CN102079694A - Preparation method of cyclohexanone from oxidation of cyclohexanol - Google Patents
Preparation method of cyclohexanone from oxidation of cyclohexanol Download PDFInfo
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Abstract
A preparation method of cyclohexanone from catalytic oxidation of cyclohexanol is characterized by contacting reactants containing cyclohexanol and hydrogen peroxide with a catalyst at a temperature of 0-180 DEG C and under the pressure of 0.1-3.0MPa, wherein the molar ratio of cyclohexanol to hydrogen peroxide is 1:(0.1 to 10.0), the catalyst is a titanium silicalite molecular sieve based catalyst, and the mass ratio of cyclohexanol and the catalyst is (1-200):1. The method has no special requirements on equipment and the production process is simple, is easy to control and is beneficial to industrial production and application. The invention has the advantages of high cyclohexanol conversion rate, good selectivity, long time stable operation.
Description
Technical field
The invention relates to the method that a kind of oxidation hexalin prepares pimelinketone, further say so about a kind of be the method that catalyst oxidation hexalin prepares pimelinketone with the titanium-silicon molecular screen material.
Background technology
Pimelinketone is a kind of important chemical material, is widely used in the industry of fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent.Particularly because the developing rapidly of polymeric amide industry, as the demand of the pimelinketone of preparation nylon 6 and nylon 66 intermediates whole world every year all more than 1,000,000 tons.
The cyclohexanone production process route mainly contains three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and benzene partial hydrogenation method.Cyclohexane oxidation process is the main process of industrial production pimelinketone, account for more than 90%, but this production process also is considered to the minimum production process of efficient, is one of the restriction key of caprolactam production and bottleneck.
Cyclohexane oxidation produces that pimelinketone is industrial generally three kinds of methods: one of method is that to adopt cobalt salt be catalyzer, and this method cyclohexane conversion is higher, but the easy fouling of reactor now is eliminated substantially because formation hexanodioic acid cobalt makes; Two of method is boric acid class catalytic oxidations, this method initial cost height, and the energy consumption height, the ratio of hexalin is too high in the product, increases the burden of postorder cyclohexanol dehydrogenation, and this method is very complicated, and operation easier is big, is easy to cause equipment and pipeline seriously to stop up; Three of method is the non-catalyst oxidations with the air direct oxidation, this method has effectively been avoided the problem of reactor fouling, in industrial extensive application, but this complex process, intermediate steps is many, cyclohexane conversion is low, and the hexanaphthene internal circulating load is big, the energy consumption height, pollute also bigger, particularly in the cyclohexyl hydroperoxide decomposition course, the pimelinketone selectivity is relatively poor, and yield is low.In addition, produce the environmental protection difficult problem of a large amount of waste lyes, difficult treatment in addition.
Above in the described cyclohexanone production process, all the companion produces hexalin, hexalin is converted into pimelinketone through the oxidative dehydrogenation process process more then, this process adopts zinc oxide etc. to make oxygenant, reacts energy consumption height, process complexity under about 300 ℃.
A kind of new catalytic oxidation material that is called as HTS (TS-1) is disclosed among the USP4410501, it has good selective oxidation (EP0230949 to hydrocarbon, alcohol, phenol etc., USP4480135, USP4396783), catalyzer with other type is compared, adopt the TS-1 molecular sieve following remarkable advantage to be arranged as the system that catalyzer carries out oxidation: (1) reaction conditions gentleness, can under normal pressure, low temperature (20-100 ℃), carry out; (2) oxidation purpose product yield height, selectivity is good; (3) technological process is simple, environmental friendliness.As oneself has realized industrialization to be applied to the oxidation of phenol preparing benzenediol.
