CN102850197A - Method for preparing cyclohexanone - Google Patents
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- CN102850197A CN102850197A CN201110183067XA CN201110183067A CN102850197A CN 102850197 A CN102850197 A CN 102850197A CN 201110183067X A CN201110183067X A CN 201110183067XA CN 201110183067 A CN201110183067 A CN 201110183067A CN 102850197 A CN102850197 A CN 102850197A
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Abstract
The invention relates to a method for preparing cyclohexanone. The method includes, under oxidation reaction condition, allowing contact of cyclohexane and hydrogen peroxide in the presence of catalyst, wherein the catalyst is obtained by allowing contact of Ti-Si molecular sieve and modification liquid at 80-200 DEG C., drying contact product, and roasting, the modification liquid is a water solution containing organic base, and the mass ratio of the Ti-Si molecular sieve to the modification liquid is of 100:(10-150), and the ratio of the Ti-Si molecular sieve accounted by gram to the organic base accounted by mole is 100:(0.005-0.2). The inventive method has high cyclohexane conversion rate and cyclohexanone selectivity. Furthermore, the catalyst used in the method has good stability, and high catalytic activity even if it is used for long time. In addition, the inventive method is simple, easy and environment friendly.
Description
Technical field
The present invention relates to a kind of method for preparing pimelinketone.
Background technology
Pimelinketone is widely used in fiber, synthetic rubber, industrial coating, medicine and the pesticide industry, can be used as industrial chemicals, for example: pimelinketone can be for the preparation of important monomer hexanodioic acid and the hexanolactam of synthesizing polyamides, can also for the preparation of softening agent and washing composition etc., also can be used as solvent and emulsifying agent in the chemical operation process.Along with the fast development of polymeric amide industry, the demand of pimelinketone also improves thereupon.At present, the consumption of the annual pimelinketone in the whole world is all more than 1,000,000 tons.
The production process route of pimelinketone mainly contains three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and partial hydrogenation of benzene method, wherein cyclohexane oxidation process is industrial main process for the production of pimelinketone, accounts for more than 90%.According to the catalyst type of whether using catalyzer and use, industrially utilize cyclohexane oxidation to produce pimelinketone three kinds of methods are generally arranged: the catalytic oxidation take cobalt salt as catalyzer, the catalytic oxidation take boric acid compound as catalyzer and with the non-catalyst oxidation method of air direct oxidation.But, use the cyclohexane oxidation production process of any method all to have inefficient shortcoming, cyclohexane oxidation process even be considered to minimum one of efficient in all chemical industry processes.The poor efficiency of cyclohexane oxidation synthesizing cyclohexanone process has become one of bottleneck that restricts the polymeric amide industry production of using hexanolactam and hexanodioic acid.
Therefore, a kind of method that can prepare pimelinketone with high cyclohexane conversion and pimelinketone selectivity of exploitation is a technical problem that needs to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method for preparing pimelinketone is provided, the method can obtain high cyclohexane conversion and pimelinketone selectivity.
HTS is a class hetero-atom molecular-sieve that is made of titanyl tetrahedron and silicon-oxy tetrahedron, has higher thermostability, resistance to acid and hydrophobicity, also has simultaneously good catalytic activity and selectivity.But, as catalyzer, when coming oxidizing ethyle alkyl with hydrogen peroxide as oxygenant, being difficult to obtain gratifying cyclohexane conversion and pimelinketone selectivity with HTS, the effective rate of utilization of hydrogen peroxide is not high yet simultaneously.
The present inventor is through in depth research, surprisingly find: in confined conditions, HTS is contacted at 80-200 ℃ with the solution that contains organic bases, and product of contact carried out drying and roasting, with the product of roasting that the obtains catalyzer when coming oxidizing ethyle alkyl with hydrogen peroxide as oxygenant, the selectivity of transformation efficiency and the pimelinketone of hexanaphthene can be significantly improved, and the effective rate of utilization of hydrogen peroxide can be significantly improved.Finished thus the present invention.
The invention provides a kind of method for preparing pimelinketone, the method is included under the oxidation reaction condition, in the presence of catalyzer, hexanaphthene is contacted with hydrogen peroxide, wherein, described catalyzer is by in confined conditions, HTS is contacted at 80-200 ℃ with modification liquid, and successively carry out product of contact dry and roasting obtains, described modification liquid is the aqueous solution that contains organic bases, the mass ratio of described HTS and described modification liquid is 100: 10-150, in the described HTS of gram with take the ratio of the organic bases of mole as 100: 0.005-0.2.
The method according to this invention has high cyclohexane conversion and pimelinketone selectivity.And the stablizing of the catalyzer that uses in the method according to this invention is even long-time use also has high catalytic activity.In addition, the method according to this invention is simple and easy to do and environmental friendliness.
Embodiment
The invention provides a kind of method for preparing pimelinketone, the method is included under the oxidation reaction condition, in the presence of catalyzer, hexanaphthene is contacted with hydrogen peroxide.
The method according to this invention, described catalyzer is by in confined conditions, HTS is contacted at 80-200 ℃ with modification liquid, and successively carry out product of contact dry and roasting obtains, described modification liquid is the aqueous solution that contains organic bases, the mass ratio of described HTS and described modification liquid is 100: 10-150, in the described HTS of gram with take the ratio of the organic bases of mole as 100: 0.005-0.2.Under such condition, HTS is processed, water base the form with saturated steam as the solvent of described modification liquid exists, this saturated steam carry solute in the modification liquid (for example: organic bases) in gas phase with HTS in commutative material exchange, after HTS drying and roasting after the above-mentioned processing, catalyzer as oxidizing ethyle alkyl, can significantly improve the transformation efficiency of hexanaphthene, the selectivity of pimelinketone in the oxidation products, and have high effective utilization ratio of hydrogen peroxide; In addition, the stability of catalytic activity of the catalyzer of employing aforesaid method preparation is high, even react for a long time, still has higher catalytic activity.
