CN107400038A - A kind of method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and cyclohexanol - Google Patents
A kind of method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and cyclohexanol Download PDFInfo
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- CN107400038A CN107400038A CN201610336050.6A CN201610336050A CN107400038A CN 107400038 A CN107400038 A CN 107400038A CN 201610336050 A CN201610336050 A CN 201610336050A CN 107400038 A CN107400038 A CN 107400038A
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- cyclohexanol
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- 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
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Abstract
The present invention relates to a kind of method for improving cyclohexyl hydroperoxide and decomposing preparing cyclohexanone and cyclohexanol keto-alcohol ratio and reducing alkaline consumption, it is characterized in that, in tubular type, autoclave or tower reactor, the first step is using the different monooctyl ester of chromic acid as catalyst, cyclohexyl hydroperoxide in cyclohexane oxide solution decomposes generation cyclohexanone and cyclohexanol, second step is using cobalt acetate as catalyst, in the presence of sodium hydroxide, solution after the first step is decomposed continues to decompose, and the hexamethylene decomposed solution after decomposition carries out the separation of organic phase and inorganic phase.Wherein cyclohexyl hydroperoxide Fen Xie Shuai≤99.5%, cyclohexanone and cyclohexanol Shou Shuai≤95.0%, for keto-alcohol ratio more than 1.3, the consumption of sodium hydroxide reduces by more than 30% than being decomposed under traditional alkalescence condition.
Description
Technical field
The present invention relates to a kind of by the method that decomposition prepares cyclohexanone and cyclohexanol under two kinds of different catalysts existence conditions of cyclohexyl hydroperoxide in cyclohexane oxide solution.
Background technology
Cyclohexane oxidation preparing cyclohexanone is by following steps：Hexamethylene is at 155~165 DEG C first, the cyclohexane solution of cyclohexyl hydroperoxide is made through air non-catalyst oxidation, cyclohexyl hydroperoxide in subsequent cyclohexane solution is under certain basicity sodium hydroxide solution, using cobalt acetate as catalyst, 1~3ppm of concentration of cobalt ions, organic phase and inorganic phase volume ratio 85：15, cyclohexanone and cyclohexanol are decomposed under the conditions of 85 ~ 110 DEG C of reaction temperature；Product after decomposition carries out the separation of organic phase and inorganic phase, organic phase enters alkane rectification system, and recovered overhead hexamethylene send stills for air blowing to recycle, and tower kettle product is thick keto-alcohol, thick keto-alcohol successively obtains cyclohexanone and cyclohexanol after rectifying, and cyclohexanol obtains cyclohexanone after dehydrogenation reaction.There are the following problems in traditional cyclohexyl hydroperoxide decomposable process at present：The keto-alcohol ratio that cyclohexyl hydroperoxide obtains after decomposing is not high, and general keto-alcohol ratio is 1：Less than 1, decomposition yield adds the load of cyclohexanol dehydrogenation below typically 89% or so；Because decomposable process is carried out in the basic conditions, a large amount of spent lyes are produced, are corroded and seriously polluted, are burned after the method use concentration of Treatment of Cyclohexanone salkali waste, high energy consumption.Therefore, there is an urgent need to employ new technology to realize that the green of cyclohexyl hydroperoxide is decomposed.
Patent CN10179826A, a kind of New technique for decomposing oxidized liquid in production of cyclohexanone, it is characterised in that：Using two sections of decomposition techniques, increase a set of new decomposition process, connected with former decomposition process, it is lst-stage precipitation flow to increase flow newly, and former decomposition process is constant, oxidation solution following current enters lst-stage precipitation, then two sections of decomposition are gone, new alkali lye then by two sections of entrance, countercurrently returns to lst-stage precipitation, by one section of waste discharge alkali so as to forming oxidation solution following current, the new technology of new alkali lye adverse current.The patent really increases by a decomposer, and the conversion ratio and yield of cyclohexyl hydroperoxide can not be improved in actual production.
