CN103497123A - Preparation method for ketoxime - Google Patents
Preparation method for ketoxime Download PDFInfo
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- CN103497123A CN103497123A CN201310416894.8A CN201310416894A CN103497123A CN 103497123 A CN103497123 A CN 103497123A CN 201310416894 A CN201310416894 A CN 201310416894A CN 103497123 A CN103497123 A CN 103497123A
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- ketoxime
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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
The present invention relates to the organic chemical synthesis technical field, especially a kind of preparation method of ketoxime.
Background technology
At present, oxime is mainly to utilize the reaction of hydroxylammonium salt and ketone to produce.Production employing oxammonium sulfate and pimelinketone reaction such as cyclohexanone-oxime.This technique needs a large amount of oxammonium sulfates, simultaneously producing ammonium sulfate byproduct (Catalysis Reviews, 2001,43 (4): 381 ~ 441.).Extremely unfriendly to environment.In order to address the above problem, development environment close friend's oxime production technique, United States Patent (USP) (US 4745221) discloses take the method that HTS or silicon-dioxide and HTS mixture be catalyzer synthesizing cyclohexane 1 ketoxime, but the selectivity of oxime is lower, only has 79.45%.
United States Patent (USP) (US 6462235) discloses a kind of with titanium-silicon molecular sieve TS-1 position catalyzer, under the condition coexisted at ammonium salt or substituted ammonium salt, the method that the liquid phase method that aldehydes or ketones, ammonia and hydrogen peroxide be raw material of take is produced oxime, the method is very effective to the macromole cyclic ketone, but in reaction, need to add promotor ammonium salt or substituted ammonium salt could obtain high transformation efficiency and selectivity, increased cost and separating difficulty.
Chinese patent (CN 1432560) discloses the method for the synthesizing cyclohexane 1 ketoxime that a kind of titanium-silicon molecular sieve TS-1 of take 0.1 ~ 0.3 μ m is catalyzer, has the shortcoming of aftertreatment complexity.Because conventional TS-1 zeolite crystal size is less than 1 μ m(A. Carati, G. Bellussi, M. A. Mantegazza, G. Petrini, US 187096), be dispersed in liquid and become emulsion, be difficult to settlement separate.Simultaneously, the filter paper adopted due to filter method or the aperture of filter core are micron order, and conventional TS-1 molecular sieve and liquid phase can directly be passed through, thereby can't adopt the method for filtration to separate, and usually adopt and add the way of ionogen flocculation to separate, the aftertreatment more complicated.
United States Patent (USP) (US 7074383) discloses a kind of forming method, can obtain the preformed catalyst that contains silicon-dioxide and TS-1 molecular sieve of particle diameter 5 ~ 100 μ m.Use this catalyzer well to solve the Separation and Recovery problem.But there are the problems such as step is many, the cycle long, final catalyzer yield is lower in this preparation process.In addition, adopt ketone, ammonia, hydroperoxidation system to produce oxime, system is strong basicity, can dissolve the silicon-dioxide in this catalyzer, finally causes this preformed catalyst to disintegrate, after completion of the reaction, and catalyst breakage, the performance when having limited it and reusing.
Chinese patent (CN 102145300) discloses a kind of microballoon TS-1 Catalysts and its preparation method, adopting ,Tai source, silicon source, organic bases template, crystallization promoting agent and water is the directly synthetic microballoon TS-1 catalyzer that obtains particle diameter 2-100 μ m of raw material, this catalyst particle size is even, physical strength is good, be easy to separate with the reaction system liquid phase substance, and there is excellent catalytic performance.This preparation method, except introducing crystallization promoting agent, without the requirement of special producing equipment and process, is easy to suitability for industrialized production.Although there is excellent catalytic performance in the process of this microballoon TS-1 catalyzer to the production of liquid phase ammonia oxidation style in carbonyl compound, ammonia and hydrogen peroxide system oxime, but can produce the macromole by product in this reaction process, for example, pimelinketone oximate process easily produces the produce things such as 2-cyclohexylcyclohxanone, cyclohexanecarbonyl amine and hexalin, these by products can stop up the TS-1 molecular sieve pore passage, and then cause catalyst activity to reduce.