The method according to this invention, the mass ratio of described HTS and described modification liquid is preferably 100: 10-120.Under such condition, not only can further improve the active and stable of the catalyzer that finally obtains, but also can further reduce the amount as the water of solvent, and then further improve the economy of method of the present invention.Further preferably, the mass ratio of described HTS and described modification liquid is 100: 10-90.
The method according to this invention, the angle of the activity of the catalyzer that finally obtains from further raising and stability is preferably 100 in the HTS of gram and ratio in the organic bases of mole: 0.01-0.15, more preferably 100: 0.05-0.15.
According to the present invention, described HTS can be this area various molecular sieve containing titaniums commonly used, for example, described HTS can for but be not limited to: the HTS of MFI structure (such as TS-1), the HTS of MEL structure (such as TS-2), the HTS of BEA structure (such as Ti-Beta), the HTS of MWW structure (such as Ti-MCM-22), the HTS of hexagonal structure is (such as Ti-MCM-41, Ti-SBA-15), the HTS of MOR structure (such as Ti-MOR), at least a in the HTS (such as Ti-ZSM-48) of the HTS of TUN structure (such as Ti-TUN) and other structure.Preferably, described HTS is the HTS of MFI structure.
The method according to this invention, the content of the titanium atom in the described HTS can for the conventional content of this area, be not particularly limited.Usually, in oxide compound, the content of titanium atom is preferably the 0.1-5 % by weight in the described HTS, more preferably 1-4 % by weight, more preferably 2-3 % by weight.
The method according to this invention, described modification liquid are the aqueous solution that contains organic bases.
In one embodiment of the invention, described modification liquid is the aqueous solution of organic bases.That is, described modification liquid is to obtain by the aqueous solution of preparing organic bases.The method of the aqueous solution of preparation organic bases is known in those skilled in the art, and this paper repeats no more.When described modification liquid is the aqueous solution of organic bases, the present invention is not particularly limited for the concentration of organic bases in the described modification liquid, as long as when HTS contacts with previously described ratio with described modification liquid, the amount of organic bases can satisfy previously described requirement and get final product.
Among the present invention, described organic bases can for various be alkalescence organic compound.Preferably, described organic bases is to be selected from quaternary ammonium hydroxide, fatty amine and the alkyl alcoholamine one or more.
Among the present invention, described quaternary ammonium hydroxide can be the compound shown in the formula I:
Among the formula I, R
1, R
2, R
3And R
4C respectively does for oneself
1-C
20Straight or branched alkyl, C
3-C
20Cycloalkyl or C
6-C
20Aryl.Preferably, R
1, R
2, R
3And R
4C respectively does for oneself
1-C
10Straight or branched alkyl and C
3-C
10Cycloalkyl.Further preferably, R
1, R
2, R
3And R
4C respectively does for oneself
1-C
6The straight or branched alkyl.Among the present invention, described C
1-C
20The straight or branched alkyl example can for but be not limited to: one or more in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, Octadecane base and the NSC 62789 base.
Among the present invention, the example of described quaternary ammonium hydroxide can for but be not limited to: TPAOH (comprising four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide and TBAH (comprising 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl-ammonium hydroxide and tetra-tert ammonium hydroxide).
Among the present invention, fatty amine can be replaced the compound (comprising primary amine, secondary amine and tertiary amine) that generates and at least two hydrogen atoms in the aliphatic hydrocarbon by aliphatic alkyl and (for example: the compound aliphatie diamine) replaced the compound that forms by amido for being selected from one or more hydrogen in the amino molecule.
Among the present invention, the one or more hydrogen in the described amino molecule are replaced by aliphatic alkyl and the compound that generates for example can be the compound shown in the formula II:
Among the formula II, R
5, R
6And R
7Can be H or C separately
1-C
16The straight or branched alkyl, and R
5, R
6And R
7Be not H simultaneously; Preferably, R
5, R
6And R
7H or C respectively do for oneself
1-C
6The straight or branched alkyl, and R
5, R
6And R
7Be not H simultaneously.Among the present invention, described C
1-C
16The straight or branched alkyl example can for but be not limited to: one or more in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base and the n-hexadecyl.
Particularly, the one or more hydrogen in the described amino molecule replaced by aliphatic alkyl and the example of the compound that generates can for but be not limited to: methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, Isopropylamine, Diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, isobutylcarbylamine, di-iso-amylamine, tri-isoamylamine, uncle's amylamine, normal hexyl Amine, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane base amine, dodecyl amine, dodecyl-dimethyl amine, n-tridecane base amine, n-tetradecane base amine, Pentadecane base amine and n-hexadecyl amine.
Among the present invention, at least two hydrogen atoms in the described aliphatic hydrocarbon replaced by amido and the compound that forms for example can quadrol, in propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine and the decamethylene diamine one or more.
Among the present invention, described alkyl alcoholamine refers to have simultaneously in the molecular structure alkyl hydrocarbon of at least one amido and at least one hydroxyl.For example, described alkyl alcoholamine can be the compound shown in the formula III:
In the formula III, R
8, R
9And R
10Can be H, C separately
1-C
16Straight or branched hydroxyalkyl or C
1-C
16The straight or branched alkyl, and R
8, R
9And R
10Be not H or C simultaneously
1-C
16The straight or branched alkyl; Preferably, R
8, R
9And R
10H, C respectively do for oneself
1-C
5Straight or branched hydroxyalkyl or C
1-C
5The straight or branched alkyl, and R
8, R
9And R
10Be not H or C simultaneously
1-C
5The straight or branched alkyl.Among the present invention, C
1-C
16The straight or branched hydroxyalkyl example can for but be not limited to: methylol, hydroxyethyl, hydroxypropyl, hydroxyl butyl and hydroxyl amyl group.