Patent CN1207381A mentions is continuously added to two kinds of catalyst of chromic nitrate and cobalt acetate simultaneously or step by step under low temperature heterogeneous catalysis process conditions to decomposition reactor, the total concentration of metal ion is in 1PPM, wherein chromium ion accounts for the 5%~40% of ion concentration, while sodium hydroxide is added into decomposition reactor（30%~50%）And desalted water, make in decomposition reactor organic phase and inorganic be in a ratio of 6：1, inorganic phase basicity is 0.4~0.7mol/kg, principle using above-mentioned technique is two kinds of metallic catalysts using cobalt and chromium, under the booster action of sodium hydroxide, the selectivity of cyclohexylhydroperoxconversion conversion generation cyclohexanone is improved, so as to improve keto-alcohol ratio, shortcoming is the serious chromium ion of effect on environment in reacted salkali waste be present, it is well known that chromium ion is to the very harmful of human body and environment, the salkali waste after burning is more difficult due to the processing containing chromium.
Spring thunder, bag Jian Hua, Li Jixin are taken charge of in " research of cyclohexyl hydroperoxide decomposition technique condition " text, studied by two kinds of approach to cyclohexylhydroperoxdecomposition decomposition reaction, inquired into reaction condition to alcohol ketone conversion ratio, alcohol ketone selectivity, alcohol ketone yield, alcohol ketone purity, alcohol ketone than influence.As a result show, conversion ratio, alcohol ketone selectivity, alcohol ketone yield and the keto-alcohol ratio of subacidity catalytic decomposition process cyclohexylhydroperoxdecomposition decomposition reaction are above alkaline saponification technique, and the alcohol ketone purity of alkaline saponification technique is higher than subacidity catalytic decomposition process.
The content of the invention
The purpose of the present invention is to propose to cyclohexyl hydroperoxide in a kind of cyclohexane oxide solution, decomposition prepares cyclohexanone and cyclohexanol under two kinds of different catalysts existence conditions, improves the keto-alcohol of decomposable process than the method with reduction alkaline consumption.
What the present invention was realized in：In tubular type, autoclave or tower reactor, the first step is using the different monooctyl ester of chromic acid as catalyst, cyclohexyl hydroperoxide in cyclohexane oxide solution decomposes generation cyclohexanone and cyclohexanol, second step is using cobalt acetate as catalyst, in the presence of sodium hydroxide, solution after the first step is decomposed continues to decompose, and the hexamethylene decomposed solution after decomposition carries out the separation of organic phase and inorganic phase.
A kind of preferable reaction condition of the present invention, which is that the first step is decomposed, is that it is 100~130 DEG C to control decomposition reaction temperature, and the addition of the different monooctyl ester of catalyst chromic acid is 5~50ppm, and the time of decomposition reaction is 80~150 minutes.Organic phase and inorganic phase volume ratio 9 in second step decomposition reaction：1~12：1, the concentration of catalyst cobalt ion is 1.5~3.0ppm in inorganic phase, and inorganic phase 0.5~1.2mol/kg of basicity, decomposition reaction temperature is 90 ~ 110 DEG C, and the time of decomposition reaction is 18~35 minutes.
The inventive method wherein cyclohexyl hydroperoxide Fen Xie Shuai≤99.5%, cyclohexanone and cyclohexanol Shou Shuai≤95.0%, for keto-alcohol ratio more than 1. 3, the consumption of sodium hydroxide reduces by more than 30% than traditional caustic digestion.
Embodiment
The present invention is described in detail in reference to embodiment.
Embodiment 1
Cyclohexane oxide solution 300ml is added in 1L reactors, the cyclohexane solution 10ml of the different monooctyl ester of chromic acid containing 5ppm is added simultaneously, 100 DEG C of controlling reaction temperature, reaction time 80min, then 60 DEG C are cooled to, into kettle add 27ml concentration of cobalt ions containing cobalt acetate be 1.5 ppm, the sodium hydroxide solution that basicity is 0.5mol/kg, 95 DEG C of controlling reaction temperature, cooling discharge after 30mim, standing separation organic phase and inorganic phase post analysis organic phase, wherein cyclohexyl hydroperoxide resolution ratio 99.56%, cyclohexanone and cyclohexanol yield 95.46%, cyclohexanone：Cyclohexanol=1.31：1.