Ulf Schuchardt etc. (J Catal, 1995,157:631-635) the titanium molecular sieve catalysis oxidizing ethyle alkyl has been carried out a series of research.Draw from research: hexanaphthene initial oxidation on TS-1 is a hexalin, reoxidizes to be pimelinketone.Because of selecting optionally reason of type, hexalin will be oxidized to pimelinketone further in the TS-1 zeolite cages, then be oxidized to multiple oxide compound at the TS-1 outside surface.After adding 2,6 di tert butyl 4 methyl phenol, can suppress the non-selective oxidation of catalyzer outside surface effectively, improve the selectivity of product pimelinketone.Tao Jialin etc. (J Natural Gas Chem 2001,10:295-307) and Ulf Schuchardt etc. (Applied Catal A:Gen 2001 211:1-17) also studies the titanium molecular sieve catalysis oxidizing ethyle alkyl.
Up to now, yet there are no utilize HTS to make catalyzer, be the research report that oxidizer catalytic oxidation hexalin prepares the pimelinketone aspect with the hydrogen peroxide.
Summary of the invention
The objective of the invention is the deficiency at existing technology, a kind of reaction conditions gentleness is provided, the oxidation hexalin that side reaction is few prepares the method for pimelinketone.
Oxidation hexalin provided by the invention prepares the method for pimelinketone, it is characterized in that this method is is that 0～180 ℃ and pressure are under the condition of 0.1～3.0MPa in temperature, hexalin, hydrogen peroxide are contacted with catalyzer at interior reaction raw materials, said catalyzer is a titanium-silicon molecular sieve catalyst, the mol ratio of hexalin and hydrogen peroxide is 1: 0.1～10.0 in the reaction raw materials, and the mass ratio of hexanaphthene and catalyzer is 1～200: 1.
In the method provided by the invention, said titanium-silicon molecular sieve catalyst can be a HTS, as in TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48 equimolecular sieve one or more, be preferably titanium-silicon molecular sieve TS-1 with MFI structure; Also can be to be the catalyzer of active ingredient with the HTS, such catalyzer be selected from titanium-containing materials, silicon-dioxide and the aluminum oxide one or more by HTS and other and forms.
The contriver finds, and is a kind of when having MFI structure of hollow HTS (HTS) when adopting in the method provided by the invention, can obtain than better transformation efficiency of general T S-1 molecular sieve catalyst and selectivity, therefore as preferred catalyzer.The hollow HTS of said HTS discloses in CN1301599A, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this molecular sieve and the desorption isotherm; Its crystal grain is hollow structure; The radical length of the cavity part of this hollow crystal grain is 5～300 nanometers.
In the method provided by the invention, can contain solvent in the reaction system, the mass ratio of solvent and catalyzer is for being not more than 1000: 1, being preferably and being not more than 500: 1.Said solvent is selected from alcohols or nitrile or their mixing such as ketone such as acetone, butanone or acetonitrile such as water or methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, is preferably one or more the mixing in acetonitrile, acetone, the first alcohol and water.
It needs to be noted: method provided by the invention can be carried out under condition of no solvent, introducing with the hexalin volume ratio is 0.0000001～0.01 emulsifying agent, and wherein emulsifying agent is to be selected from polybenzimidazole, polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, poly derivative or other tensio-active agents one or more.
More particularly, the said emulsifying agent of the present invention can be selected from the polybenzimidazole pyrrolidone, polybenzimidazole alcohol, the polybenzimidazole ether, the polybenzimidazole pyrimidine, the polypropylene pyrrolidone, POLYPROPYLENE GLYCOL, the polypropylene ether, the polypropylene pyrimidine, the polyoxyethylene glycol pyrrolidone, the polyoxyethylene glycol ether, the polyoxyethylene glycol pyrimidine, the polystyrene pyrrolidone, polystyrene alcohol, the polystyrene ether, the polystyrene pyrimidine, the polyvinyl chloride pyrrolidone, polyvinyl chloride alcohol, the polyvinyl chloride ether, the polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, in polyvinyl ethyl ether and the polyethylene pyrimidine one or more.
Said other tensio-active agents can be fatty alcohol-polyoxyethylene ether, block polyoxyethylene polyoxypropylene ether, alkylol amide, polyol ester class, tween series, sapn series, fluorocarbon surfactant series.
In the method provided by the invention, in the reaction raw materials mol ratio of hexalin and hydrogen peroxide be preferably 1: 0.2～5.0, the mass ratio of hexalin and catalyzer is preferably 5～100: 1, and temperature of reaction is preferably 20～120 ℃, and reaction pressure is preferably 0.1～2.5MPa.
Method provided by the invention can adopt periodical operation or operate continuously mode.When andnon-continuous operation manner is carried out, behind solvent, catalyzer adding reactor, add hexalin, hydrogen peroxide continuously; And continuous mode can adopt fixed-bed reactor when carrying out, and behind the catalyzer of packing into solvent, hexalin, hydrogen peroxide is added continuously; Also can adopt slurry bed reactor, catalyzer, solvent making beating back are added hexalin, hydrogen peroxide continuously, the while is separated product constantly.
Method provided by the invention can also adopt closed still reaction, and soon catalyzer, solvent, hexalin and hydrogen peroxide add simultaneously and mix afterreaction in the still.
In the method provided by the invention, do not have solvent in reaction system, when needing to add emulsifying agent, emulsifying agent can add at any time.
Oxidation hexalin provided by the invention prepares the method for pimelinketone, adopts titanium-silicon molecular sieve catalyst, the reaction conditions gentleness, reduced the generation of side reactions such as over oxidation, hexalin transformation efficiency height, pimelinketone selectivity height, reaction has the long steady running time.Particularly do not have solvent in the reaction system, and when introducing emulsifying agent, improve the mixedness between reactant on the one hand, strengthen diffusion, improve speed of reaction, can play guard catalyst on the other hand, prolong the effect of steady running time.Simultaneously, after introducing emulsifying agent, need not solvent in the reaction system, then separation costs, energy consumption etc. lower greatly, have simplified reaction, make the easier control of entire reaction, and good reproducibility is beneficial to suitability for industrialized production and application.
Embodiment
The invention will be further described by the following examples, but therefore do not limit content of the present invention.
In embodiment and the Comparative Examples, used reagent is commercially available chemically pure reagent.Used HTS (TS-1) catalyzer is by prior art Zeolites, 1992, and (TS-1) sieve sample that the method described in the Vol.12 943-950 page or leaf is prepared.Used hollow HTS HTS builds long company for the Sinopec Hunan and produces, be that (Hunan is built long company and made for the Industrial products of the described HTS of Chinese patent CN1301599A, through the X-ray diffraction analysis is the HTS of MFI structure, have hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram).
In Comparative Examples and embodiment:
Comparative Examples
Reaction result in the explanation reaction of this Comparative Examples during catalyst-free.
Is 1: 2 with hexalin, hydrogen peroxide and solvent according to the mol ratio of hexalin and hydrogen peroxide, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.
React after 2 hours, the transformation efficiency of hexalin is 0%.
React after 15 hours, the transformation efficiency of hexalin is 0%.
Embodiment 1
The present embodiment explanation is the reaction process and the result of catalyzer with HTS.
Is 1: 2 with hexalin, hydrogen peroxide, methyl alcohol and catalyzer HTS according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of methyl alcohol and catalyzer HTS is 20, the mass ratio of hexanaphthene and catalyzer is 50: 1, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 36%; The pimelinketone selectivity is 93%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 35%; The pimelinketone selectivity is 91%.
Embodiment 2
The present embodiment explanation is the reaction process and the result of catalyzer with TS-1.
Is 1: 2 with hexalin, hydrogen peroxide, methyl alcohol and catalyzer TS-1 according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer TS-1 is 20, the mass ratio of hexalin and catalyzer is 10: 1, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 23%; The pimelinketone selectivity is 89%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 15%; The pimelinketone selectivity is 85%.
Embodiment 3
The present embodiment explanation is the reaction process and the result of catalyzer with TS-1.
Is 1: 6 with hexalin, hydrogen peroxide, acetone and TS-1 according to the mol ratio of hexalin and hydrogen peroxide, and the mass ratio of acetone and catalyzer is 200, and the mass ratio of hexalin and catalyzer is 80: 1, is that 60 ℃ of pressure are to react under the 1.0MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 34%; The pimelinketone selectivity is 88%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 32%; The pimelinketone selectivity is 86%.
Embodiment 4
The present embodiment explanation is the reaction process and the result of catalyzer with HTS.
Is 1: 8 with hexalin, hydrogen peroxide, the trimethyl carbinol and HTS according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of the trimethyl carbinol and catalyzer HTS is 80, the mass ratio of hexalin and catalyzer is 100: 1, is that 40 ℃ of pressure are to react under the 0.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 82%; The pimelinketone selectivity is 94%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 78%; The pimelinketone selectivity is 91%.
Embodiment 5
The present embodiment explanation is the reaction process and the result of catalyzer with TS-1.
Is 1: 3 with hexalin, hydrogen peroxide, water and TS-1 according to the mol ratio of hexalin and hydrogen peroxide, and the mass ratio of water and catalyzer is 180, and the mass ratio of hexalin and catalyzer is 30: 1, is that 90 ℃ of pressure are to react under the 1.0MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 19%; The pimelinketone selectivity is 92%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 16%; The pimelinketone selectivity is 90%.
Embodiment 6
The present embodiment explanation is solvent-free reaction process and result in catalyzer, the reaction raw materials with TS-1.
Is 2: 1 with hexalin, hydrogen peroxide and TS-1 according to the mol ratio of hexalin and hydrogen peroxide, and the mass ratio of hexalin and catalyzer is 25, and the mass ratio of hexalin and catalyzer is 6: 1, is that 130 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 13%; The pimelinketone selectivity is 93%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 12%; The pimelinketone selectivity is 90%.
The result who reacts 120 hours is as follows: the hexalin transformation efficiency is 6%; The pimelinketone selectivity is 81%.
Embodiment 7
The present embodiment explanation is reaction process and result solvent-free in catalyzer, the reaction raw materials, that add emulsifying agent with TS-1.
Is 1: 1 with hexalin, hydrogen peroxide and TS-1 according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of hexalin and catalyzer is 15, introducing and hexalin volume ratio are 0.0001 emulsifying agent polybenzimidazole pyrrolidone, are that 60 ℃ of pressure are to react under the 0.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 64%; The pimelinketone selectivity is 95%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 62%; The pimelinketone selectivity is 92%.
The result who reacts 120 hours is as follows: the hexalin transformation efficiency is 60%; The pimelinketone selectivity is 91%.
Embodiment 8
The present embodiment explanation is reaction process and result solvent-free in catalyzer, the reaction raw materials, that add emulsifying agent with HTS.
Is 1: 1 with hexalin, hydrogen peroxide and HTS according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of hexalin and catalyzer HTS is 15, introducing and hexalin volume ratio are 0.001 emulsifier tween 60, are that 60 ℃ of pressure are to react under the 0.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 78%; The pimelinketone selectivity is 94%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 76%; The pimelinketone selectivity is 93%.
The result who reacts 120 hours is as follows: the hexalin transformation efficiency is 72%; The pimelinketone selectivity is 93%.
Embodiment 9
The present embodiment explanation is the reaction process and the result of catalyzer with TS-1.
Is 8: 1 with hexalin, hydrogen peroxide, methyl alcohol and TS-1 according to the mol ratio of hexalin and hydrogen peroxide, and the mass ratio of methyl alcohol and catalyzer is 10, and the mass ratio of hexalin and catalyzer is 10: 1, is that 40 ℃ of pressure are to react under the 0.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 12%; The pimelinketone selectivity is 91%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 11%; The pimelinketone selectivity is 87%.
Embodiment 10
The present embodiment explanation is the reaction process and the result of catalyzer with HTS.
Is 10: 1 with hexalin, hydrogen peroxide, acetone and HTS according to the mol ratio of hexalin and hydrogen peroxide, and the mass ratio of acetone and catalyzer is 80, and the mass ratio of hexalin and catalyzer is 40: 1, is that 40 ℃ of pressure are to react under the 0.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 49%; The pimelinketone selectivity is 96%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 45%; The pimelinketone selectivity is 93%.
Embodiment 11
The present embodiment explanation is the reaction process and the result of catalyzer with TS-1.
Is 2: 1 with hexalin, hydrogen peroxide, methyl alcohol and TS-1 according to the mol ratio of hexalin and hydrogen peroxide, and the mass ratio of methyl alcohol and catalyzer is 40, and the mass ratio of hexalin and catalyzer is 70: 1, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 21%; The pimelinketone selectivity is 90%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 19%; The pimelinketone selectivity is 84%.
Embodiment 12
The present embodiment explanation is the reaction process and the result of catalyzer with HTS.
Is 1: 1 with hexalin, hydrogen peroxide, methyl alcohol and HTS according to the mol ratio of hexalin and hydrogen peroxide, and the mass ratio of methyl alcohol and catalyzer HTS is 60, and the mass ratio of hexalin and catalyzer is 60: 1, is that 60 ℃ of pressure are to react under the 1.0MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 63%; The pimelinketone selectivity is 94%.
The result who reacts 15 hours is as follows: the hexalin transformation efficiency is 62%; The pimelinketone selectivity is 91%.
Embodiment 13
The present embodiment explanation is done the process that catalyzer reacts with HTS in the tank reactor of sealing.
Is 1: 4 with hexalin, hydrogen peroxide, acetone and HTS according to the mol ratio of hexalin and hydrogen peroxide, and the mass ratio of acetone and catalyzer is 50, and the mass ratio of hexalin and catalyzer is 50: 1, is that 60 ℃ of pressure are to react under the 0.6MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 26%; The pimelinketone selectivity is 95%.
The result who reacts 12 hours is as follows: the hexalin transformation efficiency is 65%, and the pimelinketone selectivity is 88%.
Embodiment 14
The present embodiment explanation is done the process that catalyzer reacts with TS-1 in the tank reactor of sealing.
Is 1: 2 with hexalin, hydrogen peroxide, solvent methanol and TS-1 according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of methyl alcohol and catalyzer is 20, the mass ratio of hexalin and catalyzer is 20: 1, is that 80 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 17%, and the pimelinketone selectivity is 90%.
The result who reacts 12 hours is as follows: the hexalin transformation efficiency is 48%; The pimelinketone selectivity is 86%.
From embodiment and Comparative Examples as can be seen: particularly adopt HTS HTS transformation efficiency height the method provided by the invention, selectivity is good, is not especially having under the situation of solvent, behind the introducing emulsifying agent, under the situation that keeps high conversion, highly selective, the steady running time prolongs greatly.
Claims (10)
1. the method for a preparing cyclohexone by catalyzing oxidating cyclohexol, it is characterized in that this method is is that 0～180 ℃ and pressure are under the condition of 0.1～3.0MPa in temperature, hexalin, hydrogen peroxide are contacted with catalyzer at interior reaction raw materials, said catalyzer is a titanium-silicon molecular sieve catalyst, the mol ratio of hexalin and hydrogen peroxide is 1: 0.1～10.0 in the reaction raw materials, and the mass ratio of hexalin and catalyzer is 1～200: 1.
2. according to the method for claim 1, it is characterized in that also containing solvent in the reaction raw materials, the mass ratio of solvent and catalyzer is for being not more than 1000: 1.
3. according to the method for claim 2, wherein, said solvent is selected from one or more the mixture in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, the acetonitrile.