Among the present invention, the example of described alkyl alcoholamine can for but be not limited to: monoethanolamine, diethanolamine, trolamine, tri-isopropanolamine, diethanolamine, two n-propyl alcohol amine, three n-propyl alcohol amine, two propyl carbinol amine and three propyl carbinol amine.
From the angle of being easy to get property of raw material, described organic bases is one or more in TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine and the trolamine.
In another embodiment of the invention, described modification liquid is by in the presence of organic bases, the silicon source mixed with water and obtains, and wherein, the mol ratio of silicon, organic bases and water in the described silicon source is 1: 0.05-5: 15-100.According to the present invention, the mol ratio of silicon, organic bases and water in the described silicon source is preferably 1: 0.3-3: 20-50, more preferably 1: 0.5-2: 20-40.The kind of described organic bases is described in detail at preamble, does not repeat them here.
According to the present invention, the condition of described mixing is not particularly limited, as long as described silicon source and water can be mixed.Preferably, the condition of described mixing comprises: temperature can be 25-90 ℃, and the time can be 2-10 hour.
Among the present invention, described silicon source refers to provide the silicon-containing compound of element silicon, and for example, described silicon source can be for being selected from the silicon ester shown in silicon sol, silica gel and the formula IV one or more,
Among the formula IV, R
11, R
12, R
13And R
14C respectively does for oneself
1-C
4The straight or branched alkyl.
Among the present invention, the example of the silicon ester shown in the formula IV can for but be not limited to: methyl silicate, tetraethoxy, positive silicic acid n-propyl, positive isopropyl silicate and the positive positive butyl ester of silicic acid.
Among the present invention, described silicon sol refers to the colloidal solution of the silicon oxide take water as disperse phase, and wherein, the content of silicon oxide can be the 10-40 % by weight.
Among the present invention, described silica gel can be the silicon oxide particle that contains a small amount of moisture that exists with solid form (wherein, water-content is generally the 0.1-10 % by weight), it also can be the silicon oxide powder that exists with substantially moisture free solid (wherein, water-content is generally below 0.1 % by weight) form.Described silica gel for example can be various types of white carbon black powder that can be commercially available.The present invention is not particularly limited for the median size of described silica gel, can be the conventional particle diameter of this area.Preferably, the median size of described silica gel is 20nm-2mm, is preferably the 100-1000 micron.Among the present invention, described median size is to adopt scanning electronic microscope (SEM) to measure.That is, when adopting scanning electronic microscope to measure, the length of particle and the graduated scale on the scanning electronic microscope are compared, with the maximum length of the particle particle diameter as particle.
Preferably, described silicon source is the silicon ester shown in the formula IV.
In another embodiment of the present invention, described modification liquid is by in the presence of organic bases, silicon source and titanium source mixed with water and obtain, the mol ratio of titanium, organic bases and water in the silicon in the described silicon source, the described titanium source is 1: 0.01-0.1: 0.05-5: 15-100.Preferably, the silicon in the described silicon source, the mol ratio of titanium, organic bases and water in the described titanium source are 1: 0.01-0.05: 0.3-3: 20-50.Further preferably, the silicon in the described silicon source, the mol ratio of titanium, organic bases and water in the described titanium source are 1: 0.01-0.03: 0.5-2: 20-40.The kind in described organic bases and silicon source is described in detail at preamble, does not repeat them here.
According to the present invention, in the presence of organic bases, silicon source and titanium source are mixed with water and can first described silicon source be mixed with water in the presence of organic bases, and then mix in adding titanium source; Can also be in the presence of organic bases, silicon source and titanium source are mixed with water simultaneously.
Among the present invention, described titanium source refers to provide the titanium-containing compound of titanium elements, and for example, described titanium source can be for being selected from TiCl
4, Ti (SO
4)
2, TiOCl
2With in the titanic acid ester shown in the formula V one or more,
Among the formula V, R
15, R
16, R
17And R
18Can be C separately
1-C
6The straight or branched alkyl, be preferably C
2-C
4The straight or branched alkyl, more preferably ethyl, propyl group (comprising n-propyl and sec.-propyl) or butyl (comprising normal-butyl, sec-butyl, isobutyl-and the tertiary butyl).
Among the present invention, the example of the titanic acid ester shown in the formula V can for but be not limited to: titanium isopropylate, tetra-n-butyl titanate and tetraethyl titanate.
According to the present invention, described titanium source is preferably the titanic acid ester shown in the formula V.
The method according to this invention, the condition of the mixing of described silicon source, titanium source and water is not particularly limited.Usually, the condition of described mixing comprises: temperature can be 25-90 ℃, and the time can be 2-10 hour.
According to the present invention, from the transformation efficiency of further raising hexanaphthene, the effective rate of utilization of hydrogen peroxide and the optionally angle of pimelinketone, described modification liquid is preferably the aqueous solution of organic bases; Or by in the presence of organic bases, silicon source, titanium source mixed with water and obtain, and the mol ratio of titanium, organic bases and water in the silicon in the described silicon source, described titanium source is 1: 0.01-0.1: 0.05-5: 15-100.More preferably, described modification liquid is by in the presence of organic bases, silicon source, titanium source mixed with water and obtain, and the mol ratio of titanium, organic bases and water in the silicon in the described silicon source, described titanium source is 1: 0.01-0.1: 0.05-5: 15-100; Further preferably, described modification liquid is by in the presence of organic bases, titanic acid ester shown in silicon source, the formula V mixed with water and obtain, and the mol ratio of titanium, organic bases and water in the silicon in the described silicon source, described titanium source is 1: 0.01-0.1: 0.05-5: 15-100.
The method according to this invention, described catalyzer are by in confined conditions, HTS is contacted at 80-200 ℃ with modification liquid, and successively carry out product of contact dry and roasting obtains.
