generate cyclohexanol and cyclohexanone by using a porphyrin metal-organic framework material as a catalyst. Background technique [0002] The selective oxidation of cyclohexane to cyclohexanol and cyclohexanone has been a hotspot in production and research. Because it not only involves the activation of saturated carbon-hydrogen bonds, but also cyclohexanol and cyclohexanone are important chemical raw materials, widely used in industries such as fiber, medicine, industrial coatings, synthetic rubber, pesticides and organic solvents. The traditional process of producing cyclohexanol and cyclohexanone has low conversion rate of cyclohexane, poor selectivity of alcohol and ketone, complex process, serious pollution, and needs to be improved. Therefore, the research and development of new catalysts has become the focus. [0003] Porphyrins have important application...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C27/16C07C35/08C07C29/48C07C49/403C07C45/28B01J31/22
CPCC07C27/16C07C29/48C07C35/08C07C45/28C07C49/403C07C2601/14
Inventor 吴传德张天釜解明华马安杨秀丽阎立军
Owner PETROCHINA CO LTD