CN1623971A - Method for selecting oxydation preparing cyclohexone by cyclohexane - Google Patents
Method for selecting oxydation preparing cyclohexone by cyclohexane Download PDFInfo
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- CN1623971A CN1623971A CN 200310119328 CN200310119328A CN1623971A CN 1623971 A CN1623971 A CN 1623971A CN 200310119328 CN200310119328 CN 200310119328 CN 200310119328 A CN200310119328 A CN 200310119328A CN 1623971 A CN1623971 A CN 1623971A
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- Prior art keywords
- sba
- cyclohexane
- pimelinketone
- molecular sieve
- hexanaphthene
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Abstract
A process for preparing cyclohexanone by selectively oxidizing cyclohexane features that under existance of meso-porous Si-based molecular sieve carrying Ru and in the at mosphere of low-pressure oxygen, the cyclohexane is selectively oxidized at 100-200 deg.C to obtain cyclohexanone. Its advantages are high selectivity and conversion rate, and no pollution.
Description
Technical field
The present invention relates to a kind ofly under the atmosphere of low oxygen, hexanaphthene one step selective oxidation prepares the method for pimelinketone.
Background technology
Pimelinketone is an important chemical material, is widely used in industry such as fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent.At present, because the polymeric amide industry develops rapidly, pimelinketone has also obtained fast development as the raw material of producing hexanolactam.The production of China's pimelinketone mainly is in order to satisfy the needs of caprolactam production.The method of traditional mode of production pimelinketone is that benzene hydrogenation is generated hexanaphthene, again it catalyzed oxidation is made hexalin, pimelinketone, or phenol hydrogenation is generated hexalin, and hexalin obtains pimelinketone through catalytic dehydrogenation.At present, the main method of producing pimelinketone both at home and abroad is a cyclohexane oxidation process.Wherein, the most important with the catalyzed oxidation of hexanaphthene again.At present, the industrial route that cyclohexane oxidation is produced pimelinketone has two, and the one, the catalyzed oxidation of hexanaphthene, another is the non-catalyst oxidation of hexanaphthene.It is catalyzer that catalytic oxidation adopts cobalt salt, boric acid or metaboric acid.It is catalyzer that the catalysis of cobalt salt catalysis of cobalt salt generally adopts cobalt salts such as cobalt naphthenate, cobalt octoate, cobalt oleate, cobalt stearate, cobalt naphthenate chromium complexes.Hexanaphthene under catalyst action with air generation oxidizing reaction, generate primary product pimelinketone, hexalin.The process of oxidizing reaction is at first to form cyclohexyl hydroperoxide by free radical reaction, superoxide is heated under catalyst action and decomposes then, generate pimelinketone, hexalin, simultaneously because pimelinketone, hexalin than the easier oxidation of hexanaphthene, have many by products to generate.In order to reduce the generation of by product, improve product selectivity and yield, must the control conversion of cyclohexane, and the residence time of pimelinketone, hexalin.But, if transformation efficiency is too low, a large amount of hexanaphthene unreacteds, the sepn process investment is big, deficiency in economic performance.The residence time is oversize, and pimelinketone, hexalin are by deep oxidation, and its selectivity and yield all descend.The exploitation of catalyzer and research become improved emphasis, have studied multiple catalyst system up till now.Along with people's environmental requirement is more and more high, the eco-friendly cyclohexane oxidation catalyst of development of new has become the task of top priority.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of cyclohexane selectively oxidizing to prepare the method for pimelinketone.
Our invention thinking is that the mesopore molecular sieve that utilizes ruthenium to modify prepares pimelinketone as the catalyst selectivity oxidizing ethyle alkyl.There is the molecular sieve catalyst of ruthenium to realize catalytic selective oxidation hexanaphthene preparing cyclohexanone by load.Mesoporous molecular sieve catalyst can with solution separating, reuse, environmentally safe and whole reaction system be by any solvent, hexanaphthene be reactant be again the solvent of id reaction.
A kind of method of catalytic selective oxidation hexanaphthene preparing cyclohexanone, this method is to be reactant with cyclohexane give in reactor, aerating oxygen, back adding molecular sieve catalyst stirs, molecular sieve catalyst be selected from Ru-SBA-15, Ru-MCM-41, Ru-HMS, Ru-SBA-1 one of them, control reaction temperature 100-200 ℃, reaction pressure 1-3MPa reacted 4-10 hour.
After reaction finished, product was qualitative with GC-MS, the GC detection by quantitative.
The method of the catalytic selective oxidation hexanaphthene preparing cyclohexanone that is provided among the present invention, the consumption of molecular sieve catalyst Ru-SBA-15, Ru-MCM-41, Ru-HMS, Ru-SBA-1 are the 0.005-0.015% of hexanaphthene weight.
Molecular sieve catalyst Ru-SBA-15, Ru-MCM-41, Ru-HMS, the loading of reactive metal Ru is less than 8 * 10 among the Ru-SBA-1
-5Wt%.
Whole reaction system is carried out under condition of no solvent, hexanaphthene be reactant be again the solvent of id reaction.The pimelinketone selectivity that the present invention obtains can reach 74%, the overall selectivity that generates hexalin and pimelinketone can reach 92%, conversion of cyclohexane can reach 10-15%, and molecular sieve catalyst can be recycled, environmentally safe is a kind of easy, economic, the eco-friendly method that selective oxidation prepares pimelinketone.
The present invention has following advantage: (1) conversion of cyclohexane can reach 10-15%; (2) the pimelinketone selectivity can reach 74%; (3) overall selectivity of generation hexalin and pimelinketone can reach 92%; (4) one step of reaction finishes, and process is simple; (5) oxygen as oxygenant more cheap and environmentally safe; (6) catalyzer can reuse.