Embodiment 2
Cyclohexane oxide solution 300ml is added in 1L reactors, the cyclohexane solution 10ml of the different monooctyl ester of chromic acid containing 20ppm is added simultaneously, 110 DEG C of controlling reaction temperature, reaction time 90min, then 60 DEG C are cooled to, it is 2.5 ppm that 30ml concentration of cobalt ions containing cobalt acetate is added into kettle, basicity be 1.5mol/kg sodium hydroxide solution, 95 DEG C of controlling reaction temperature, cooling discharge after 30mim, standing separation organic phase and inorganic phase post analysis organic phase, wherein cyclohexyl hydroperoxide resolution ratio 99.81%, cyclohexanone and cyclohexanol yield 98.56%, cyclohexanone：Cyclohexanol=1.38：1.
Embodiment 3
Cyclohexane oxide solution 300ml is added in 1L reactors, the cyclohexane solution 10ml of the different monooctyl ester of chromic acid containing 40ppm is added simultaneously, 120 DEG C of controlling reaction temperature, reaction time 120min, then 60 DEG C are cooled to, it is 2.5 ppm that 32ml concentration of cobalt ions containing cobalt acetate is added into kettle, basicity be 1.0mol/kg sodium hydroxide solution, 97 DEG C of controlling reaction temperature, cooling discharge after 35mim, standing separation organic phase and inorganic phase post analysis organic phase, wherein cyclohexyl hydroperoxide resolution ratio 99.73%, cyclohexanone and cyclohexanol yield 96.50%, cyclohexanone：Cyclohexanol=1.33：1.
Embodiment 4
Cyclohexane oxide solution 300ml is added in 1L reactors, the cyclohexane solution 10ml of the different monooctyl ester of chromic acid containing 50ppm is added simultaneously, 130 DEG C of controlling reaction temperature, reaction time 150min, then 60 DEG C are cooled to, it is 2.5 ppm that 36ml concentration of cobalt ions containing cobalt acetate is added into kettle, basicity be 1.2mol/kg sodium hydroxide solution, 96 DEG C of controlling reaction temperature, cooling discharge after 30mim, standing separation organic phase and inorganic phase post analysis organic phase, wherein cyclohexyl hydroperoxide resolution ratio 99.51%, cyclohexanone and cyclohexanol yield 96.36%, cyclohexanone：Cyclohexanol=1.32：1.
Embodiment 5
Cyclohexane oxide solution 300ml is added in 1L reactors, the cyclohexane solution 10ml of the different monooctyl ester of chromic acid containing 40ppm is added simultaneously, 112 DEG C of controlling reaction temperature, reaction time 100min, then 60 DEG C are cooled to, it is 2.0 ppm that 27ml concentration of cobalt ions containing cobalt acetate is added into kettle, basicity be 0.9 mol/kg sodium hydroxide solution, 95 DEG C of controlling reaction temperature, cooling discharge after 30mim, standing separation organic phase and inorganic phase post analysis organic phase, wherein cyclohexyl hydroperoxide resolution ratio 99.72%, cyclohexanone and cyclohexanol yield 97.35%, cyclohexanone：Cyclohexanol=1.34：1.
Embodiment 6
Cyclohexane oxide solution 300ml is added in 1L reactors, the cyclohexane solution 10ml of the different monooctyl ester of chromic acid containing 45ppm is added simultaneously, 110 DEG C of controlling reaction temperature, reaction time 100min, then 60 DEG C are cooled to, it is 2.0 ppm that 27ml concentration of cobalt ions containing cobalt acetate is added into kettle, basicity be 0.9 mol/kg sodium hydroxide solution, 90 DEG C of controlling reaction temperature, cooling discharge after 35mim, standing separation organic phase and inorganic phase post analysis organic phase, wherein cyclohexyl hydroperoxide resolution ratio 99.65%, cyclohexanone and cyclohexanol yield 96.31%, cyclohexanone：Cyclohexanol=1.31：1.