Summary of the invention
The preparation method that a kind of ketoxime of providing for the deficiencies in the prior art is provided, adopt microballoon TS-1 catalyzer ketone, ammonia and hydroperoxidation system to be carried out to the ketoxime combination reaction of highly selective, the transformation efficiency of ketone and hydrogen peroxide utilization ratio are high, by product is few, can not result in blockage to the TS-1 molecular sieve pore passage, guarantees catalyst activity, especially catalyzer is convenient to separate and reclaim, last handling process is very simple, and the reaction process environmental friendliness, be easy to industrializing implementation.
The concrete technical scheme that realizes the object of the invention is: a kind of preparation method of ketoxime, be characterized in that the method adopts microballoon TS-1 catalyzer ketone, ammonia and hydroperoxidation system to be carried out to the ketoxime combination reaction of highly selective, and concrete preparation comprises the following steps:
The outfit of a, reaction system
Microballoon TS-1 catalyzer and organic solvent, ketone and ammonia are added to reactor in proportion successively, through being uniformly mixed as the ketoxime reaction system; Described organic solvent is one or more the mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol and the trimethyl carbinol; Described ketone is one or more the mixing in aliphatic ketone, alicyclic ketone and aromatic ketone; The weight ratio of described ketone and catalyzer and organic solvent is 1:0.03 ~ 0.15:1 ~ 10; The mol ratio of described ketone and ammonia is 1:1 ~ 3.
The combination reaction of b, ketoxime
Above-mentioned ketoxime reaction system is heated, start to drip the hydrogen peroxide that mass concentration is 1 ~ 50% when temperature of reaction is raised to 30 ~ 150 ℃, time for adding is 1 ~ 5 hour, dropwises rear continuation reaction 0.1 ~ 3 hour, and the pressure of ketoxime reaction system is 1 ~ 5atm; The mol ratio of described hydrogen peroxide and ketone is 1 ~ 2:1.
The purification of c, ketoxime
The ketoxime combination reaction is isolated the catalyst recovery utilization after finishing, and it is the crystalloid ketoxime that filtrate obtains product after distilling, extract and revolving steaming.
Described microballoon TS-1 catalyzer by tetraethyl orthosilicate and tetrabutyl titanate, TPAOH, pure water and triblock polyether by mole being than 1:0.05 ~ 0.4:0.005 ~ 0.2:10 ~ 30:1.0 * 10
-3~ 4.0 * 10
-3mix, carry out the hydrolysis plastic reaction of 0.5 ~ 1 hour at 50 ~ 60 ℃ of temperature, then at 80 ~ 90 ℃, 110 ~ 130 ℃ and 160 ~ 180 ℃ of three temperature sections, carry out respectively 10 ~ 20 hours, 2 ~ 10 hours and 10 ~ 20 hours crystallization, the mixture after crystallization after filtration, after washing, drying and roasting the diameter microballoon that is 2 ~ 100 μ m
3.
It is good that the present invention compared with prior art has the oxime selectivity, ketone transformation efficiency and hydrogen peroxide utilization ratio are high, by product is few, can not result in blockage to the TS-1 molecular sieve pore passage, catalyst stability is good, and catalyzer is convenient to separate and reclaims, and last handling process is very simple, the reaction process environmental friendliness, be easy to industrializing implementation.
Embodiment
Below by specific embodiment, preparation of the present invention is described in further detail.
Embodiment 1
The preparation of a, catalyzer
By tetraethyl orthosilicate and tetrabutyl titanate, TPAOH, pure water and triblock polyether, be 1:0.2:0.033:15:2.5 * 10 in molar ratio
-3mixed in molar ratio, carry out the hydrolysis plastic reaction of 0.6 hour at 55 ℃ of temperature, then at 80 ℃, 120 ℃ and 170 ℃ of three temperature sections, carry out respectively 20 hours, 5 hours and 12 hours crystallization, the mixture after crystallization after filtration, after washing, drying and roasting the mean diameter microsphere particle that is 10 μ m.
