Method for preparing cyclohexanone-oxime from cyclohexanone through liquid-phase ammoximation

A technology of cyclohexanone liquid-phase ammonia oxime and cyclohexanone oxime, which is applied in the field of green chemistry, can solve problems such as weak alkali resistance, easy inactivation, and difficult separation and recovery, and achieve the effect of reducing separation costs and low cost

Active Publication Date: 2016-01-06
HEBEI UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] The technical problem to be solved in the present invention is that the preparation process is cumbersome, time-consuming, expensive template agent, small particle size, difficult to separate and recover, weak alkali resistance, easy inactivation, etc. Problem, find a new catalyst zirconium hydrogen phosphate / titanium hydrogen phosphate, replace TS-1 to catalyze the ammoximation reaction of cyclohexanone, and invent a microemulsion system suitable for zirconium hydrogen phosphate catalyzed ammoximation reaction of cyclohexanone: water -cyclohexanone-polyethylene glycol 6000-tert-butanol, wherein through the selection of surfactant and the addition of hydrogen peroxide, hydrogen peroxide, cyclohexanone and solvent can share a delivery channel, so that the process can save the delivery device of hydrogen peroxide, Save on equipment costs

Method used

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  • Method for preparing cyclohexanone-oxime from cyclohexanone through liquid-phase ammoximation
  • Method for preparing cyclohexanone-oxime from cyclohexanone through liquid-phase ammoximation
  • Method for preparing cyclohexanone-oxime from cyclohexanone through liquid-phase ammoximation

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Embodiment 1

[0016] Stir and mix butyl titanate and phosphoric acid according to different molar ratios, transfer the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, put it in a constant temperature drying oven at 180°C for 6 hours, cool to room temperature, and centrifuge. Fully washed to neutral, vacuum dried overnight at 80°C. The titanium hydrogen phosphate catalysts synthesized with Ti / P molar ratios of 1:28.4, 1:38, 1:50, and 1:65.4 were designated as TP-1, TP-2, TP-3, and TP-4, respectively.

Embodiment 2

[0018] In the phosphoric acid solution, add ethyl orthosilicate (containing an equal volume of absolute ethanol), CTAB and butyl titanate, stir vigorously at different temperatures for 8 hours, cool to room temperature, centrifuge, and fully wash until neutral. Dry overnight at 80°C under vacuum. Among them, the molar ratio of butyl titanate, phosphoric acid, ethyl orthosilicate and CTAB is 1:4:3.93:0.018. The titanium hydrogen phosphate catalysts synthesized at 110°C, 140°C, and 180°C are designated as TP-5, TP-6, and TP-7, respectively.

Embodiment 3

[0020] In a 100ml round-bottomed three-neck flask equipped with a condenser tube and a thermometer, add 0.5g of zirconium hydrogen phosphate (the catalyst for zirconium hydrogen phosphate is commercially available, and dry it overnight before use), 1ml of surfactant AEO-9, co-surfactant 2ml of tert-butanol, 4ml of water, 0.01mol of cyclohexanone (0.9814g, the molar mass of cyclohexanone is 98.14g / mol), put it in a constant temperature water bath at 70°C, stir at a speed of 495r / min, and make a disposable Add 0.05molNH 3 (mass fraction is 25% ammonia solution), then dropwise add 0.02mol of H 2 o 2 (Hydrogen peroxide solution with a mass fraction of 30%), the dropwise addition time is 25 minutes, and after the dropwise addition is completed, the reaction is carried out at a constant temperature of 70° C. for 4 hours. After the reaction, the temperature of the reaction solution was down to room temperature, the reaction solution was extracted several times with toluene, the ext...

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Abstract

The invention relates to a method for preparing cyclohexanone-oxime from cyclohexanone through liquid-phase ammoximation. The method includes the following steps that cyclohexanone, ammonia water, hydrogen peroxide, a catalyst, a surfactant, solvent and cosurfactant are added into a reactor and react for 2.5-4.5 h on the stirring condition at the temperature of 55 DEG C-80 DEG C; after the reaction is finished, cyclohexanone-oxime is obtained when the temperature falls to the room temperature; the catalyst is zirconium hydrogen phosphate or titanium hydrogen phosphate. The problems of equipment corrosion and generation of a great number of useless ammonium salt side products are solved by using the catalyst, the conversion rate of cyclohexanone can reach 95.3%, and the yield and selectivity of cyclohexanone are 69.1% and 72.5% respectively.

Description

technical field [0001] The invention relates to the technical field of green chemistry, uses zirconium hydrogen phosphate or titanium hydrogen phosphate with strong acid and strong alkali resistance as a catalyst to catalyze cyclohexanone liquid-phase ammoximation to synthesize cyclohexanone oxime, is environmentally friendly, has low cost, and is suitable for industrial production. Background technique [0002] Cyclohexanone oxime is an important chemical intermediate and fine chemical, and a key intermediate in the synthesis of caprolactam. Caprolactam is a monomer for synthesizing nylon-6, engineering plastics, etc. As the market demand for caprolactam increases, the demand for cyclohexanone oxime also increases accordingly. The methods for producing cyclohexanone oxime mainly include: cyclohexanone-hydroxylamine method, nitrocyclohexane catalytic hydrogenation method, toluene method, and cyclohexane photonitrosation method. The industry adopts cyclohexanone-hydroxylami...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C251/44C07C249/04
Inventor 程庆彦朱响林王延吉赵新强
Owner HEBEI UNIV OF TECH
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