Embodiment 7
Cyclohexane oxide solution 300ml is added in 1L reactors, the cyclohexane solution 10ml of the different monooctyl ester of chromic acid containing 45ppm is added simultaneously, 115 DEG C of controlling reaction temperature, reaction time 120min, then 60 DEG C are cooled to, it is 2.0 ppm that 27ml concentration of cobalt ions containing cobalt acetate is added into kettle, basicity be 0.9 mol/kg sodium hydroxide solution, 110 DEG C of controlling reaction temperature, cooling discharge after 18mim, standing separation organic phase and inorganic phase post analysis organic phase, wherein cyclohexyl hydroperoxide resolution ratio 99.45%, cyclohexanone and cyclohexanol yield 96.27%, cyclohexanone：Cyclohexanol=1.30：1.
Claims (4)
1. a kind of method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and cyclohexanol, it is characterized in that in tubular type, autoclave or tower reactor, the first step is using the different monooctyl ester of chromic acid as catalyst, cyclohexyl hydroperoxide in cyclohexane oxide solution decomposes generation cyclohexanone and cyclohexanol, second step is using cobalt acetate as catalyst, in the presence of sodium hydroxide, the solution after the first step is decomposed continues to decompose, and the hexamethylene decomposed solution after decomposition carries out the separation of organic phase and inorganic phase.
2. the method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and cyclohexanol according to claim 1, it is characterized in that the first step, which is decomposed, controls decomposition reaction temperature as 100~130 DEG C, the addition of the different monooctyl ester of catalyst chromic acid is 5~50ppm, and the time of decomposition reaction is 80~150 minutes.
3. the method that cyclohexyl hydroperoxide decomposes preparing cyclohexanone and cyclohexanol according to claim 1, it is characterised in that organic phase and inorganic phase volume ratio are 9 in second step decomposition reaction：1~12：1, the concentration of catalyst cobalt ion is 1.5~3.0ppm, 0.5~1.2mol/kg of inorganic phase basicity in inorganic phase.
4. the method that preparing cyclohexanone and hexamethylene alcohol ketone are decomposed according to the cyclohexyl hydroperoxide of claim 1 or 3, it is characterised in that second step decomposition reaction temperature is 90 ~ 110 DEG C, and the time of decomposition reaction is 18~35 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851483A (en) * | 2021-01-20 | 2021-05-28 | 山东省科学院菏泽分院 | Preparation method of cyclohexanone and cyclohexanol |
| CN114085134A (en) * | 2021-10-26 | 2022-02-25 | 中国石油化工股份有限公司 | Method for preparing cyclohexanone by cyclohexane oxidation |
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| JPS57169438A (en) * | 1981-04-14 | 1982-10-19 | Ube Ind Ltd | Preparation of cyclohexanol and cyclohexanone |
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| JP2004059515A (en) * | 2002-07-30 | 2004-02-26 | Sumitomo Chem Co Ltd | Method for producing cycloalkanone and cycloalkanol |
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| JPS57169438A (en) * | 1981-04-14 | 1982-10-19 | Ube Ind Ltd | Preparation of cyclohexanol and cyclohexanone |
| CN1105970A (en) * | 1994-04-22 | 1995-08-02 | 肖藻生 | Technology for preparation of cyclohexanol and cyclohexanone from cyclohexane |
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| CN1621398A (en) * | 2003-11-25 | 2005-06-01 | 肖藻生 | Method for preparing cyclohexanone and cyclohexanol by cyclohexane oxidation |
| CN101172931A (en) * | 2006-11-01 | 2008-05-07 | 肖藻生 | Improved process for producing cyclohexanol and pimelinketone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112851483A (en) * | 2021-01-20 | 2021-05-28 | 山东省科学院菏泽分院 | Preparation method of cyclohexanone and cyclohexanol |
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| CN114085134A (en) * | 2021-10-26 | 2022-02-25 | 中国石油化工股份有限公司 | Method for preparing cyclohexanone by cyclohexane oxidation |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |