CN102079694B - 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 a kind of method that hexalin is prepared pimelinketone that is oxidized, further say about a kind of and take titanium-silicon molecular screen material and prepare the method for pimelinketone as catalyst oxidation hexalin.
Background technology
Pimelinketone is a kind of important industrial chemicals, is widely used in the industry of fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent.Particularly due to the developing rapidly of polymeric amide industry, as the demand of pimelinketone of preparing nylon 6 and nylon 66 intermediates in the whole world every year all more than 1,000,000 tons.
Cyclohexanone production process route mainly contains three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and partial hydrogenation of benzene method.Cyclohexane oxidation process is the main process of industrial production pimelinketone, account for more than 90%, but this production process is also considered to the production process that efficiency is minimum, 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 the method cyclohexane conversion is higher, but makes the easy fouling of reactor owing to forming hexanodioic acid cobalt, is now substantially eliminated; Two of method is boric acid class catalytic oxidations, and this method initial cost is high, and energy consumption is high, and in product, the ratio of hexalin is too high, increase the burden of postorder cyclohexanol dehydrogenation, and this method is very complicated, and operation easier is large, is easy to cause e-quipment and pipe seriously to stop up; Three of method is the non-catalyst oxidations with 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 hexanaphthene internal circulating load is large, and energy consumption is high, pollute also larger, particularly, in decomposing cyclohexyl hydrogen peroxide process, pimelinketone selectivity is poor, and yield is low.In addition produce in addition, the difficult problem of environmental protection of a large amount of waste lyes, difficult treatment.
Above in described cyclohexanone production process, all companion produces hexalin, then hexalin is converted into pimelinketone through oxidative dehydrogenation process process again, this process adopts zinc oxide etc. to make oxygenant, under 300 ℃ of left and right, reacts, energy consumption is high, process is complicated.
A kind of new catalytic oxidation material that is called as HTS (TS-1) is disclosed in USP4410501, it has good selective oxidation (EP0230949 to hydrocarbon, alcohol, phenol etc., USP4480135, USP4396783), catalyzer with other type is compared, the system that adopts TS-1 molecular sieve to be oxidized as catalyzer has following remarkable advantage: (1) reaction conditions is gentle, can under normal pressure, low temperature (20-100 ℃), carry out; (2) oxidation object product yield is high, and selectivity is good; (3) technological process is simple, environmental friendliness.As oneself has realized industrialization to be applied to oxidation of phenol preparing benzenediol.
Ulf Schuchardt etc. (J Catal, 1995,157:631-635) titanium molecular sieve catalysis oxidizing ethyle alkyl has been carried out to a series of research.From research, draw: hexanaphthene initial oxidation on TS-1 is hexalin, reoxidizes as pimelinketone.Because selecting optionally reason of type, hexalin will be oxidized to further pimelinketone in TS-1 zeolite cages, at TS-1 outside surface, be oxidized to many oxide.By adding after 2,6 di tert butyl 4 methyl phenol, can effectively suppress the non-selective oxidation of catalyzer outside surface, 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) is also studied titanium molecular sieve catalysis oxidizing ethyle alkyl.
Up to now, yet there are no and utilize the research that HTS is made catalyzer, the hydrogen peroxide of take is prepared pimelinketone aspect as oxidizer catalytic oxidation hexalin to report.
Summary of the invention
The object of the invention is the deficiency for existing technique, provide a kind of reaction conditions gentle, the oxidation hexalin that side reaction is few is prepared the method for pimelinketone.
Oxidation hexalin provided by the invention is prepared the method for pimelinketone, it is characterized in that the method is is under 0～180 ℃ and the pressure condition that is 0.1～3.0MPa in temperature, hexalin, hydrogen peroxide are contacted with catalyzer at interior reaction raw materials, said catalyzer is titanium-silicon molecular sieve catalyst, in reaction raw materials, the mol ratio of hexalin and hydrogen peroxide is 1: 0.1～10.0, and the mass ratio of hexanaphthene and catalyzer is 1～200: 1.
In method provided by the invention, said titanium-silicon molecular sieve catalyst can be HTS, as one or more in TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, Ti-ZSM-48 equimolecular sieve, be preferably the titanium-silicon molecular sieve TS-1 with MFI structure; Also can be to take the catalyzer that HTS is active ingredient, such catalyzer be selected from one or more in titanium-containing materials, silicon-dioxide and aluminum oxide by HTS and other and forms.
Contriver finds, in method provided by the invention, when adopting a kind of hollow HTS (HTS) with MFI structure, can obtain compared with the 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, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, has hysteresis loop; Its crystal grain is hollow structure; The radical length of the cavity part of this hollow crystal grain is 5～300 nanometers.
In method provided by the invention, in reaction system, can contain solvent, the mass ratio of solvent and catalyzer for being not more than 1000: 1, be preferably and be not more than 500: 1.Said solvent is selected from alcohols or nitrile or their mixing such as the 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, first alcohol and water.
It needs to be noted: method provided by the invention can be carried out under condition of no solvent, the emulsifying agent that introducing and hexalin volume ratio are 0.0000001～0.01, wherein emulsifying agent is one or more that are selected from polybenzimidazole, polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, poly derivative or other tensio-active agents.
More particularly, the said emulsifying agent of the present invention can be selected from polybenzimidazole pyrrolidone, polybenzimidazole alcohol, polybenzimidazole ether, polybenzimidazole pyrimidine, polypropylene pyrrolidone, POLYPROPYLENE GLYCOL, polypropylene ether, polypropylene pyrimidine, polyoxyethylene glycol pyrrolidone, polyoxyethylene glycol ether, polyoxyethylene glycol pyrimidine, polystyrene pyrrolidone, polystyrene alcohol, polystyrene ether, polystyrene pyrimidine, polyvinyl chloride pyrrolidone, polyvinyl chloride alcohol, polyvinyl chloride ether, polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, one or more in polyvinyl ethyl ether and polyethylene pyrimidine.
Said other tensio-active agents can be fatty alcohol-polyoxyethylene ether, block polyoxyethylene polyoxypropylene ether, alkylol amide, polyol ester class, tween series, sapn is serial, fluorocarbon surfactant is serial.
In method provided by the invention, in reaction raw materials the 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, solvent, catalyzer are added after reactor, add continuously hexalin, hydrogen peroxide; And continuous mode can adopt fixed-bed reactor while carrying out, solvent, hexalin, hydrogen peroxide are added continuously after packing catalyzer into; Also can adopt slurry bed reactor, will catalyzer, add continuously hexalin, hydrogen peroxide after solvent making beating, continuous separated product simultaneously.
Method provided by the invention can also adopt closed still reaction, is about to catalyzer, solvent, hexalin and hydrogen peroxide and adds reaction after mixing in still simultaneously.
In method provided by the invention, there is no solvent in reaction system, in the time of need to adding emulsifying agent, emulsifying agent can add at any time.
Oxidation hexalin provided by the invention is prepared the method for pimelinketone, adopts titanium-silicon molecular sieve catalyst, and reaction conditions is gentle, reduced the generation of the side reactions such as over oxidation, hexalin transformation efficiency is high, and pimelinketone selectivity is high, and reaction has the longer steady running time.Particularly there is no solvent in the reaction system, and while introducing emulsifying agent, improve the mixedness between reactant on the one hand, enhanced dispersion, improves speed of reaction, can play on the other hand guard catalyst, extends the effect of steady running time.Meanwhile, after introducing emulsifying agent, in reaction system, without solvent, separation costs, energy consumption etc. lower greatly, have simplified reaction, and whole reaction is more easily controlled, reproducible, are 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 comparative example, reagent used is commercially available chemically pure reagent.HTS used (TS-1) catalyzer is by prior art Zeolites, (TS-1) sieve sample that the method described in 1992, Vol.12 943-950 page is prepared.Hollow HTS HTS used is that Sinopec Hunan Jian Chang company produces, be that (Hunan Jian Chang company manufactures for the Industrial products of HTS described in Chinese patent CN1301599A, it through X-ray diffraction analysis, is the HTS of MFI structure, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, 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 recording under the adsorption time condition of 1 hour is 78 milligrams/gram).
In comparative example and embodiment:
Comparative example
Reaction result in the explanation reaction of this comparative example during catalyst-free.
By hexalin, hydrogen peroxide and solvent, according to the mol ratio of hexalin and hydrogen peroxide, being 1: 2, is that 30 ℃ of pressure are to react under 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
Reaction process and the result that HTS is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, methyl alcohol and catalyzer HTS, according to the mol ratio of hexalin and hydrogen peroxide, it is 1: 2, the mass ratio of methyl alcohol and catalyzer HTS is 20, the mass ratio of hexanaphthene and catalyzer is 50: 1, in temperature, is that 30 ℃ of pressure are to react under 1.5MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 36%; Pimelinketone selectivity is 93%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 35%; Pimelinketone selectivity is 91%.
Embodiment 2
Reaction process and the result that TS-1 is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, methyl alcohol and catalyzer TS-1, according to the mol ratio of hexalin and hydrogen peroxide, it is 1: 2, the mass ratio of solvent methanol and catalyzer TS-1 is 20, the mass ratio of hexalin and catalyzer is 10: 1, in temperature, is that 30 ℃ of pressure are to react under 1.5MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 23%; Pimelinketone selectivity is 89%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 15%; Pimelinketone selectivity is 85%.
Embodiment 3
Reaction process and the result that TS-1 is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, acetone and TS-1, according to the mol ratio of hexalin and hydrogen peroxide, be 1: 6, the mass ratio of acetone and catalyzer is 200, and the mass ratio of hexalin and catalyzer is 80: 1, in temperature, is that 60 ℃ of pressure are to react under 1.0MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 34%; Pimelinketone selectivity is 88%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 32%; Pimelinketone selectivity is 86%.
Embodiment 4
Reaction process and the result that HTS is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, the trimethyl carbinol and HTS, according to the mol ratio of hexalin and hydrogen peroxide, it is 1: 8, the mass ratio of the trimethyl carbinol and catalyzer HTS is 80, the mass ratio of hexalin and catalyzer is 100: 1, in temperature, is that 40 ℃ of pressure are to react under 0.5MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 82%; Pimelinketone selectivity is 94%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 78%; Pimelinketone selectivity is 91%.
Embodiment 5
Reaction process and the result that TS-1 is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, water and TS-1, according to the mol ratio of hexalin and hydrogen peroxide, be 1: 3, the mass ratio of water and catalyzer is 180, and the mass ratio of hexalin and catalyzer is 30: 1, in temperature, is that 90 ℃ of pressure are to react under 1.0MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 19%; Pimelinketone selectivity is 92%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 16%; Pimelinketone selectivity is 90%.
Embodiment 6
TS-1 solvent-free reaction process and result in catalyzer, reaction raw materials are take in the present embodiment explanation.
By hexalin, hydrogen peroxide and TS-1, according to the mol ratio of hexalin and hydrogen peroxide, be 2: 1, the mass ratio of hexalin and catalyzer is 25, and the mass ratio of hexalin and catalyzer is 6: 1, in temperature, is that 130 ℃ of pressure are to react under 1.5MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 13%; Pimelinketone selectivity is 93%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 12%; Pimelinketone selectivity is 90%.
The result of reacting 120 hours is as follows: hexalin transformation efficiency is 6%; Pimelinketone selectivity is 81%.
Embodiment 7
Reaction process and the result that TS-1 is solvent-free in catalyzer, reaction raw materials, add emulsifying agent take in the present embodiment explanation.
By hexalin, hydrogen peroxide and TS-1, according to the mol ratio of hexalin and hydrogen peroxide, it is 1: 1, the mass ratio of hexalin and catalyzer is 15, introducing and the emulsifying agent polybenzimidazole pyrrolidone that hexalin volume ratio is 0.0001 are that 60 ℃ of pressure are to react under 0.5MPa in temperature.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 64%; Pimelinketone selectivity is 95%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 62%; Pimelinketone selectivity is 92%.
The result of reacting 120 hours is as follows: hexalin transformation efficiency is 60%; Pimelinketone selectivity is 91%.
Embodiment 8
Reaction process and the result that HTS is solvent-free in catalyzer, reaction raw materials, add emulsifying agent take in the present embodiment explanation.
By hexalin, hydrogen peroxide and HTS, according to the mol ratio of hexalin and hydrogen peroxide, it is 1: 1, the mass ratio of hexalin and catalyzer HTS is 15, introducing and the emulsifier tween 60 that hexalin volume ratio is 0.001 are that 60 ℃ of pressure are to react under 0.5MPa in temperature.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 78%; Pimelinketone selectivity is 94%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 76%; Pimelinketone selectivity is 93%.
The result of reacting 120 hours is as follows: hexalin transformation efficiency is 72%; Pimelinketone selectivity is 93%.
Embodiment 9
Reaction process and the result that TS-1 is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, methyl alcohol and TS-1, according to the mol ratio of hexalin and hydrogen peroxide, be 8: 1, the mass ratio of methyl alcohol and catalyzer is 10, and the mass ratio of hexalin and catalyzer is 10: 1, in temperature, is that 40 ℃ of pressure are to react under 0.5MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 12%; Pimelinketone selectivity is 91%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 11%; Pimelinketone selectivity is 87%.
Embodiment 10
Reaction process and the result that HTS is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, acetone and HTS, according to the mol ratio of hexalin and hydrogen peroxide, be 10: 1, the mass ratio of acetone and catalyzer is 80, and the mass ratio of hexalin and catalyzer is 40: 1, in temperature, is that 40 ℃ of pressure are to react under 0.5MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 49%; Pimelinketone selectivity is 96%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 45%; Pimelinketone selectivity is 93%.
Embodiment 11
Reaction process and the result that TS-1 is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, methyl alcohol and TS-1, according to the mol ratio of hexalin and hydrogen peroxide, be 2: 1, the mass ratio of methyl alcohol and catalyzer is 40, and the mass ratio of hexalin and catalyzer is 70: 1, in temperature, is that 30 ℃ of pressure are to react under 1.5MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 21%; Pimelinketone selectivity is 90%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 19%; Pimelinketone selectivity is 84%.
Embodiment 12
Reaction process and the result that HTS is catalyzer take in the present embodiment explanation.
By hexalin, hydrogen peroxide, methyl alcohol and HTS, according to the mol ratio of hexalin and hydrogen peroxide, be 1: 1, the mass ratio of methyl alcohol and catalyzer HTS is 60, and the mass ratio of hexalin and catalyzer is 60: 1, in temperature, is that 60 ℃ of pressure are to react under 1.0MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 63%; Pimelinketone selectivity is 94%.
The result of reacting 15 hours is as follows: hexalin transformation efficiency is 62%; Pimelinketone selectivity is 91%.
Embodiment 13
The present embodiment explanation does with HTS the process that catalyzer reacts in the tank reactor of sealing.
By hexalin, hydrogen peroxide, acetone and HTS, according to the mol ratio of hexalin and hydrogen peroxide, be 1: 4, the mass ratio of acetone and catalyzer is 50, and the mass ratio of hexalin and catalyzer is 50: 1, in temperature, is that 60 ℃ of pressure are to react under 0.6MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 26%; Pimelinketone selectivity is 95%.
The result of reacting 12 hours is as follows: hexalin transformation efficiency is 65%, and pimelinketone selectivity is 88%.
Embodiment 14
The present embodiment explanation does with TS-1 the process that catalyzer reacts in the tank reactor of sealing.
By hexalin, hydrogen peroxide, solvent methanol and TS-1, according to the mol ratio of hexalin and hydrogen peroxide, it is 1: 2, the mass ratio of methyl alcohol and catalyzer is 20, the mass ratio of hexalin and catalyzer is 20: 1, in temperature, is that 80 ℃ of pressure are to react under 1.5MPa.
The result of reacting 2 hours is as follows: hexalin transformation efficiency is 17%, and pimelinketone selectivity is 90%.
The result of reacting 12 hours is as follows: hexalin transformation efficiency is 48%; Pimelinketone selectivity is 86%.
From embodiment and comparative example, can find out: method provided by the invention, particularly adopt HTS HTS transformation efficiency high, selectivity is good, especially, in the situation that there is no solvent, introduces after emulsifying agent, in the situation that keeping high conversion, highly selective, the steady running time extends greatly.
Claims (5)
1. the method for a preparing cyclohexone by catalyzing oxidating cyclohexol, it is characterized in that the method is is under 0～180 ℃ and the pressure condition that is 0.1～3.0MPa in temperature, hexalin, hydrogen peroxide are contacted with catalyzer at interior reaction raw materials, said catalyzer is hollow HTS HTS, in reaction raw materials, the mol ratio of hexalin and hydrogen peroxide is 1:0.1～10.0, 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 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, 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 hexalin and catalyzer is 5～100:1.
5. according to the method for claim 1, while it is characterized in that in reaction raw materials containing solvent, the emulsifying agent that to add with hexalin volume ratio be 0.0000001～0.01.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| CN109384656B (en) * | 2017-08-09 | 2021-12-17 | 中国石油化工股份有限公司 | Process for preparing cyclohexanone |
| CN109721467B (en) * | 2017-10-27 | 2022-03-11 | 中国石油化工股份有限公司 | Process for preparing halohydrins |
| 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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| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
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| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
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