The method according to this invention, the Contact Temperature of described HTS and described modification liquid can be 80-200 ℃, is preferably 135-180 ℃.Can carry out appropriate selection the duration of contact of described HTS and described modification liquid, is generally at least 2 hours, for example can be 6-72 hour.
The present invention is not particularly limited for method and the condition of described drying and roasting, can be the ordinary method of this area.Usually, the condition of described drying comprises: temperature can be 25-200 ℃, is preferably 70-160 ℃; Time can be 2-12 hour, is preferably 2-6 hour.The condition of described roasting comprises: temperature can be 300-800 ℃, is preferably 500-700 ℃; Time can be 2-12 hour, is preferably 2-6 hour.
In addition, can also be with reference to disclosed method preparation in the applicant's Chinese patent application 201010213601.2 and the Chinese patent application 201010213605.0 about the catalyzer that uses in the method for the present invention.
The method according to this invention, described oxygenant are hydrogen peroxide.The method according to this invention, described hydrogen peroxide can be this area hydrogen peroxide that exists with various forms commonly used.From the angle of the security of further raising the method according to this invention, the method according to this invention is preferably used the hydrogen peroxide that exists with aqueous solution form.The method according to this invention, when described hydrogen peroxide provided with aqueous solution form, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, for example: the 20-80 % by weight.The aqueous solution that concentration satisfies the hydrogen peroxide of above-mentioned requirements can adopt the ordinary method preparation, also can be commercially available, for example: can be hydrogen peroxide, the hydrogen peroxide of 50 % by weight or the hydrogen peroxide of 70 % by weight of 30 % by weight that can be commercially available.The hydrogen peroxide that uses in the embodiment of the invention and the Comparative Examples is the hydrogen peroxide of 30 % by weight as concentration.
The method according to this invention, hexanaphthene carries out in the presence of solvent with contacting preferably of hydrogen peroxide, can regulate the severe degree of reaction more easily so on the one hand, thereby so that the method according to this invention has higher security; Can also make on the other hand the contact of each reactant more abundant.The present invention is not particularly limited for the kind of described solvent, can be this area all kinds of SOLVENTS commonly used.Preferably, described solvent is C
1-C
10Alcohol, C
3-C
10Ketone and C
2-C
10Nitrile in one or more, for example: described solvent can be in methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and the acetonitrile one or more.More preferably, described solvent is C
1-C
5Fatty alcohol and C
3-C
5Aliphatic ketone in one or more, for example: described solvent can be in acetone, methyl alcohol and the trimethyl carbinol one or more.
The method according to this invention, the consumption of described solvent can be the conventional amount used of this area.Preferably, the mol ratio of hexanaphthene and described solvent is 1: 1-100.More preferably, the mol ratio of hexanaphthene and described solvent is 1: 5-50.
The method according to this invention, hexanaphthene can carry out under oxygen-containing atmosphere (for example: air atmosphere or oxygen atmosphere) with contacting of hydrogen peroxide, also can carry out under anoxic condition.In embodiments of the invention and the Comparative Examples, hexanaphthene carries out under air atmosphere with contacting all of hydrogen peroxide.
The method according to this invention is not particularly limited for described oxidation reaction condition.Usually, described oxidation reaction condition comprises: temperature can be 0-150 ℃, is preferably 30-120 ℃, more preferably 30-70 ℃; Pressure can be 0.1-3MPa, is preferably 0.1-2.5MPa, more preferably 0.5-2.5MPa; The mol ratio of hexanaphthene and hydrogen peroxide can be 1: 0.1-10 is preferably 1: 0.2-8, more preferably 1: 1-8; The mass ratio of hexanaphthene and described catalyzer can be 2-100: 1, be preferably 2-50: and 1,10-50 more preferably: 1.
The method according to this invention can adopt periodical operation, also can adopt operate continuously etc., and the present invention is not particularly limited this.The method according to this invention, feed way also can be any suitable mode well known by persons skilled in the art, as when carrying out with andnon-continuous operation manner, and can be after solvent and catalyzer be added reactor, add continuously hexanaphthene and oxygenant, to react; When in the tank reactor of sealing, carrying out rhythmic reaction, catalyzer, hexanaphthene and hydrogen peroxide and optional solvent can be added in the reactor simultaneously, to react.When carrying out in a continuous manner, can adopt the reactor commonly used such as fixed-bed reactor or slurry bed reactor.Wherein, when implementing method of the present invention in fixed-bed reactor, feed way can be for after in fixed-bed reactor that catalyzer is packed into, and hexanaphthene and hydrogen peroxide and optional solvent are added continuously; When in slurry bed reactor, implementing method of the present invention, after catalysts and solvents can being pulled an oar, add continuously hexanaphthene and hydrogen peroxide, to react in reactor.
The method according to this invention can adopt the ordinary method of this area that pimelinketone is separated from the product of contact of hexanaphthene and hydrogen peroxide, for example: can be by product of contact be distilled, thus pimelinketone is separated from reaction product.The method of described distillation and condition are known in the field, and this paper repeats no more.
The invention will be further described for following embodiment, but therefore do not limit content of the present invention.
In following examples and the Comparative Examples, as not specifying, used reagent is commercially available analytical reagent.
In following examples, used titanium-silicon molecular sieve TS-1 is according to Zeolites, the method preparation described in 1992, the 12 volumes, 943-950 page or leaf.
In following examples, used HTS Ti-MCM-41 be according to Corma etc. at Chem.Commun., the method preparation described in 1994, the 147-148, in oxide compound, the titanium content in this HTS is 3 % by weight.
In following examples, used HTS Ti-Beta be according to Takashi Tatsumi etc. at J.Chem.Soc.Chem.Commun., the method preparation described in 1997, the 677-678, in oxide compound, the titanium content in this HTS is 2.6 % by weight.