The combination reaction of b, ketoxime
The liquefied ammonia mix and blend in reactor that is 25% by the microballoon TS-1 catalyzer of above-mentioned preparation and pimelinketone, the trimethyl carbinol aqueous solution and weight concentration, the combination reaction of ketoxime is carried out in heating, temperature of reaction is 76 ℃, start to drip the hydrogen peroxide that mass concentration is 30% when being heated to 76 ℃, time for adding is 1 hour, dropwise rear continuation reaction 0.5 hour, the pressure of ketoxime reaction is 1atm.The weight ratio of described pimelinketone and microballoon TS-1 catalyzer and the trimethyl carbinol aqueous solution is 1:0.03:5; The water-content of the described trimethyl carbinol aqueous solution is the 20%(volume ratio); The mol ratio of described pimelinketone and liquefied ammonia is 1:1.15; The mol ratio of described pimelinketone and hydrogen peroxide is 1:1.06.
The purification of c, ketoxime
After the ketoxime combination reaction finishes, reaction solution goes out catalyzer utilization to be recycled through standing separation, and it is the crystalloid cyclohexanone-oxime that the reaction clear liquid obtains product after distilling, extract and revolving steaming.
Product is through stratographic analysis: the pimelinketone transformation efficiency is 99.6%, and the cyclohexanone-oxime selectivity is 99.9%, and the hydrogen peroxide utilization ratio is 99.8%.The catalyzer reclaimed adopts the Hitachi S-4800 of HIT awkward silence at a meeting Emission High Resolution rate scanning electronic microscope observation, and it is complete that the microballoon shape keeps, and there is no fragmentation, reusable.
Embodiment 2
The preparation of a, catalyzer
A step with embodiment 1.
The combination reaction of b, ketoxime
The liquefied ammonia mix and blend in reactor that is 25% by the microballoon TS-1 catalyzer of above-mentioned preparation and pimelinketone, the trimethyl carbinol aqueous solution and weight concentration, the combination reaction of ketoxime is carried out in heating, temperature of reaction is 76 ℃, start to drip the hydrogen peroxide that mass concentration is 30% when being heated to 76 ℃, time for adding is 1 hour, dropwise rear continuation reaction 0.5 hour, the pressure of ketoxime reaction is 1atm.The weight ratio of described pimelinketone and microballoon TS-1 catalyzer and the trimethyl carbinol aqueous solution is 1:0.05:10; The water-content of the described trimethyl carbinol aqueous solution is the 30%(volume ratio); The mol ratio of described pimelinketone and liquefied ammonia is 1:1.15; The mol ratio of described pimelinketone and hydrogen peroxide is 1:1.
The purification of c, ketoxime
After the ketoxime combination reaction finishes, reaction solution goes out catalyzer utilization to be recycled through standing separation, and it is the crystalloid cyclohexanone-oxime that the reaction clear liquid obtains product after distilling, extract and revolving steaming.
Product is through stratographic analysis: the pimelinketone transformation efficiency is 98.7%, and the cyclohexanone-oxime selectivity is 99.6%, and the hydrogen peroxide utilization ratio is 99.4%.
Embodiment 3
The preparation of a, catalyzer
A step with embodiment 1.
The combination reaction of b, ketoxime
The combination reaction of ketoxime is carried out in the liquefied ammonia that is 25% by the microballoon TS-1 catalyzer of above-mentioned preparation and butanone, the trimethyl carbinol aqueous solution and weight concentration mix and blend heating in reactor, temperature of reaction is 62 ℃, start to drip the hydrogen peroxide that mass concentration is 30% when being heated to 62 ℃, time for adding is 1 hour, dropwise rear continuation reaction 0.5 hour, the pressure of ketoxime reaction is 1atm.The weight ratio of described butanone and microballoon TS-1 catalyzer and the trimethyl carbinol aqueous solution is 1:0.14:4; The water-content of the described trimethyl carbinol aqueous solution is the 30%(volume ratio); The mol ratio of described butanone and liquefied ammonia is 1:1.15; The mol ratio of described butanone and hydrogen peroxide is 1:1.2.
