CN103172535A - Liquid-phase fixed bed preparation method of cyclohexanone oxime - Google Patents
Liquid-phase fixed bed preparation method of cyclohexanone oxime Download PDFInfo
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Abstract
The invention discloses a liquid-phase fixed bed preparation method of cyclohexanone oxime. The liquid-phase fixed bed preparation method has the characteristic that high-selectivity cyclohexanone oxime combination reaction is carried out on cyclohexanone, hydrogen peroxide, ammonia gas and a tertiary butanol aqueous solution in a fixed-bed reactor under the catalytic action of titanium silicalite molecular sieve, wherein the mass concentration of the hydrogen peroxide is 5%-50%; the mass concentration of the tertiary butanol aqueous solution is 30%-90%; the weight ratio of the cyclohexanone to the hydrogen peroxide to the ammonia gas to the tertiary butanol aqueous solution is 1:(0.35-1.74):(0.19-0.70):3. Compared with the prior art, the liquid-phase fixed bed preparation method of the cyclohexanone oxime is good in selectivity, high in conversion rate, capable of separating reaction liquid without catalyst, simple in process, capable of continuously charging and discharging, environment-friendly and easy for industrial implementation.
Description
Technical field
The present invention relates to the organic chemical synthesis technical field, especially a kind of liquid phase fixed bed preparation method of cyclohexanone-oxime.
Background technology
Cyclohexanone-oxime is a kind of important intermediate of hexanolactam building-up process.Hexanolactam can generate nylon-6 by polymerization, and nylon-6 can further be processed into Deng eng such as nylon fibre, plastics film and Other Engineering plastics.Hexanolactam is also the raw material of antiplatelet drug 6-aminocaprolc acid, the tall and erect ketone of bay ammonia etc. in addition.90% hexanolactam is all to adopt pimelinketone and hydroxylammonium salt reaction preparation cyclohexanone-oxime in the world, then synthesizes by Beckmann rearrangement.The reaction process of the Ammoximation reaction of catalysis of pimelinketone and the Beckmann rearrangement of catalysis of pimelinketone oxime is the critical process process of producing hexanolactam, and larger breakthrough has also been arranged at present.
Current, the production method of industrial cyclohexanone-oxime mainly contains three kinds of oxammonium sulfate method, nitrogen oxide catalytic reduction method and phosphatic hydroxylamine methods.The main drawback that these production technique exist is: reaction process is complicated, long flow path, and also by product is more, relates in particular to SO
2With the environmentally harmful material discharging such as NO, its production belongs to the unfriendly process of environment.
HTS is the novel hetero-atom molecular-sieve that last century, at first early eighties was developed by Italian Eni company.The HTS with microvoid structure that the research group of present various countries has reported has TS-1, Ti-MOR, Ti-MWW, Ti-Beta, TS-2 etc.The characteristic that has oxidation-reduction catalysis due to the four-coordination titanium in the HTS skeleton, what add framework of molecular sieve self selects the shape selectivity, thereby HTS has good directional catalyzing oxidation susceptibility.