Among the present invention, adopt gas-chromatography to analyze the content of each composition in the reaction solution that obtains, adopt respectively on this basis following formula to calculate cyclohexane conversion, effective utilization ratio of hydrogen peroxide and pimelinketone selectivity:
Embodiment 1
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Restrain the TS-1 HTS (in oxide compound with 10, titanium content in this HTS is 2.5 % by weight), 4.8 gram concentration are that to place liner be the autoclave of tetrafluoroethylene for the aqueous solution of the tetraethyl ammonium hydroxide of 28 quality %, and in above-mentioned autoclave, add again the 2mL deionized water, then close autoclave, temperature in the reactor is elevated to 145 ℃, and under this temperature, reacted 12 hours.Reaction product 100 ℃ of dryings 180 minutes, then with desciccate roasting 3 hours under 650 ℃ of air atmospheres, thereby is obtained catalyst A.
Hexanaphthene, hydrogen peroxide, acetone and catalyst A are placed autoclave, are that 30 ℃ and pressure are reaction 12 hours under the condition of 1.5MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and acetone is 1: 2: 10, and the mass ratio of hexanaphthene and catalyst A is 20: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 36%, and effective utilization ratio of hydrogen peroxide is 61%, and the pimelinketone selectivity is 59%; The test result of reacting 12 hours is: cyclohexane conversion is 35%, and effective utilization ratio of hydrogen peroxide is 60%, and the pimelinketone selectivity is 57%.
Comparative Examples 1
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 1 to prepare pimelinketone, different is not use catalyzer.Adopt gas-chromatography to come the composition of 2 hours reaction solution of assaying reaction, test result is: cyclohexane conversion is 0.3%, and the pimelinketone selectivity is 0%.
Comparative Examples 2
Adopt the method identical with embodiment 1 to prepare pimelinketone, different is that use TS-1 HTS is as catalyzer.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 27%, and effective utilization ratio of hydrogen peroxide is 32%, and the pimelinketone selectivity is 38%; The test result of reacting 12 hours is: cyclohexane conversion is 21%, and effective utilization ratio of hydrogen peroxide is 27%, and the pimelinketone selectivity is 42%.
Comparative Examples 3
Adopt the method identical with embodiment 1 to prepare pimelinketone, different is when Kaolinite Preparation of Catalyst, to add the 20mL deionized water again in above-mentioned autoclave, thereby obtain catalyzer.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 31%, and effective utilization ratio of hydrogen peroxide is 45%, and the pimelinketone selectivity is 48%; The test result of reacting 12 hours is: cyclohexane conversion is 28%, and effective utilization ratio of hydrogen peroxide is 42%, and the pimelinketone selectivity is 41%.
Embodiment 2
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Restrain the TS-1 HTS (in oxide compound with 12, titanium content in this HTS is 1.2 % by weight), 1 gram trolamine and 5 gram concentration are that to place liner be the autoclave of tetrafluoroethylene for the aqueous solution of the four n-propyl ammonium hydroxide of 16.3 quality %, and in above-mentioned autoclave, add again the 3mL deionized water, then close autoclave, temperature in the reactor is elevated to 160 ℃, and under this temperature, reacted 56 hours.Reaction product 150 ℃ of dryings 120 minutes, then with desciccate roasting 6 hours under 540 ℃ of air atmospheres, thereby is obtained catalyst B.
Hexanaphthene, hydrogen peroxide, the trimethyl carbinol and catalyst B are placed autoclave, are that 70 ℃ and pressure are reaction 12 hours under the condition of 2.5MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and the trimethyl carbinol is 1: 1: 20, and the mass ratio of hexanaphthene and catalyst B is 10: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 33%, and effective utilization ratio of hydrogen peroxide is 55%, and the pimelinketone selectivity is 62%; The test result of reacting 12 hours is: cyclohexane conversion is 31%, and effective utilization ratio of hydrogen peroxide is 53%, and the pimelinketone selectivity is 60%.
Embodiment 3
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Restrain the TS-1 HTS (in oxide compound with 12, titanium content in this HTS is 3.2 % by weight), 0.5 gram Tri N-Propyl Amine and 7.5 gram concentration are that to place liner be the autoclave of tetrafluoroethylene for the aqueous solution of the four n-propyl ammonium hydroxide of 16.3 quality %, then close autoclave, temperature in the reactor is elevated to 175 ℃, and under this temperature, reacted 48 hours.Reaction product 90 ℃ of dryings 240 minutes, then with desciccate roasting 2 hours under 700 ℃ of air atmospheres, thereby is obtained catalyzer C.
Hexanaphthene, hydrogen peroxide, methyl alcohol and catalyzer C are placed autoclave, are that 50 ℃ and pressure are reaction 12 hours under the condition of 0.5MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and methyl alcohol is 1: 2: 25, and the mass ratio of hexanaphthene and catalyzer C is 50: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 48%, and effective utilization ratio of hydrogen peroxide is 71%, and the pimelinketone selectivity is 69%; The test result of reacting 12 hours is: cyclohexane conversion is 46%, and effective utilization ratio of hydrogen peroxide is 68%, and the pimelinketone selectivity is 66%.
Embodiment 4
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method Kaolinite Preparation of Catalyst A identical with embodiment 1.
Hexanaphthene, hydrogen peroxide, acetone and catalyst A are placed autoclave, are that 40 ℃ and pressure are reaction 12 hours under the condition of 1.5MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and acetone is 1: 8: 50, and the mass ratio of hexanaphthene and catalyst A is 15: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 65%, and effective utilization ratio of hydrogen peroxide is 57%, and the pimelinketone selectivity is 83%; The test result of reacting 12 hours is: cyclohexane conversion is 62%, and effective utilization ratio of hydrogen peroxide is 54%, and the pimelinketone selectivity is 81%.
Embodiment 5
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method Kaolinite Preparation of Catalyst B identical with embodiment 2.