The purification of c, ketoxime
After the ketoxime combination reaction finishes, reaction solution goes out catalyzer utilization to be recycled through standing separation, and it is the crystalloid Diacetylmonoxime that the reaction clear liquid obtains product after distilling, extract and revolving steaming.
Product is through stratographic analysis: the butanone transformation efficiency is 99.5%, and the Diacetylmonoxime selectivity is 99.3%, and the hydrogen peroxide utilization ratio is 99.4%.
Embodiment 4
The preparation of a, catalyzer
A step with embodiment 1.
The combination reaction of b, ketoxime
The liquefied ammonia mix and blend in reactor that is 25% by the microballoon TS-1 catalyzer of above-mentioned preparation and butanone, aqueous ethanolic solution and weight concentration, the combination reaction of ketoxime is carried out in heating, temperature of reaction is 76 ℃, start to drip the hydrogen peroxide that mass concentration is 30% when being heated to 76 ℃, time for adding is 1 hour, dropwise rear continuation reaction 0.5 hour, the pressure of ketoxime reaction is 1atm.。The weight ratio of described butanone and microballoon TS-1 catalyzer and aqueous ethanolic solution is 1:0.1:12; The water-content of described aqueous ethanolic solution is the 30%(volume ratio); The mol ratio of described butanone and liquefied ammonia is 1:1.2; The mol ratio of described butanone and hydrogen peroxide is 1:1.2.
The purification of c, ketoxime
After the ketoxime combination reaction finishes, reaction solution goes out catalyzer utilization to be recycled through standing separation, and it is the crystalloid Diacetylmonoxime that the reaction clear liquid obtains product after distilling, extract and revolving steaming.
Product is through stratographic analysis: the butanone transformation efficiency is 99.5%, and the Diacetylmonoxime selectivity is 99.3%, and the hydrogen peroxide utilization ratio is 99.4%.
Embodiment 5
The preparation of a, catalyzer
A step with embodiment 1.
The combination reaction of b, ketoxime
The combination reaction of ketoxime is carried out in the liquefied ammonia that is 25% by the microballoon TS-1 catalyzer of above-mentioned preparation and cyclooctanone, the trimethyl carbinol aqueous solution and weight concentration mix and blend heating in reactor, temperature of reaction is 82 ℃, start to drip the hydrogen peroxide that mass concentration is 30% when being heated to 82 ℃, time for adding is 2 hours, dropwise rear continuation reaction 0.5 hour, the pressure of ketoxime reaction is 1atm.The weight ratio of described cyclooctanone and microballoon TS-1 catalyzer and tertiary aqueous ethanolic solution is 1:0.1:10; The water-content of the described trimethyl carbinol aqueous solution is the 30%(volume ratio); The mol ratio of described cyclooctanone and liquefied ammonia is 1:1.3; The mol ratio of described cyclooctanone and hydrogen peroxide is 1:1.3.
The purification of c, ketoxime
After the ketoxime combination reaction finishes, reaction solution goes out catalyzer utilization to be recycled through standing separation, and it is the crystalloid cyclooctanone oxime that the reaction clear liquid obtains product after distilling, extract and revolving steaming.
Product is through stratographic analysis: the cyclooctanone transformation efficiency is 97.9%, and the cyclooctanone oxime selectivity is 99.5%, and the hydrogen peroxide utilization ratio is 99.4%.
Embodiment 6
The preparation of a, catalyzer
A step with embodiment 1.
The combination reaction of b, ketoxime
The microballoon TS-1 catalyzer of above-mentioned preparation and pimelinketone and the trimethyl carbinol aqueous solution mix and blend heating in reactor are carried out to the combination reaction of ketoxime, temperature of reaction is 76 ℃, start to drip respectively the hydrogen peroxide that liquefied ammonia that weight concentration is 25% and mass concentration are 30% when being heated to 76 ℃, time for adding is 1 hour, dropwise rear continuation reaction 0.5 hour, the pressure of ketoxime reaction is 1atm.The weight ratio of described pimelinketone and microballoon TS-1 catalyzer and the trimethyl carbinol aqueous solution is 1:0.03:5; The water-content of the described trimethyl carbinol aqueous solution is the 20%(volume ratio); The mol ratio of described pimelinketone and liquefied ammonia is 1:1.15; The mol ratio of described pimelinketone and hydrogen peroxide is 1:1.06.
The purification of c, ketoxime
After the ketoxime combination reaction finishes, reaction solution goes out catalyzer utilization to be recycled through standing separation, and it is the crystalloid cyclohexanone-oxime that the reaction clear liquid obtains product after distilling, extract and revolving steaming.
Product is through stratographic analysis: the pimelinketone transformation efficiency is 99.3%, and the cyclohexanone-oxime selectivity is 99.5%, and the hydrogen peroxide utilization ratio is 99.6%.
Embodiment 7
The preparation of a, catalyzer
A step with embodiment 1.
The combination reaction of b, ketoxime
By the microballoon TS-1 catalyzer of above-mentioned preparation and the trimethyl carbinol aqueous solution, mix and blend in reactor also heats the combination reaction of carrying out ketoxime, temperature of reaction is 76 ℃, the hydrogen peroxide that the liquefied ammonia that to start to drip respectively pimelinketone, weight concentration when being heated to 76 ℃ be 25% and mass concentration are 30%, time for adding is 1 hour, dropwise rear continuation reaction 0.5 hour, the pressure of ketoxime reaction is 1atm.The weight ratio of described pimelinketone and microballoon TS-1 catalyzer and the trimethyl carbinol aqueous solution is 1:0.03:5; The water-content of the described trimethyl carbinol aqueous solution is the 20%(volume ratio); The mol ratio of described pimelinketone and liquefied ammonia is 1:1.15; The mol ratio of described pimelinketone and hydrogen peroxide is 1:1.06.
The purification of c, ketoxime
After the ketoxime combination reaction finishes, reaction solution goes out catalyzer utilization to be recycled through standing separation, and it is the crystalloid cyclohexanone-oxime that the reaction clear liquid obtains product after distilling, extract and revolving steaming.
Product is through stratographic analysis: the pimelinketone transformation efficiency is 97.0%, and the cyclohexanone-oxime selectivity is 99.2%, and the hydrogen peroxide utilization ratio is 99.3%.
Embodiment 8
The preparation of a, catalyzer
A step with embodiment 1.
The combination reaction of b, ketoxime
The combination reaction of ketoxime is carried out in the liquefied ammonia that is 25% by the microballoon TS-1 catalyzer of above-mentioned preparation and pimelinketone, the trimethyl carbinol aqueous solution and weight concentration mix and blend heating in reactor, temperature of reaction is 72 ℃, start to drip the hydrogen peroxide that mass concentration is 30% when being heated to 72 ℃, time for adding is 1.5 hours, dropwise rear continuation reaction 0.5 hour, the pressure of ketoxime reaction is 1atm.The weight ratio of described pimelinketone and microballoon TS-1 catalyzer and the trimethyl carbinol aqueous solution is 1:0.1:5; The water-content of the described trimethyl carbinol aqueous solution is the 30%(volume ratio); The mol ratio of described pimelinketone and liquefied ammonia is 1:1.3; The mol ratio of described pimelinketone and hydrogen peroxide is 1:1.2.
The purification of c, ketoxime
After the ketoxime combination reaction finishes, reaction solution goes out catalyzer utilization to be recycled through standing separation, and it is the crystalloid cyclohexanone-oxime that the reaction clear liquid obtains product after distilling, extract and revolving steaming.
Product is through stratographic analysis: the pimelinketone transformation efficiency is 98.9%, and the cyclohexanone-oxime selectivity is 99.5%, and the hydrogen peroxide utilization ratio is 99.7%.
Just the present invention will be further described for above each embodiment, and not in order to limit patent of the present invention, all is the present invention's equivalence enforcement, within all should being contained in the claim scope of patent of the present invention.