Embodiment
Embodiment 1-4: the comparison of different catalysts catalytic selective oxidation hexanaphthene preparing cyclohexanone.Experiment condition is: 25ml stainless steel autoclave, 2mlC
6H
12, catalyzer Ru-SBA-15 (embodiment 1), Ru-MCM-41 (embodiment 2), Ru-HMS (embodiment 3), Ru-SBA-1 (embodiment 4) 10mg, 1.0MPa O
2, 150 ℃ of reaction 8h.
Cyclohexane conversion hexalin selectivity pimelinketone selectivity other
Catalyzer
(％) (％) (％) (％)
1 Ru-SBA-15 15 18 76 8
2 Ru-MCM-41 13 16 73 11
3 Ru-HMS 11 23 68 9
4 Ru-SBA-1 11 20 70 10
Embodiment 4-6: ruthenium content is to the influence of reaction result on the same catalyst: experiment condition is 25ml stainless steel autoclave, 2mlC
6H
12, 1MPaO
2, 150 ℃ of reaction 8h.
Cyclohexane ring hexanol pimelinketone
Catalyzer Ru * 10
-5Wt other
Transformation efficiency selectivity selectivity
(0.01 gram) % (%)
(％) (％) (％)
5?Ru-SBA-15 7.7 15 10 78 12
6?Ru-SBA-15 5.1 14 16 75 9
7?Ru-SBA-15 2.7 14 24 68 8
Embodiment 8-11: the influence of catalyst levels to reacting: experiment condition is 25ml stainless steel autoclave, 2mlC
6H
12, catalyzer Ru-SBA-150.01-0.04g (embodiment 9-12), 1.0MPaO
2, 150 ℃ of reaction 8h.
The hexalin pimelinketone is selected
The catalyzer cyclohexane conversion other
Selectivity
(gram) be (%) (%)
(％) (％)
8 0.01 12 23 71 6
9 0.02 13 20 75 5
10 0.03 15 20 73 7
11 0.04 15 13 77 10
Embodiment 12-15: the influence of reaction times to reacting: experiment condition is:: 25ml stainless steel autoclave, 2ml C
6H
12, catalyzer Ru-SBA-15 0.01g (embodiment 13-17), 1.0MPaO
2, 150 ℃ of reactions 4,6,8,10h.
The hexalin pimelinketone is selected
Cyclohexane conversion other
Time (h) selectivity
(％) (％)
(％) (％)
12 4 11.8 23 68 6
13 6 12.0 20 73 7
14 8 13.1 15 76 9
15 10 15.2 12 74 14
Claims (3)
1, a kind of method of catalytic selective oxidation hexanaphthene preparing cyclohexanone, this method is to be reactant with cyclohexane give in reactor, aerating oxygen, back adding molecular sieve catalyst stirs, molecular sieve catalyst be selected from Ru-SBA-15, Ru-MCM-41, Ru-HMS, Ru-SBA-1 one of them, control reaction temperature 100-200 ℃, reaction pressure 1-3MPa reacted 4-10 hour.
2, as the said method of claim 1, the consumption that it is characterized in that molecular sieve catalyst Ru-SBA-15, Ru-MCM-41, Ru-HMS, Ru-SBA-1 is the 0.005-0.015% of hexanaphthene weight.
3, as the said method of claim 1, it is characterized in that molecular sieve catalyst Ru-SBA-15, Ru-MCM-41, Ru-HMS, the loading of reactive metal Ru is less than 8 * 10 among the Ru-SBA-1
-5Wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310119328 CN1240659C (en) | 2003-12-04 | 2003-12-04 | Method for selecting oxydation preparing cyclohexone by cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310119328 CN1240659C (en) | 2003-12-04 | 2003-12-04 | Method for selecting oxydation preparing cyclohexone by cyclohexane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1623971A true CN1623971A (en) | 2005-06-08 |
| CN1240659C CN1240659C (en) | 2006-02-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310119328 Expired - Fee Related CN1240659C (en) | 2003-12-04 | 2003-12-04 | Method for selecting oxydation preparing cyclohexone by cyclohexane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102012188A (en) * | 2010-10-28 | 2011-04-13 | 中国石油化工股份有限公司 | Anti-corrosion method for tail gas heat exchange tower in cyclohexane oxidation technology |
| CN109248699A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | The method of cyclohexane oxidation KA oil |
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN114369007A (en) * | 2022-01-04 | 2022-04-19 | 中国科学院大连化学物理研究所 | Method for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation |
-
2003
- 2003-12-04 CN CN 200310119328 patent/CN1240659C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102012188A (en) * | 2010-10-28 | 2011-04-13 | 中国石油化工股份有限公司 | Anti-corrosion method for tail gas heat exchange tower in cyclohexane oxidation technology |
| CN102012188B (en) * | 2010-10-28 | 2012-11-28 | 中国石油化工股份有限公司 | Anti-corrosion method for tail gas heat exchange tower in cyclohexane oxidation technology |
| CN109248699A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | The method of cyclohexane oxidation KA oil |
| CN109248699B (en) * | 2017-07-14 | 2022-08-12 | 中国石油化工股份有限公司 | Method for preparing KA oil by cyclohexane oxidation |
| 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 |
| CN114369007A (en) * | 2022-01-04 | 2022-04-19 | 中国科学院大连化学物理研究所 | Method for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation |
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| Publication number | Publication date |
|---|---|
| CN1240659C (en) | 2006-02-08 |
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