Hexanaphthene, hydrogen peroxide, butanone and catalyst B are placed autoclave, are that 60 ℃ and pressure are reaction 12 hours under the condition of 0.5MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and butanone is 1: 2: 40, and the mass ratio of hexanaphthene and catalyst B is 25: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 46%, and effective utilization ratio of hydrogen peroxide is 55%, and the pimelinketone selectivity is 56%; The test result of reacting 12 hours is: cyclohexane conversion is 45%, and effective utilization ratio of hydrogen peroxide is 52%, and the pimelinketone selectivity is 54%.
Embodiment 6
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method Kaolinite Preparation of Catalyst C identical with embodiment 3.
Hexanaphthene, hydrogen peroxide, acetone and catalyzer C are placed autoclave, are that 30 ℃ and pressure are reaction 12 hours under the condition of 1.5MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and acetone is 1: 2: 15, and the mass ratio of hexanaphthene and catalyzer C is 40: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 53%, and effective utilization ratio of hydrogen peroxide is 58%, and the pimelinketone selectivity is 59%; The test result of reacting 12 hours is: cyclohexane conversion is 49%, and effective utilization ratio of hydrogen peroxide is 55%, and the pimelinketone selectivity is 57%.
Embodiment 7
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
With tetraethyl orthosilicate, tetraethyl ammonium hydroxide and deionized water (wherein, take the mol ratio of silicon source, tetraethyl ammonium hydroxide and the water of silicon as 1: 0.85: 20) place liner as the autoclave of tetrafluoroethylene, 25 ℃ of lower stirrings 1 hour, then the temperature in the autoclave is increased to 75 ℃, and under this temperature restir 3 hours, thereby obtain modification liquid A.
10 gram modification liquid A and 12 are restrained the TS-1 HTS (in oxide compound, titanium content in this HTS is 4.5 % by weight) place another autoclave, then close autoclave, the temperature of autoclave is elevated to 175 ℃, and under this temperature, reacted 12 hours.With reaction product directly 150 ℃ of dryings 120 minutes, and then roasting 5 hours under 580 ℃ of air atmospheres, thus obtain catalyzer D.
Hexanaphthene, hydrogen peroxide, acetone and catalyzer D are placed autoclave, are that 40 ℃ and pressure are reaction 12 hours under the condition of 1MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and acetone is 1: 2: 10, and the mass ratio of hexanaphthene and catalyzer D is 40: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 44%, and effective utilization ratio of hydrogen peroxide is 56%, and the pimelinketone selectivity is 53%; The test result of reacting 12 hours is: cyclohexane conversion is 42%, and effective utilization ratio of hydrogen peroxide is 54%, and the pimelinketone selectivity is 52%.
Embodiment 8
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
With tetraethyl orthosilicate, tetraethyl titanate, tetraethyl ammonium hydroxide and deionized water (wherein, in the tetraethyl orthosilicate of silicon, the mol ratio of tetraethyl titanate, tetraethyl ammonium hydroxide and water take titanium as 1: 0.02: 0.75: 35) place liner as the autoclave of tetrafluoroethylene, 25 ℃ of lower stirrings 1 hour, then the temperature in the autoclave is increased to 80 ℃, and under this temperature restir 3 hours, thereby obtain modification liquid B.
The 13 above-mentioned modification liquid B of gram and 15 are restrained the TS-1 HTS (in oxide compound, titanium content in this HTS is 2.8 % by weight) place another autoclave, then close autoclave, the temperature of autoclave is elevated to 160 ℃, and under this temperature, reacted 62 hours.With reaction product directly 135 ℃ of dryings 240 minutes, and then roasting 3 hours under 560 ℃ of air atmospheres, thus obtain catalyzer E.
Hexanaphthene, hydrogen peroxide, acetone and catalyzer E are placed autoclave, are that 40 ℃ and pressure are reaction 12 hours under the condition of 1MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and acetone is 1: 4: 15, and the mass ratio of hexanaphthene and catalyzer E is 10: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 73%, and effective utilization ratio of hydrogen peroxide is 65%, and the pimelinketone selectivity is 79%; The test result of reacting 12 hours is: cyclohexane conversion is 70%, and effective utilization ratio of hydrogen peroxide is 61%, and the pimelinketone selectivity is 75%.
Embodiment 9
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Silica gel (is purchased from Qingdao silica gel factory, spheroidal particle, the 180-830 micron), di-n-propylamine, four n-propyl ammonium hydroxide and deionized water are (wherein, silica gel in silicon, di-n-propylamine, the mol ratio of four n-propyl ammonium hydroxide and water is 1: 0.35: 1.2: 30) placing liner is the autoclave of tetrafluoroethylene, 25 ℃ of lower stirrings 1.5 hours, then in autoclave, add tetraethyl titanate (wherein, in the silica gel of silicon with take the mol ratio of the tetraethyl titanate of titanium as 1: 0.025), the temperature of autoclave is increased to 65 ℃, and under this temperature, stirred 5 hours, thereby obtain modification liquid C.
The 5 above-mentioned modification liquid C of gram and 10 are restrained the TS-1 HTS (in oxide compound, titanium content in this HTS is 3.1 % by weight) place another autoclave, then close autoclave, the temperature of autoclave is elevated to 150 ℃, and under this temperature, reacted 65 hours.With reaction product directly 135 ℃ of dryings 240 minutes, and then roasting 3 hours under 560 ℃ of air atmospheres, thus obtain catalyzer F.
Hexanaphthene, hydrogen peroxide, acetone and catalyzer F are placed autoclave, are that 40 ℃ and pressure are reaction 12 hours under the condition of 1MPa in temperature.Wherein, the mol ratio of hexanaphthene, hydrogen peroxide and acetone is 1: 3: 5, and the mass ratio of hexanaphthene and catalyzer F is 30: 1.The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 68%, and effective utilization ratio of hydrogen peroxide is 65%, and the pimelinketone selectivity is 72%; The test result of reacting 12 hours is: cyclohexane conversion is 64%, and effective utilization ratio of hydrogen peroxide is 61%, and the pimelinketone selectivity is 68%.
