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Preparation method for ketoxime

A technology of ketoxime and reaction system, which is applied in the field of organic chemical synthesis, can solve the problems of complex post-treatment, reduced catalyst activity, and blockage of TS-1 molecular sieve channels, etc., and achieves simple post-treatment process, less by-products, and easy industrial implementation Effect

Inactive Publication Date: 2014-01-08
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Chinese patent (CN 1432560) discloses a method for synthesizing cyclohexanone oxime using 0.1-0.3 μm titanium-silicon molecular sieve TS-1 as a catalyst, which has the disadvantage of complicated post-treatment
Although the microsphere TS-1 catalyst has excellent catalytic performance in the process of producing oxime by liquid phase ammoxidation in carbonyl compound, ammonia and hydrogen peroxide system, macromolecular by-products will be produced in the reaction process, for example, The oximation process of cyclohexanone tends to produce 2-cyclohexylcyclohexanone, cyclohexanecarboxamide and cyclohexanol, etc., these by-products will block the pores of TS-1 molecular sieve, which will lead to the reduction of catalyst activity

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] a. Preparation of catalyst

[0020] The molar ratio of tetraethyl orthosilicate to tetrabutyl titanate, tetrapropylammonium hydroxide, pure water and triblock polyether is 1:0.2:0.033:15:2.5×10 -3 Molar ratio mixing, 0.6 hours of hydrolysis and gelation reaction at 55 ° C, and then crystallization at 80 ° C, 120 ° C and 170 ° C for 20 hours, 5 hours and 12 hours respectively, after the crystallization reaction After the mixture is filtered, washed, dried and calcined, microsphere particles with an average diameter of 10 μm are obtained.

[0021] b. Combination reaction of ketoxime

[0022] Mix the microsphere TS-1 catalyst prepared above with cyclohexanone, tert-butanol aqueous solution and liquid ammonia with a weight concentration of 25% in the reactor, heat to carry out the compound reaction of ketoxime, the reaction temperature is 76 ° C, when When heated to 76°C, hydrogen peroxide with a mass concentration of 30% was added dropwise, and the dropwise addition tim...

Embodiment 2

[0027] a. Preparation of catalyst

[0028] With the a step of embodiment 1.

[0029] b. Combination reaction of ketoxime

[0030] Mix the microsphere TS-1 catalyst prepared above with cyclohexanone, tert-butanol aqueous solution and liquid ammonia with a weight concentration of 25% in the reactor, heat to carry out the compound reaction of ketoxime, the reaction temperature is 76 ° C, when When heated to 76°C, hydrogen peroxide with a mass concentration of 30% was added dropwise, and the dropwise addition time was 1 hour. After the dropwise addition, the reaction was continued for 0.5 hour, and the pressure of the ketoxime reaction was 1 atm. The weight ratio of described cyclohexanone and microsphere TS-1 catalyst and tert-butanol aqueous solution is 1:0.05:10; The water content of described tert-butanol aqueous solution is 30% (volume ratio); Described cyclohexanone and The molar ratio of liquid ammonia is 1:1.15; the molar ratio of cyclohexanone and hydrogen peroxid...

Embodiment 3

[0035] a. Preparation of catalyst

[0036] With the a step of embodiment 1.

[0037] b. Combination reaction of ketoxime

[0038] Mix the microsphere TS-1 catalyst prepared above with butanone, tert-butanol aqueous solution and liquid ammonia with a weight concentration of 25% in the reactor and heat to carry out the compound reaction of ketoxime. The reaction temperature is 62 ° C. When heated When the temperature reached 62°C, hydrogen peroxide with a mass concentration of 30% was added dropwise for 1 hour. After the dropwise addition, the reaction was continued for 0.5 hour, and the pressure of the ketoxime reaction was 1 atm. The weight ratio of the butanone to the microsphere TS-1 catalyst and the tert-butanol aqueous solution is 1:0.14:4; the water content of the tert-butanol aqueous solution is 30% (volume ratio); the butanone and liquid ammonia The mol ratio of is 1: 1.15; The mol ratio of described butanone and hydrogen peroxide is 1: 1.2.

[0039] c, purific...

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Abstract

The invention discloses a preparation method for ketoxime. The method is characterized in that a microspherical TS-1 catalyst is used for performing ketoxime combination reaction on a ketone, ammonia and hydrogen peroxide reaction system, wherein the weight ratio of ketone to the catalyst to an organic solvent is 1:(0.03-0.15):(1-10); the molar ratio of ketone to ammonia is 1:(1-3); the molar ratio of hydrogen peroxide to ketone is (1-2):1. Compared with the prior art, the preparation method has the advantages that the method is high in oxime selectivity, ketone conversion rate and hydrogen peroxide utilization rate and easy to industrially implement, a few byproducts are produced, TS-1 molecular sieve channels can be prevented from being blocked, the catalyst is high in stability and convenient to separate and recover, a post-treatment process is simple, and an environment for a reaction process is friendly.

Description

technical field [0001] The invention relates to the technical field of organic chemical synthesis, in particular to a preparation method of ketoxime. Background technique [0002] At present, oximes are mainly produced by the reaction of hydroxylamine salts and ketones. For example, the production of cyclohexanone oxime adopts the reaction of hydroxylamine sulfate and cyclohexanone. This process requires a large amount of hydroxylamine sulfate, and ammonium sulfate is a by-product (Catalysis Reviews, 2001, 43(4): 381~441.). Very unfriendly to the environment. In order to solve the above problems and develop an environmentally friendly oxime production process, the US patent (US 4745221) discloses a method for synthesizing cyclohexanone oxime using titanium-silicon molecular sieve or a mixture of silicon dioxide and titanium-silicon molecular sieve as a catalyst, but the selectivity of oxime is relatively low. Low, only 79.45%. [0003] U.S. Patent (US 6462235) discloses ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C251/44C07C251/38C07C249/04
CPCY02P20/584
Inventor 吴鹏王振东徐乐吴海虹刘月明何鸣元
Owner EAST CHINA NORMAL UNIV
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