CN102001966A - Method for synthesizing cyclohexanone-oxime from cyclohexane in one step - Google Patents
Method for synthesizing cyclohexanone-oxime from cyclohexane in one step Download PDFInfo
- Publication number
- CN102001966A CN102001966A CN2010105341682A CN201010534168A CN102001966A CN 102001966 A CN102001966 A CN 102001966A CN 2010105341682 A CN2010105341682 A CN 2010105341682A CN 201010534168 A CN201010534168 A CN 201010534168A CN 102001966 A CN102001966 A CN 102001966A
- Authority
- CN
- China
- Prior art keywords
- hexanaphthene
- oxime
- cyclohexane
- cyclohexanone
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing cyclohexanone-oxime from cyclohexane in one step, relating to the field of chemical synthesis. The method comprises the following steps of: adding a titanium-silicate molecular sieve TS-1 used as a catalyst into a synthesis reactor at normal pressure with cyclohexane, H2O2 and ammonia water as raw materials, wherein 0.2g of the catalyst titanium-silicate molecular sieve TS-1is added in 1 mmol of cyclohexane; and controlling the reaction temperature at 25-80 DEG C and the reaction time for 1-30h to synthesize cyclohexanone-oxime in one step, wherein the molar ratio of cyclohexane to H2O2 to ammonia water is 1:1.5-3.5:1.5-2. The method has simple process conditions and mild reaction conditions. Byproducts generated in the reaction process are KA oil and hexanedioic acid which have higher application value, and can greatly improve the utilization rate of resources. The whole process is basically free of environmental pollution and truly realizes zero emission.
Description
Technical field
The present invention relates to the synthetic field of chemical industry, specifically is the method for one step of raw material liquid phase synthesizing cyclohexane 1 ketoxime with the hexanaphthene.
Background technology
At present industrial mainly is by multistep processes synthesizing cyclohexane 1 ketoxime, as nitrogen oxide reduction method, oxammonium sulfate method and the phosphatic hydroxylamine method etc. of pimelinketone-azanol route, all there is the processing condition complexity in these synthetic methods, environmental pollution is serious and the shortcomings such as ammonium sulfate byproduct of a large amount of low values of association.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, proposed that a kind of processing condition are simple, reaction conditions is gentle, non-environmental-pollution, can increase substantially the method from hexanaphthene one-step synthesis cyclohexanone-oxime of resource utilization.
The objective of the invention is to realize: in synthesis reactor by following manner, with hexanaphthene, hydrogen peroxide and ammoniacal liquor is raw material, under normal pressure, add titanium-silicon molecular sieve TS-1 as catalyzer, catalyst consumption is 0.2g titanium-silicon molecular sieve TS-1/mmol cyclohexane; Control reaction temperature is 25～80 ℃, and the reaction times is 1～30 hour, the one-step synthesis cyclohexanone-oxime, and the mol ratio of each raw material is a hexanaphthene: H
2O
2: ammoniacal liquor=1:1.5～3.5:1.5～2.
Ti/Si=1:10～1:60 in the described titanium-silicon molecular sieve TS-1.
Described temperature of reaction is 60-75 ℃, and the described reaction times is 6-18h.
Described hexanaphthene is dissolved in the organic solvent, and hexanaphthene is 1:2～8 with the volume of organic solvent ratio.
Described organic solvent is a kind of or its mixture in the trimethyl carbinol, acetonitrile, ethanol, ether, acetone, the benzene.
The present invention generates cyclohexanone-oxime by one step of reaction of hexanaphthene and hydrogen peroxide and ammoniacal liquor, and processing condition are simple, the reaction conditions gentleness.The byproduct that generates in the reaction process is KA oil and hexanodioic acid, KA oil wherein is the mixture of hexalin and pimelinketone, it has many uses general, can be applied to industries such as rubber ingredients, printing ink, coating, daily use chemicals, medicine, printing and dyeing, hexanodioic acid also has higher using value, can improve the utilization ratio of resource significantly.The essentially no environmental pollution of whole technological process has really realized zero release.