Embodiment 10
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 8 to prepare pimelinketone, different is during Kaolinite Preparation of Catalyst, to use Ti-MCM-41 HTS replacement TS-1 HTS.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 60%, and effective utilization ratio of hydrogen peroxide is 53%, and the pimelinketone selectivity is 71%; The test result of reacting 12 hours is: cyclohexane conversion is 57%, and effective utilization ratio of hydrogen peroxide is 50%, and the pimelinketone selectivity is 68%.
Embodiment 11
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 8 to prepare pimelinketone, different is during Kaolinite Preparation of Catalyst, to use Ti-Beta HTS replacement TS-1 HTS.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 62%, and effective utilization ratio of hydrogen peroxide is 61%, and the pimelinketone selectivity is 60%; The test result of reacting 12 hours is: cyclohexane conversion is 58%, and effective utilization ratio of hydrogen peroxide is 57%, and the pimelinketone selectivity is 55%.
Embodiment 12
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 3 to prepare pimelinketone, different is that catalyzer is to adopt following method to prepare:
Silica gel (is purchased from Qingdao silica gel factory, spheroidal particle, the 180-830 micron), Tri N-Propyl Amine, four n-propyl ammonium hydroxide and deionized water are (wherein, take the mol ratio of silica gel, Tri N-Propyl Amine, four n-propyl ammonium hydroxide and the water of silicon as 1: 0.3: 1.5: 20) place liner as the autoclave of tetrafluoroethylene, 25 ℃ of lower stirrings 1 hour, the temperature of autoclave is increased to 65 ℃, and under this temperature restir 5 hours, thereby obtain modification liquid D.
The 5 above-mentioned modification liquid D of gram and 12 are restrained the TS-1 HTS (in oxide compound, titanium content in this HTS is 0.8 % by weight) place another autoclave, then close autoclave, the temperature of autoclave is elevated to 150 ℃, and under this temperature, reacted 65 hours.With reaction product directly 95 ℃ of dryings 240 minutes, and then roasting 2 hours under 700 ℃ of air atmospheres, thus obtain catalyzer G.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 43%, and effective utilization ratio of hydrogen peroxide is 62%, and the pimelinketone selectivity is 64%; The test result of reacting 12 hours is: cyclohexane conversion is 41%, and effective utilization ratio of hydrogen peroxide is 58%, and the pimelinketone selectivity is 61%.
Embodiment 13
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 3 to prepare pimelinketone, different is that catalyzer is to adopt following method to prepare:
Silicon sol (is purchased from Qingdao silica gel factory, SiO
2Content is 28 quality %), di-n-propylamine, four n-propyl ammonium hydroxide and deionized water (wherein, take the mol ratio of silicon sol, di-n-propylamine, four n-propyl ammonium hydroxide and the water of silicon as 1: 0.3: 1.5: 20) place liner as the autoclave of tetrafluoroethylene, 25 ℃ of lower stirrings 1 hour; In autoclave, add tetra-n-butyl titanate (wherein, in the silicon sol of silicon with take the mol ratio of the tetra-n-butyl titanate of titanium as 1: 0.02) temperature of autoclave is increased to 65 ℃, and under this temperature restir 5 hours, thereby obtain modification liquid E.
The 5 above-mentioned modification liquid E of gram and 12 are restrained the TS-1 HTS (in oxide compound, titanium content in this HTS is 3.5 % by weight) place another autoclave, then close autoclave, the temperature of autoclave is elevated to 150 ℃, and under this temperature, reacted 65 hours.With reaction product directly 95 ℃ of dryings 240 minutes, and then roasting 2 hours under 700 ℃ of air atmospheres, thus obtain catalyzer G.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 68%, and effective utilization ratio of hydrogen peroxide is 84%, and the pimelinketone selectivity is 71%; The test result of reacting 12 hours is: cyclohexane conversion is 64%, and effective utilization ratio of hydrogen peroxide is 81%, and the pimelinketone selectivity is 66%.
Embodiment 14
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 7 to prepare pimelinketone, different is, during the preparation modification liquid, with positive silicic acid four n-propyls replacement silica gel.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 41%, and effective utilization ratio of hydrogen peroxide is 56%, and the pimelinketone selectivity is 58%; The test result of reacting 12 hours is: cyclohexane conversion is 40%, and effective utilization ratio of hydrogen peroxide is 55%, and the pimelinketone selectivity is 58%.
Embodiment 15
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 7 to prepare pimelinketone, different is, during the preparation modification liquid, with white carbon black (be purchased from Qingdao silica gel factory, vapour deposition process prepares, and median size is 100nm) replacement silica gel.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 36%, and effective utilization ratio of hydrogen peroxide is 52%, and the pimelinketone selectivity is 50%; The test result of reacting 12 hours is: cyclohexane conversion is 35%, and effective utilization ratio of hydrogen peroxide is 51%, and the pimelinketone selectivity is 47%.
Embodiment 16
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 8 to prepare pimelinketone, different is during the preparation modification liquid, to use titanium tetrachloride replacement tetraethyl titanate.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 68%, and effective utilization ratio of hydrogen peroxide is 62%, and the pimelinketone selectivity is 65%; The test result of reacting 12 hours is: cyclohexane conversion is 65%, and effective utilization ratio of hydrogen peroxide is 59%, and the pimelinketone selectivity is 63%.
Embodiment 17
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 8 to prepare pimelinketone, different is, during the preparation modification liquid, and use Ti (SO
4)
2Replace tetraethyl titanate.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 62%, and effective utilization ratio of hydrogen peroxide is 64%, and the pimelinketone selectivity is 60%; The test result of reacting 12 hours is: cyclohexane conversion is 57%, and effective utilization ratio of hydrogen peroxide is 60%, and the pimelinketone selectivity is 56%.