It is catalyzer that Italy Enichem company adopts titanium-silicon molecular sieve TS-1, obtain good result take pimelinketone, hydrogen peroxide, ammoniacal liquor as raw material one-step synthesis cyclohexanone-oxime, and realized industrial applications (Sci. Catal., 1990,55,43.).This process reaction condition is gentleer, pimelinketone transformation efficiency 99.9%, and the cyclohexanone-oxime selectivity is 98.2%, water is unique by product of this process, so the liquid phase ammonia oximate process is very friendly to environment substantially without the waste gas and waste liquid discharging.The shortcoming that this process exists is: the production cost of catalyzer TS-1 is too high, need to use expensive template TPAOH and organosilicon source tetraethoxy, and this catalyst system must use the cosolvent of volatile organic solvent trimethyl carbinol and water could obtain high activity.The said firm adopts slurry attitude bed to carry out ketone oximation reaction again take the TS-1 of spray shaping as catalyzer, and the pimelinketone transformation efficiency is 98.3%, and the cyclohexanone-oxime selectivity is 99.6%(EP 0 564 040 A2).Wu etc. are take HTS Ti-MOR as catalyzer, and the catalyzing ketone amidoxime has been studied the active sites of reacting, and has confirmed that this reaction is NH
2OH mechanism has constructive meaning (J. Catal., 1997,168,400.) to the research of ketone amidoxime.Wu etc. are again take novel titanosilicate Ti-MWW as catalyzer, H
2O
2Be oxygenant, designed the slurry-bed reaction technique of the amidoxime of ketone, studied the reaction rule of this technological process from the physicochemical characteristic of Ti-MWW molecular sieve catalyst and reaction process parameter two aspects, and reason and the renovation process of HTS inactivation in this reaction process have further been explored, obtained result (the Applied Catalysis A:General 2011 with certain guidance and practical application meaning, 394,1-8).
So far, Ti-Si nano molecular sieve powder or micron order spray shaping titanium-silicon molecular sieve catalyst are all adopted in the different titanium molecular sieve catalysis cyclohexanone oxamidinating reactions of report, exist the shortcomings such as separation difficulty in actual mechanical process.
Summary of the invention
The liquid phase fixed bed preparation method that a kind of cyclohexanone-oxime of providing for the deficiencies in the prior art is provided, carry out the cyclohexanone-oxime combination reaction of highly selective under the katalysis of fixed-bed reactor and HTS with pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution, the transformation efficiency of pimelinketone is high, selectivity is good, and reaction solution need not to carry out catalyst separating, and technique is simple, can throw continuously, discharging, environmental friendliness is easy to industrializing implementation.
The concrete technical scheme that realizes the object of the invention is: a kind of liquid phase fixed bed preparation method of cyclohexanone-oxime, be characterized in that the method adopts fixed-bed reactor, pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution are carried out the highly selective reaction of cyclohexanone-oxime chemical combination under the katalysis of HTS, concrete preparation comprises the following steps:
The preparation of a, catalyzer
With HTS with add binding agent and suitable quantity of water after pore-forming material evenly mixes, roasting becomes beaded catalyst after kneading, moulding, described HTS is Ti-MOR, Ti-MWW or TS-1; Described pore-forming material is sesbania powder, methylcellulose gum, polyoxyethylene glycol or activated carbon; Described binding agent is water glass, silicon sol, be fuming silica gel or aluminum oxide; The mass ratio of described HTS and pore-forming material and binding agent is 100:2 ~ 40:10 ~ 85;
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 40 ~ 80 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 5 ~ 50%; The mass concentration of the trimethyl carbinol aqueous solution is 30 ~ 90%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.35 ~ 1.74:0.19 ~ 0.70:3;
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal.
It is good that the present invention compared with prior art has selectivity, and transformation efficiency is high, and reaction solution need not to carry out catalyst separating, and technique is simple, can throw continuously, discharging, and environmental friendliness is easy to industrializing implementation.
Embodiment
Below by specific embodiment, preparation of the present invention and application are described in further detail.
Embodiment 1
The preparation of a, catalyzer
With the Ti-MOR HTS with add water glass and suitable quantity of water after activated carbon evenly mixes, dried 10 hours at 120 ℃ of temperature after kneading, moulding, then became beaded catalyst in 10 hours at 6000 ℃ of roasting temperatures, the mass ratio of described Ti-MOR HTS and activated carbon and water glass is 100:6:20.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 70 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 28%; The mass concentration of the trimethyl carbinol aqueous solution is 85%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.45:0.35:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.5 %, and transformation efficiency is 95.7 %, and selectivity is 99.6 %.