Claims (2)
1. the preparation method of a ketoxime, is characterized in that the method adopts microballoon TS-1 catalyzer ketone, ammonia and hydroperoxidation system to be carried out to the ketoxime combination reaction of highly selective, and concrete preparation comprises the following steps:
The outfit of a, reaction system
Microballoon TS-1 catalyzer and organic solvent, ketone and ammonia are added to reactor in proportion successively, through being uniformly mixed as the ketoxime reaction system; Described organic solvent is one or more the mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol and the trimethyl carbinol; Described ketone is one or more the mixing in aliphatic ketone, alicyclic ketone and aromatic ketone; The weight ratio of described ketone and catalyzer and organic solvent is 1:0.03 ~ 0.15:1 ~ 10; The mol ratio of described ketone and ammonia is 1:1 ~ 3;
The combination reaction of b, ketoxime
Above-mentioned ketoxime reaction system is heated, start to drip the hydrogen peroxide that mass concentration is 1 ~ 50% when temperature of reaction is raised to 30 ~ 150 ℃, time for adding is 1 ~ 5 hour, dropwises rear continuation reaction 0.1 ~ 3 hour, and the pressure of ketoxime reaction system is 1 ~ 5atm; The mol ratio of described hydrogen peroxide and ketone is 1 ~ 2:1;
The purification of c, ketoxime
The ketoxime combination reaction is isolated the catalyst recovery utilization after finishing, and it is the crystalloid ketoxime that filtrate obtains product after distilling, extract and revolving steaming.
2. the preparation method of ketoxime according to claim 1, is characterized in that described microballoon TS-1 catalyzer is 1:0.05 ~ 0.4:0.005 ~ 0.2:10 ~ 30:1.0 * 10 by tetraethyl orthosilicate and tetrabutyl titanate, TPAOH, pure water and triblock polyether in molar ratio
-3~ 4.0 * 10
-3mix, carry out the hydrolysis plastic reaction of 0.5 ~ 1 hour at 50 ~ 60 ℃ of temperature, then at 80 ~ 90 ℃, 110 ~ 130 ℃ and 160 ~ 180 ℃ of three temperature sections, carry out respectively 10 ~ 20 hours, 2 ~ 10 hours and 10 ~ 20 hours crystallization, the mixture after crystallization after filtration, after washing, drying and roasting the diameter microballoon that is 2 ~ 100 μ m.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130157A (en) * | 2014-07-08 | 2014-11-05 | 华东师范大学 | Method for preparing cyclohexanone-oxime |
| CN105152968A (en) * | 2015-07-24 | 2015-12-16 | 常州大学 | Method for continuously producing ketoxime by using microchannel reactor |
| CN105837468A (en) * | 2015-01-15 | 2016-08-10 | 湖北金湘宁化工科技有限公司 | Preparation method of cyclohexanone-oxime |
| CN113173866A (en) * | 2021-04-23 | 2021-07-27 | 衢州巨化锦纶有限责任公司 | Method for treating heavy residual liquid in ketoxime production |
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| CN1793112A (en) * | 2005-12-28 | 2006-06-28 | 华东师范大学 | Process for producing oxime |
| CN102145300B (en) * | 2011-03-08 | 2012-11-28 | 华东师范大学 | Microsphere TS-1 catalyst and preparation method of microsphere TS-1 catalyst |
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| CN1793112A (en) * | 2005-12-28 | 2006-06-28 | 华东师范大学 | Process for producing oxime |
| CN102145300B (en) * | 2011-03-08 | 2012-11-28 | 华东师范大学 | Microsphere TS-1 catalyst and preparation method of microsphere TS-1 catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130157A (en) * | 2014-07-08 | 2014-11-05 | 华东师范大学 | Method for preparing cyclohexanone-oxime |
| CN105837468A (en) * | 2015-01-15 | 2016-08-10 | 湖北金湘宁化工科技有限公司 | Preparation method of cyclohexanone-oxime |
| CN105152968A (en) * | 2015-07-24 | 2015-12-16 | 常州大学 | Method for continuously producing ketoxime by using microchannel reactor |
| CN113173866A (en) * | 2021-04-23 | 2021-07-27 | 衢州巨化锦纶有限责任公司 | Method for treating heavy residual liquid in ketoxime production |
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Application publication date: 20140108 |