CN104177222A - Method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide - Google Patents
Method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide Download PDFInfo
- Publication number
- CN104177222A CN104177222A CN201310195936.XA CN201310195936A CN104177222A CN 104177222 A CN104177222 A CN 104177222A CN 201310195936 A CN201310195936 A CN 201310195936A CN 104177222 A CN104177222 A CN 104177222A
- Authority
- CN
- China
- Prior art keywords
- decomposition
- tubular reactor
- inorganic phase
- hexalin
- inorganic
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide in a cyclohexane oxidation liquid, and the method is characterized in that, a sodium hydroxide solution and a cobalt acetate solution are added in different feeding ports of a tubular reactor, cobalt ion concentration of the inorganic phase is 1.5-10ppm, the volume ratio of organic phase to inorganic phase in the decomposition reactor is 5.0-7.0: 1, and the basicity is 0.7-3.0mol / kg. The decomposition reactor temperature is controlled at 85-120 DEG C, the cyclohexyl hydroperoxide decomposition rate is greater than or equal to 99.5%, the cyclohexanone and cyclohexanol yield is greater than or equal to 90%, and the ketone-alcohol ratio is more than 1.0.
Description
Technical field
The present invention relates to a kind of method of preparing pimelinketone and hexalin of being decomposed by cyclohexyl hydroperoxide in cyclohexane oxide solution in tubular reactor.
Background technology
Cyclohexane oxidation preparing cyclohexanone is by following step: first hexanaphthene is at 155～165 DEG C, make the cyclohexane solution of cyclohexyl hydroperoxide through air non-catalyst oxidation, cyclohexyl hydroperoxide in cyclohexane solution is under certain basicity subsequently, taking Cobaltous diacetate as catalyzer, concentration of cobalt ions 1～3ppm, organic phase and inorganic phase volume ratio 85:15, be decomposed into pimelinketone and hexalin under 85 ~ 110 DEG C of conditions of temperature of reaction; Product after decomposition carries out separating of organic phase and inorganic phase, and organic phase enters alkane rectification system, and recovered overhead hexanaphthene send stills for air blowing to recycle, and tower kettle product is thick keto-alcohol, and thick keto-alcohol successively obtains pimelinketone and hexalin after rectifying; Hexalin obtains pimelinketone after dehydrogenation reaction.In decomposing cyclohexyl hydrogen peroxide process, there are the following problems at present: the keto-alcohol ratio obtaining after decomposing cyclohexyl hydrogen peroxide is not high, and general keto-alcohol, than below 1:1, has increased the load of cyclohexanol dehydrogenation below.
Patent 201110351845.1 inventions relate to a kind of method and apparatus of decomposing cyclohexyl hydrogen peroxide.Be characterized in: adopt three step decomposition technique methods, decompose the oxidation mixture containing cyclohexyl hydroperoxide, the separate chamber that decomposed solution flows into the 3rd step decomposition reactor bottom carry out two be separated after, carry out contact process three times with strong alkali solution, soda-wash water, recycle-water from saponification again, compoundly complete decomposition reaction and separate with efficient salkali waste, follow-up salkali waste separation system is not set; The pH value of major control the first step decomposition reaction is controlled the soda balance of decomposing system; Salt and the catalyzer in washing tower washing steam, carried secretly for the flash distillation that the first step is decomposed; The first step decomposition reactor is the vertical equipment that is longitudinally divided into two portions San Ge district with dividing plate; The tower that second step decomposition reactor is made up of filler and special baffle; The 3rd step decomposition reactor is tray column.Positively effect of the present invention is that technical process is short, and soda balance is easily controlled, and quantity of alkali consumption is low.The shortcoming of this patent is decomposition reactor complex structure, and floor space is large, and the large operation of investment is more difficult etc.
Patent CN201120306207.3 utility model discloses a kind of cyclohexylhydroperoxdecomposition decomposition reaction device, it is characterized in that: include decomposing pot, stirring, in described decomposing pot, be provided with 1～3 layer by stirring the blade driving, the discharge port baffle plate of decomposing pot is provided with Anti-swirl device, and the pipeline before decomposing pot is respectively equipped with circulation alkali water cooler and line mixer.The utility model can be eliminated the situation that is increased in the eddy flow of decomposing pot discharge port generation due to mixing speed effectively, solves decomposing pot discharging pump and has the not potential safety hazard of material loading; In addition, also can, by regulating the temperature of circulation alkali, realize the controlled of cyclohexylhydroperoxdecomposition decomposition reaction temperature, reduce alcohol ketone condensation.The shortcoming of this patent is decomposing pot complex structure, needs the shortcomings such as many cover decomposing pots could be realized the decomposition completely of cyclohexyl hydroperoxide, and floor space is large.
Summary of the invention
The object of the invention is to propose a kind of improved method of preparing pimelinketone and hexalin of being decomposed by cyclohexyl hydroperoxide in cyclohexane oxide solution in tubular reactor.
The present invention is achieved in that and in tubular type decomposition reactor, adds continuously the inorganic phase alkaline solution and the organic phase cyclohexane oxide solution that contain Cobaltous diacetate, in inorganic phase, concentration of cobalt ions is 1.5～10ppm, in decomposition reactor, organic phase and inorganic phase volume ratio are 5.0～7.0:1, basicity 0.7～3.0mol/kg.Control 85～120 DEG C of decomposition reaction actuator temperatures, the time of decomposition reaction is 15～60 minutes, and the pressure that enters tubular reactor is being 0.1～0.5 Mpa.
A kind of preferred reaction conditions of the present invention is, decomposition reaction temperature is 92～98 DEG C, organic phase and inorganic phase volume ratio are 5.6～6.0:1, in inorganic phase, the concentration of catalyst cobalt ion is 2.5～3.0ppm, machine phase basicity is 1.2～2.5mol/kg, the time of decomposition reaction is 30～45 minutes, and the pressure of tubular reactor is 0.4～0.5 MPa.
In the inventive method, normally add sodium hydroxide solution and cobalt acetate solution according to reaction process by high-pressure pump at the different charging openings of tubular reactor axis direction.
The inventive method decomposing cyclohexyl hydrogen peroxide Shuai≤99.5%, pimelinketone and hexalin Shou Shuai≤and 90.0%, keto-alcohol is than more than 1. 0.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
It is 85m that the tubular reactor entrance that embodiment 1. is 30 meters in length adds inbound traffics
3the cyclohexane oxide solution of/h adds inbound traffics 10m simultaneously
3the inorganic phase alkali lye that/h contains catalyst acetic acid cobalt, concentration of cobalt ions 1.5 ppm, basicity 0.7mol/kg, 90 DEG C of import temperature of reaction, tubular reactor intake pressure 0.1MPa, adding inbound traffics at 15 meters of of tubular reactor entrance is 5m
3/ h alkali lye, decomposing cyclohexyl hydrogen peroxide rate 99.54%, pimelinketone and hexalin yield 90.47%, pimelinketone: hexalin=1.01:1.
It is 85m that the tubular reactor entrance that embodiment 2. is 30 meters in length adds inbound traffics
3the cyclohexane oxide solution of/h adds inbound traffics 8m simultaneously
3the inorganic phase alkali lye that/h contains catalyst acetic acid cobalt, concentration of cobalt ions 2.5 ppm, 92 DEG C of basicity 1.2mol/kg import temperature of reaction, tubular reactor intake pressure 0.2MPa, adding respectively inbound traffics at 15 meters of tubular reactor entrances and 20 meters of is 5m
3/ h and 8m
3the alkali lye of/h, decomposing cyclohexyl hydrogen peroxide rate 99.62%, pimelinketone and hexalin yield 91.47%, pimelinketone: hexalin=1.08:1.
It is 100m that the tubular reactor entrance that embodiment 3. is 45 meters in length adds inbound traffics
3the cyclohexane oxide solution of/h adds inbound traffics 10m simultaneously
3the inorganic phase alkali lye that/h contains catalyst acetic acid cobalt, concentration of cobalt ions 3.5 ppm, 91 DEG C of basicity 3.0mol/kg import temperature of reaction, tubular reactor intake pressure 0.5MPa, adding respectively inbound traffics at 5 meters of tubular reactor entrances and 10 meters of is 8m
3/ h and 5m
3the alkali lye of/h, decomposing cyclohexyl hydrogen peroxide rate 99.70%, pimelinketone and hexalin yield 91.50%, pimelinketone: hexalin=1.05:1.
It is 100m that the tubular reactor entrance that embodiment 4 is 45 meters in length adds inbound traffics
3the cyclohexane oxide solution of/h adds inbound traffics 10m simultaneously
3the inorganic phase alkali lye that/h contains catalyst acetic acid cobalt, concentration of cobalt ions 3.5 ppm, 91 DEG C of basicity 2.5mol/kg import temperature of reaction, tubular reactor intake pressure 0.5MPa, adding respectively inbound traffics at 5 meters of tubular reactor entrances and 10 meters of is 8m
3/ h and 5m
3the alkali lye of/h, decomposing cyclohexyl hydrogen peroxide rate 99.53%, pimelinketone and hexalin yield 90.50%, pimelinketone: hexalin=1.02:1.
It is 100m that the tubular reactor entrance that embodiment 5 is 45 meters in length adds inbound traffics
3the cyclohexane oxide solution of/h adds inbound traffics 9m simultaneously
3the inorganic phase alkali lye that/h contains catalyst acetic acid cobalt, concentration of cobalt ions 10 ppm, 95 DEG C of basicity 7.0mol/kg import temperature of reaction, tubular reactor intake pressure 0.5MPa, adding respectively inbound traffics at 5 meters of tubular reactor entrances and 10 meters of is 10m
3/ h and 5m
3the alkali lye of/h, decomposing cyclohexyl hydrogen peroxide rate 99.56%, pimelinketone and hexalin yield 90.50%, pimelinketone: hexalin=1.04:1.
Claims (8)
1. the method for a decomposing cyclohexyl hydrogen peroxide preparing cyclohexanone and hexalin, it is characterized in that, in tubular reactor, under sodium hydroxide exists, taking Cobaltous diacetate as catalyzer, cyclohexyl hydroperoxide in cyclohexane oxide solution decomposes generation pimelinketone and hexalin in tubular reactor, wherein decomposition condition is: 85～120 DEG C of temperature, organic phase and the inorganic 5.0～7.0:1 that is in a ratio of, in inorganic phase, the concentration of catalyst cobalt ion is 1.0～3.0ppm, inorganic phase basicity is 0.7～3.0mol/kg, the time of decomposition reaction is 15～60 minutes, pressure is 0.1～0.6MPa.
2. method according to claim 1, it is characterized in that controlling decomposition reaction temperature is 92～98 DEG C.
3. method according to claim 1, is characterized in that in decomposition reactor that organic phase and inorganic phase volume ratio are 5.6～6.0:1.
4. method according to claim 1, the concentration that it is characterized in that catalyst cobalt ion in inorganic phase is 2.5～3.0ppm.
5. method according to claim 1, is characterized in that inorganic phase basicity is 1.2～2.5mol/kg.
6. method according to claim 1, the time that it is characterized in that decomposition reaction is 30～45 minutes.
7. method according to claim 1, the pressure that it is characterized in that tubular reactor is 0.4～0.5 MPa.
8. method according to claim 1, is characterized in that adding sodium hydroxide solution and cobalt acetate solution at the different charging openings of tubular reactor axis direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310195936.XA CN104177222A (en) | 2013-05-24 | 2013-05-24 | Method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310195936.XA CN104177222A (en) | 2013-05-24 | 2013-05-24 | Method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104177222A true CN104177222A (en) | 2014-12-03 |
Family
ID=51958606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310195936.XA Pending CN104177222A (en) | 2013-05-24 | 2013-05-24 | Method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104177222A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542980A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | The method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and Hexalin under slightly acidic condition |
| CN110526798A (en) * | 2018-05-23 | 2019-12-03 | 中国科学院大连化学物理研究所 | A kind of decomposition method of cyclohexyl hydroperoxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184097A (en) * | 1996-12-04 | 1998-06-10 | 肖藻生 | Preparation process of cyclohexanol and cyclohexanone |
| US20030229253A1 (en) * | 2002-06-05 | 2003-12-11 | Ludovic Fodor | High yield cyclohexyl hydroperoxide decompostition process |
-
2013
- 2013-05-24 CN CN201310195936.XA patent/CN104177222A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184097A (en) * | 1996-12-04 | 1998-06-10 | 肖藻生 | Preparation process of cyclohexanol and cyclohexanone |
| US20030229253A1 (en) * | 2002-06-05 | 2003-12-11 | Ludovic Fodor | High yield cyclohexyl hydroperoxide decompostition process |
Non-Patent Citations (2)
| Title |
|---|
| 王松汉主编: "《石油化工设计手册 第3卷 化工单元过程》", 31 January 2002, article "汽-液反应器的基本类型", pages: 1835 * |
| 黄风林主编: "《石油天然气化工工艺》", 30 September 2011, article "无催化剂氧化工艺", pages: 185 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542980A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | The method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and Hexalin under slightly acidic condition |
| CN110526798A (en) * | 2018-05-23 | 2019-12-03 | 中国科学院大连化学物理研究所 | A kind of decomposition method of cyclohexyl hydroperoxide |
| CN110526798B (en) * | 2018-05-23 | 2021-03-02 | 中国科学院大连化学物理研究所 | Decomposition method of cyclohexyl hydroperoxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102115433B (en) | Synthesis method of propionaldehyde by low-pressure carbonyl of ethylene | |
| CN102627525B (en) | Preparation process for preparing hexamethylene and cyclohexanone by cyclohexane oxidation | |
| CN103992206B (en) | The method and system of prenol are prepared in a kind of ester exchange | |
| CN112876395A (en) | Preparation method of vitamin A acetate | |
| CN104387234B (en) | A kind of synthetic method of 3-methyl-3-butene-1-alcohol | |
| CN108341941B (en) | Continuous production method and device for high-purity alkali metal catalyzed polyether polyol | |
| CN104177222A (en) | Method for preparation of cyclohexanone and cyclohexanol by decomposition of cyclohexyl hydroperoxide | |
| CN104383949B (en) | A kind of Ketocyclopentane catalyst for synthesizing and preparation method thereof and the application in Ketocyclopentane synthesizes | |
| CN109134217B (en) | Oxidation device and oxidation process improvement method in cyclohexanone production process by cyclohexane oxidation method | |
| CN104230635B (en) | The method of hydrogenation of acetophenone ethylbenzene processed | |
| CN204342435U (en) | The hydrogenation fluidized-bed reactor of anthraquinone legal system hydrogen peroxide | |
| CN105601486A (en) | Method for preparing cyclohexanone with cyclohexane liquid-phase oxidation process | |
| CN108516934B (en) | Production process for producing cyclohexyl formate through bulkhead reaction rectification | |
| CN101481304A (en) | Process for preparing aminic acid by methyl formate hydrolysis | |
| CN203448102U (en) | Gas-liquid spraying circulating reaction device for preparing glyoxylic acid by oxygen oxidization method | |
| CN104230636B (en) | Low content hydrogenation of acetophenone is prepared the method for ethylbenzene | |
| CN103709010B (en) | A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method | |
| CN106397365A (en) | Purifying apparatus for 1,2-epoxybutane | |
| CN104028177A (en) | Method for reinforcing mixing effect of hydraulic reaction apparatus | |
| CN212076906U (en) | Side-line reaction type dioxolane production process device | |
| CN106946678A (en) | A kind of method that cyclohexane oxide solution decomposes preparing cyclohexanone and cyclohexanol | |
| CN104513152B (en) | A kind of method and apparatus of nitric acid oxidation alcohol ketone adipic acid | |
| CN203938621U (en) | A kind of by the refining isobutyric suite of equipment of isobutyric aldehyde | |
| CN105056943B (en) | A kind of production system and preparation method of producing cyclohexene with benzene selective hydrogenation catalyst | |
| CN107365245B (en) | A kind of methallyl alcohol production system and method |
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: 20141203 |