4. according to claim 1,2 or 3 method, wherein, the mol ratio of hexalin and hydrogen peroxide is 1: 0.2～5.0, and the mass ratio of solvent and catalyzer is 0.5～500, and the mass ratio of hexanaphthene and catalyzer is 5～100: 1.
5. according to the method for claim 1, it is characterized in that when not containing solvent in the reaction raw materials that adding and hexalin volume ratio are 0.0000001～0.01 emulsifying agent.
6. according to the method for claim 5, wherein said emulsifying agent is selected from one or more in polybenzimidazole, polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, poly derivative or other nonionogenic tensides.
7. according to the method for claim 5, wherein said emulsifying agent is selected from the polybenzimidazole pyrrolidone, polybenzimidazole alcohol, the polybenzimidazole ether, the polybenzimidazole pyrimidine, the polypropylene pyrrolidone, POLYPROPYLENE GLYCOL, the polypropylene ether, the polypropylene pyrimidine, the polyoxyethylene glycol pyrrolidone, the polyoxyethylene glycol ether, the polyoxyethylene glycol pyrimidine, the polystyrene pyrrolidone, polystyrene alcohol, the polystyrene ether, the polystyrene pyrimidine, the polyvinyl chloride pyrrolidone, polyvinyl chloride alcohol, the polyvinyl chloride ether, the polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, in polyvinyl ethyl ether and the polyethylene pyrimidine one or more.
8. according to the method for claim 6, wherein, said other tensio-active agents are selected from fatty alcohol-polyoxyethylene ether, block polyoxyethylene polyoxypropylene ether, alkylol amide, polyol ester class, tween, sapn and fluorocarbon surfactant.
9. according to the method for claim 1, it is characterized in that said HTS is one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48.
10. according to the method for claim 1, it is characterized in that said HTS is hollow HTS HTS.
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Cited By (8)
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| CN102850198A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Cyclohexanol oxidation method |
| CN103204769A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Method for production of cyclohexanone from cyclohexanol |
| 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 |
| CN104557450A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for oxidizing cyclohexane |
| CN109384656A (en) * | 2017-08-09 | 2019-02-26 | 中国石油化工股份有限公司 | The method for preparing cyclohexanone |
| CN109721467A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The method for preparing halohydrin |
| CN110128250A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | The method for preparing cyclohexanone |
| CN116120157A (en) * | 2023-02-24 | 2023-05-16 | 山东京博石油化工有限公司 | Method for preparing cyclopentanone by selective oxidation of cyclopentane |
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| CN102850198A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Cyclohexanol oxidation method |
| CN102850198B (en) * | 2011-06-30 | 2015-01-14 | 中国石油化工股份有限公司 | Cyclohexanol oxidation method |
| CN103204769B (en) * | 2012-01-13 | 2015-03-18 | 中国石油化工股份有限公司 | Method for production of cyclohexanone from cyclohexanol |
| CN103204769A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Method for production of cyclohexanone from cyclohexanol |
| 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 |
| 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 |
| CN104557450A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for oxidizing cyclohexane |
| CN104557450B (en) * | 2013-10-29 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of method of oxidizing ethyle alkyl |
| CN109384656A (en) * | 2017-08-09 | 2019-02-26 | 中国石油化工股份有限公司 | The method for preparing cyclohexanone |
| CN109384656B (en) * | 2017-08-09 | 2021-12-17 | 中国石油化工股份有限公司 | Process for preparing cyclohexanone |
| CN109721467A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The method for preparing halohydrin |
| CN109721467B (en) * | 2017-10-27 | 2022-03-11 | 中国石油化工股份有限公司 | Process for preparing halohydrins |
| CN110128250A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | The method for preparing cyclohexanone |
| CN110128250B (en) * | 2018-02-09 | 2021-10-08 | 中国石油化工股份有限公司 | Process for preparing cyclohexanone |
| CN116120157A (en) * | 2023-02-24 | 2023-05-16 | 山东京博石油化工有限公司 | Method for preparing cyclopentanone by selective oxidation of cyclopentane |
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