Embodiment
Embodiment 1:
By hexanaphthene: the proportioning of hydrogen peroxide: ammoniacal liquor=1mL:2.5mL:2mL is packed material in the 100mL glass reactor successively by the order of hexanaphthene, solvent, catalyzer, hydrogen peroxide, ammoniacal liquor, the 6mL trimethyl carbinol is a solvent, 75 ℃ of temperature of reaction, reaction times 8h, the amount of catalyzer accounts for 25% of hexanaphthene.
Post reaction mixture gas chromatographic analysis, conversion of cyclohexane are 18.8%, and the selectivity of cyclohexanone-oxime is 11.7%, and the selectivity of KA oil is 38.9%, and the selectivity of hexanodioic acid is 25.7%.
Reacted mixed solution separates cyclohexanone-oxime product and 0.48 byproduct that restrains that obtains 0.32 gram through suction filtration separating catalyst, underpressure distillation.
Embodiment 2:
Hexanaphthene: hydrogen peroxide: ammoniacal liquor=1mL:5mL:4mL, step is with embodiment 1, and difference is that adding the 6mL acetonitrile is solvent, 75 ℃ of temperature of reaction, reaction times 8h, the amount of catalyzer accounts for 25% of hexanaphthene.
Post reaction mixture gas chromatographic analysis, conversion of cyclohexane are 6.8%, and the selectivity of cyclohexanone-oxime is 10.4%, and the selectivity of KA oil is 36.1%, and the selectivity of hexanodioic acid is 17.3%.
Reacted mixed solution separates cyclohexanone-oxime product and 0.18 byproduct that restrains that obtains 0.08 gram through suction filtration separating catalyst, underpressure distillation.
Embodiment 3:
Hexanaphthene: hydrogen peroxide: ammoniacal liquor=1mL:1mL:1mL, step is with embodiment 1, and difference is that temperature of reaction is 60 ℃, reaction times 16h, the amount of catalyzer accounts for 20% of hexanaphthene.
Post reaction mixture gas chromatographic analysis, conversion of cyclohexane are 10.1%, and the selectivity of cyclohexanone-oxime is 13.3%, and the selectivity of KA oil is 39.8%, and the selectivity of hexanodioic acid is 28.7%.
Reacted mixed solution separates cyclohexanone-oxime product and 0.16 byproduct that restrains that obtains 0.21 gram through suction filtration separating catalyst, underpressure distillation.
Claims (5)
1. the method from hexanaphthene one-step synthesis cyclohexanone-oxime is characterized in that, in synthesis reactor, with hexanaphthene, hydrogen peroxide and ammoniacal liquor is raw material, under normal pressure, add titanium-silicon molecular sieve TS-1 as catalyzer, catalyst consumption is 0.2g titanium-silicon molecular sieve TS-1/mmol cyclohexane; Control reaction temperature is 25～80 ℃, and the reaction times is 1～30 hour, the one-step synthesis cyclohexanone-oxime, and the mol ratio of each raw material is a hexanaphthene: H
2O
2: ammoniacal liquor=1:1.5～3.5:1.5～2.
2. the method from hexanaphthene one-step synthesis cyclohexanone-oxime according to claim 1 is characterized in that, Ti/Si=1:10～1:60 in the described titanium-silicon molecular sieve TS-1.
3. the method from hexanaphthene one-step synthesis cyclohexanone-oxime according to claim 1 is characterized in that, described temperature of reaction is 60-75 ℃, and the described reaction times is 6-18h.
4. the method from hexanaphthene one-step synthesis cyclohexanone-oxime according to claim 1 is characterized in that described hexanaphthene is dissolved in the organic solvent, and hexanaphthene is 1:2～8 with the volume of organic solvent ratio.