Embodiment 2
The preparation of a, catalyzer
With the Ti-MWW HTS with add silicon sol and suitable quantity of water after polyoxyethylene glycol evenly mixes, dried 10 hours at 120 ℃ of temperature after kneading, moulding, then became beaded catalyst in 10 hours at 6000 ℃ of roasting temperatures, the mass ratio of described Ti-MWW HTS and polyoxyethylene glycol and silicon sol is 100:5:15.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 60 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 35%; The mass concentration of the trimethyl carbinol aqueous solution is 80%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.52:0.35:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.6 %, and transformation efficiency is 97.6 %, and selectivity is 99.6 %.
Embodiment 3
The preparation of a, catalyzer
With the TS-1 HTS with add be fuming silica gel and suitable quantity of water after methylcellulose gum evenly mixes, dried 10 hours at 120 ℃ of temperature after kneading, moulding, then became beaded catalyst in 10 hours at 6000 ℃ of roasting temperatures, the mass ratio of described Ti-MOR HTS and methylcellulose gum and the silica gel of being fuming is 100:10:30.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 75 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 40%; The mass concentration of the trimethyl carbinol aqueous solution is 90%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.69:0.55:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.7 %, and transformation efficiency is 98.9 %, and selectivity is 99.7 %.
Embodiment 4
The preparation of a, catalyzer
Identical with embodiment 1.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 70 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 28%; The mass concentration of the trimethyl carbinol aqueous solution is 85%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:1.01:0.55:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.6 %, and transformation efficiency is 99.1 %, and selectivity is 99.8 %.
Embodiment 5
The preparation of a, catalyzer
Identical with embodiment 1.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 60 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 28%; The mass concentration of the trimethyl carbinol aqueous solution is 85%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:1.01:0.55:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.4 %, and transformation efficiency is 94.6 %, and selectivity is 99.6 %.
Embodiment 6
The preparation of a, catalyzer
Identical with embodiment 1.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 60 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 28%; The mass concentration of the trimethyl carbinol aqueous solution is 85%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.45:0.33:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.5 %, and transformation efficiency is 95.6 %, and selectivity is 99.5 %.
Embodiment 7
The preparation of a, catalyzer
Identical with embodiment 1.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 60 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 28%; The mass concentration of the trimethyl carbinol aqueous solution is 85%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.45:0.61:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.6 %, and transformation efficiency is 97.6 %, and selectivity is 99.5 %.
Embodiment 8
The preparation of a, catalyzer
Identical with embodiment 1.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 70 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 5%; The mass concentration of the trimethyl carbinol aqueous solution is 85%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.45:0.35:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.3 %, and transformation efficiency is 94.1 %, and selectivity is 99.5 %.
Embodiment 9
The preparation of a, catalyzer
With the Ti-MWW HTS with add silicon sol and suitable quantity of water after polyoxyethylene glycol evenly mixes, dried 10 hours at 120 ℃ of temperature after kneading, moulding, then became beaded catalyst in 10 hours at 6000 ℃ of roasting temperatures, the mass ratio of described Ti-MWW HTS and polyoxyethylene glycol and silicon sol is 100:16:40.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 70 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 28%; The mass concentration of the trimethyl carbinol aqueous solution is 85%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.45:0.35:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.4 %, and transformation efficiency is 92.1 %, and selectivity is 99.2 %.
Embodiment 10
The preparation of a, catalyzer
With the TS-1 HTS with add be fuming silica gel and suitable quantity of water after methylcellulose gum evenly mixes, dried 10 hours at 120 ℃ of temperature after kneading, moulding, then became beaded catalyst in 10 hours at 6000 ℃ of roasting temperatures, the mass ratio of described Ti-MOR HTS and methylcellulose gum and the silica gel of being fuming is 100:20:50.
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 70 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 28%; The mass concentration of the trimethyl carbinol aqueous solution is 85%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.45:0.35:3.
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal, and the trimethyl carbinol that distills out recycles.
Product is through stratographic analysis: the purity of cyclohexanone-oxime is 99.5 %, and transformation efficiency is 91.2 %, and selectivity is 99.0 %.
Just the present invention will be further described for above each embodiment, is not to limit patent of the present invention, and all the present invention of being equivalences are implemented, within all should being contained in the claim scope of patent of the present invention.