Embodiment 18
The present embodiment is used for illustrating the method for preparing pimelinketone according to of the present invention.
Adopt the method identical with embodiment 8 to prepare pimelinketone, different is, during the preparation modification liquid, and use TiOCl
2Replace tetraethyl titanate.
The employing gas-chromatography is come the composition of 2 hours reaction solution of assaying reaction and is reacted the composition of 12 hours reaction solution.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 65%, and effective utilization ratio of hydrogen peroxide is 63%, and the pimelinketone selectivity is 62%; The test result of reacting 12 hours is: cyclohexane conversion is 61%, and effective utilization ratio of hydrogen peroxide is 58%, and the pimelinketone selectivity is 59%.
Claims (19)
1. method for preparing pimelinketone, the method is included under the oxidation reaction condition, in the presence of catalyzer, hexanaphthene is contacted with hydrogen peroxide, it is characterized in that, described catalyzer is by in confined conditions, HTS is contacted at 80-200 ℃ with modification liquid, and successively carry out product of contact dry and roasting obtains, described modification liquid is the aqueous solution that contains organic bases, the mass ratio of described HTS and described modification liquid is 100: 10-150, in the described HTS of gram with take the ratio of the organic bases of mole as 100: 0.005-0.2.
2. method according to claim 1, wherein, the mass ratio of described HTS and described modification liquid is 100: 10-120.
3. method according to claim 1, wherein, in the described HTS of gram with take the ratio of the organic bases of mole as 100: 0.01-0.15.
4. method according to claim 1, wherein, described modification liquid is the aqueous solution of organic bases.
5. method according to claim 1, wherein, described modification liquid is by in the presence of organic bases, the silicon source is mixed with water and obtains, the mol ratio of the silicon in the described silicon source, described organic bases and water is 1: 0.05-5: 15-100.
6. method according to claim 5, wherein, the mol ratio of the silicon in the described silicon source, described organic bases and water is 1: 0.3-3: 20-50.
7. method according to claim 1, wherein, described modification liquid is by in the presence of organic bases, silicon source, titanium source mixed with water and obtains, and the mol ratio of titanium, organic bases and water in the silicon in the described silicon source, the described titanium source is 1: 0.01-0.1: 0.05-5: 15-100.
8. method according to claim 7, wherein, the mol ratio of titanium, organic bases and water in the silicon in the described silicon source, the described titanium source is 1: 0.01-0.05: 0.3-3: 20-50.
9. according to claim 7 or 8 described methods, wherein, described titanium source is for being selected from TiCl
4, Ti (SO
4)
2, TiOCl
2With in the titanic acid ester shown in the formula V one or more,
Among the formula V, R
15, R
16, R
17And R
18C respectively does for oneself
1-C
6Alkyl.
10. according to claim 5 or 7 described methods, wherein, the condition of described mixing comprises: temperature is 25-90 ℃, and the time is 2-10 hour.
11. the described method of any one according to claim 5-8, wherein, described silicon source is to be selected from the silicon ester shown in silicon sol, silica gel and the formula IV one or more,
Among the formula IV, R
11, R
12, R
13And R
14C respectively does for oneself
1-C
4Alkyl.
12. according to claim 1 with 3-8 in the described method of any one, wherein, described organic bases is to be selected from quaternary ammonium hydroxide, fatty amine and the alkyl alcoholamine one or more.
13. method according to claim 12, wherein, described organic bases is one or more in TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine and the trolamine.
14. method according to claim 1, wherein, described HTS and described modification liquid carry out 6-72 hour contact at 135-180 ℃.
15. the described method of any one according to claim 1-3 and in 14, wherein, described HTS is at least a in the HTS of the HTS of HTS, TUN structure of HTS, the MOR structure of HTS, the MWW structure of HTS, the BEA structure of HTS, the MEL structure of MFI structure and two-dimentional hexagonal structure.
16. method according to claim 1, wherein, the condition of described roasting comprises: temperature is 300-800 ℃, and the time is 2-12 hour.
17. method according to claim 1, wherein, hexanaphthene carries out with contacting in the presence of solvent of oxygenant, and the mol ratio of hexanaphthene and described solvent is 1: 1-100.
18. method according to claim 17, wherein, described solvent is C
1-C
10Alcohol, C
3-C
10Ketone and C
2-C
10Nitrile in one or more.
19. method according to claim 1, wherein, described oxidation reaction condition comprises: temperature is 0-150 ℃, and pressure is 0.1-3MPa, and the mol ratio of hexanaphthene and described oxygenant is 1: 0.1-10, the mass ratio of hexanaphthene and described catalyzer are 2-100: 1.
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| CN104418702A (en) * | 2013-09-06 | 2015-03-18 | 中国石油化工股份有限公司 | Method for oxidation of cyclohexane |
| CN105085462A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Cyclohexanone oxidation method |
| CN105984879A (en) * | 2015-01-29 | 2016-10-05 | 中国石油化工股份有限公司 | MWW-structure molecular sieve and preparation method thereof |
| 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 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418702A (en) * | 2013-09-06 | 2015-03-18 | 中国石油化工股份有限公司 | Method for oxidation of cyclohexane |
| CN104418702B (en) * | 2013-09-06 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of method of oxidizing ethyle alkyl |
| CN105085462A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Cyclohexanone oxidation method |
| CN105085462B (en) * | 2014-05-08 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of method of oxidizing cyclohexanone |
| CN105984879A (en) * | 2015-01-29 | 2016-10-05 | 中国石油化工股份有限公司 | MWW-structure molecular sieve and preparation method thereof |
| CN105984879B (en) * | 2015-01-29 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of MWW structure molecular screen and preparation method thereof |
| 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 |
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