5. the method from hexanaphthene one-step synthesis cyclohexanone-oxime according to claim 4 is characterized in that, described organic solvent is a kind of or two kinds of mixtures in the trimethyl carbinol, acetonitrile, ethanol, ether, acetone, the benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105341682A CN102001966A (en) | 2010-11-08 | 2010-11-08 | Method for synthesizing cyclohexanone-oxime from cyclohexane in one step |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105341682A CN102001966A (en) | 2010-11-08 | 2010-11-08 | Method for synthesizing cyclohexanone-oxime from cyclohexane in one step |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102001966A true CN102001966A (en) | 2011-04-06 |
Family
ID=43809705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105341682A Pending CN102001966A (en) | 2010-11-08 | 2010-11-08 | Method for synthesizing cyclohexanone-oxime from cyclohexane in one step |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102001966A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395757A (en) * | 2013-08-12 | 2013-11-20 | 河北工业大学 | Method for synthesizing hydroxylamine salt |
| CN103420869A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Method of ammoxidation of cyclohexane |
| CN103864643A (en) * | 2014-03-04 | 2014-06-18 | 华东师范大学 | Preparation method of oxime |
| CN107235857A (en) * | 2017-07-17 | 2017-10-10 | 湖南工程学院 | A kind of preparation method of cyclohexanone oxime |
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN180725B (en) * | 1990-11-07 | 1998-03-14 | Council Scient Ind Res |
-
2010
- 2010-11-08 CN CN2010105341682A patent/CN102001966A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN180725B (en) * | 1990-11-07 | 1998-03-14 | Council Scient Ind Res |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420869A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Method of ammoxidation of cyclohexane |
| CN103420869B (en) * | 2012-05-23 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of method of ammoxidation of cyclohexane |
| CN103395757A (en) * | 2013-08-12 | 2013-11-20 | 河北工业大学 | Method for synthesizing hydroxylamine salt |
| CN103395757B (en) * | 2013-08-12 | 2015-05-06 | 河北工业大学 | Method for synthesizing hydroxylamine salt |
| CN103864643A (en) * | 2014-03-04 | 2014-06-18 | 华东师范大学 | Preparation method of oxime |
| CN103864643B (en) * | 2014-03-04 | 2015-11-18 | 华东师范大学 | A kind of preparation method of oxime |
| CN107235857A (en) * | 2017-07-17 | 2017-10-10 | 湖南工程学院 | A kind of preparation method of cyclohexanone oxime |
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN111153831B (en) * | 2020-02-19 | 2022-11-01 | 湘潭大学 | Preparation method of cyclohexanone oxime |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105197956B (en) | The preparation method of the HTSs of TS 1 | |
| CN102001966A (en) | Method for synthesizing cyclohexanone-oxime from cyclohexane in one step | |
| CN103864643B (en) | A kind of preparation method of oxime | |
| CN103395757B (en) | Method for synthesizing hydroxylamine salt | |
| CN103483221A (en) | Preparation method of cyclohexanone oxime | |
| CN110372639A (en) | A kind of method that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0 | |
| CN103172535A (en) | Liquid-phase fixed bed preparation method of cyclohexanone oxime | |
| CN109942457A (en) | A kind of heterogeneous cyclohexanone oxime preparation method | |
| CN103708494A (en) | Novel modification method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve | |
| CN106006665B (en) | A kind of preparation method of titanium-silicon molecular sieve TS-1 | |
| CN107162932A (en) | A kind of method by benzaldehyde and ionic liquid type hydroxylamine salt one-step synthesis benzonitrile | |
| CN105728034A (en) | Ti-ECNU-5 titanium silicalite molecular sieve as well as preparation method and application thereof | |
| CN109180437A (en) | The method that cumyl hydroperoxide decomposition prepares phenol in tubular type continuous flow reactor | |
| CN111153831A (en) | Preparation method of cyclohexanone oxime | |
| CN109641862B (en) | Method for reactivating homogeneous oxidation catalyst | |
| CN111253281B (en) | Preparation method of cyclohexanone oxime | |
| CN1793113A (en) | Process for producing cyclohexanone oxime | |
| CN103012262B (en) | Caprolactam production method | |
| CN105111044B (en) | The method that prenol is synthesized by butenol | |
| CN111320545A (en) | Microchannel reaction process of p \ m-nitrobenzaldehyde | |
| CN102850198A (en) | Cyclohexanol oxidation method | |
| CN114671808A (en) | Preparation method of caprolactam | |
| CN102452890B (en) | Method for preparing methylcyclohexane through hydrogenolysis of methylcyclohexanol | |
| CN107628957A (en) | A kind of new method research of the direct ammonification synthesizing cyclohexane 1 amine of cyclohexene | |
| CN104341318B (en) | Method for synthesizing cyclohexanone-oxime and caprolactam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110406 |