Claims (1)
1. the liquid phase fixed bed preparation method of a cyclohexanone-oxime, it is characterized in that the method adopts fixed-bed reactor, pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution are carried out the highly selective reaction of cyclohexanone-oxime chemical combination under the katalysis of HTS, concrete preparation comprises the following steps:
The preparation of a, catalyzer
With HTS with add binding agent and suitable quantity of water after pore-forming material evenly mixes, roasting becomes beaded catalyst after kneading, moulding, described HTS is Ti-MOR, Ti-MWW or TS-1; Described pore-forming material is sesbania powder, methylcellulose gum, polyoxyethylene glycol or activated carbon; Described binding agent is water glass, silicon sol, be fuming silica gel or aluminum oxide; The mass ratio of described HTS and pore-forming material and binding agent is 100:2 ~ 40:10 ~ 85;
The building-up reactions of b, cyclohexanone-oxime
Adopt fixed-bed reactor, fill the HTS beaded catalyst of above-mentioned preparation in it, and when heating to 40 ~ 80 ℃, add continuously respectively pimelinketone, hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution to fixed-bed reactor, carry out the cyclohexanone-oxime combination reaction under normal pressure, the cyclohexanone-oxime that reaction generates is the reaction solution of continuous discharge, and wherein the mass concentration of hydrogen peroxide is 5 ~ 50%; The mass concentration of the trimethyl carbinol aqueous solution is 30 ~ 90%; The mass ratio of pimelinketone and hydrogen peroxide, ammonia and the trimethyl carbinol aqueous solution is 1:0.35 ~ 1.74:0.19 ~ 0.70:3;
The purification of c, cyclohexanone-oxime
With above-mentioned reaction solution distillation, distillate gets product after extracting, revolving steaming be the cyclohexanone-oxime of colourless needle crystal.
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| CN104130157A (en) * | 2014-07-08 | 2014-11-05 | 华东师范大学 | Method for preparing cyclohexanone-oxime |
| CN105693551A (en) * | 2016-03-23 | 2016-06-22 | 华东师范大学 | Method for synthesizing cyclohexanone oxime under catalytic action of molecular sieve |
| CN105949083A (en) * | 2016-05-11 | 2016-09-21 | 中国天辰工程有限公司 | Cyclohexanone ammoximation method |
| CN106278940A (en) * | 2015-05-29 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of production cyclohexanone-oxime and the method for acetone simultaneously |
| CN108530316A (en) * | 2018-05-10 | 2018-09-14 | 中国平煤神马集团尼龙科技有限公司 | A kind of fixed bed heat reclamation type Ammoximation reaction system |
| CN110372536A (en) * | 2019-08-15 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone |
| CN110981749A (en) * | 2019-12-30 | 2020-04-10 | 岳阳昌德环境科技有限公司 | Process for producing cyclohexanone oxime |
| CN113105358A (en) * | 2021-04-15 | 2021-07-13 | 河南资环检测科技有限公司 | Method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water |
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| CN108530316A (en) * | 2018-05-10 | 2018-09-14 | 中国平煤神马集团尼龙科技有限公司 | A kind of fixed bed heat reclamation type Ammoximation reaction system |
| CN108530316B (en) * | 2018-05-10 | 2023-07-04 | 中国平煤神马集团尼龙科技有限公司 | Fixed bed heat recovery type ammoximation reaction system |
| CN110372536A (en) * | 2019-08-15 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone |
| CN110981749A (en) * | 2019-12-30 | 2020-04-10 | 岳阳昌德环境科技有限公司 | Process for producing cyclohexanone oxime |
| CN110981749B (en) * | 2019-12-30 | 2022-11-15 | 昌德新材科技股份有限公司 | Process for producing cyclohexanone oxime |
| CN113105358A (en) * | 2021-04-15 | 2021-07-13 | 河南资环检测科技有限公司 | Method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water |
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