CN102850197B - Method for preparing cyclohexanone - Google Patents
Method for preparing cyclohexanone Download PDFInfo
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- CN102850197B CN102850197B CN201110183067.XA CN201110183067A CN102850197B CN 102850197 B CN102850197 B CN 102850197B CN 201110183067 A CN201110183067 A CN 201110183067A CN 102850197 B CN102850197 B CN 102850197B
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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 preparing pimelinketone.
Background technology
Pimelinketone is widely used in fiber, synthetic rubber, industrial coating, medicine and pesticide industry, industrial chemicals can be used as, such as: pimelinketone may be used for important monomer hexanodioic acid and the hexanolactam of preparing synthesizing polyamides, for the preparation of softening agent and washing composition etc., also can also can be used as the solvent in chemical operation process and emulsifying agent.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, and wherein cyclohexane oxidation process is the industrial main process for the production of pimelinketone, accounts for more than 90%.According to the catalyst type whether using catalyzer and use, the industrial cyclohexane oxidation that utilizes generally has three kinds of methods to produce pimelinketone: take cobalt salt as the catalytic oxidation of catalyzer, take boric acid compound as the catalytic oxidation of catalyzer and the non-catalyst oxidation method with air direct oxidation.But use the cyclohexane oxidation production process of any method all to there is inefficient shortcoming, cyclohexane oxidation process is even considered to minimum one of efficiency in all chemical industry processes.The poor efficiency of cyclohexane oxidation synthesizing cyclohexanone process has become restriction and has used one of bottleneck of the polymeric amide industry production of hexanolactam and hexanodioic acid.
Therefore, developing a kind of can be a technical problem urgently to be resolved hurrily to prepare the method for pimelinketone with high cyclohexane conversion and pimelinketone selectivity.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of method preparing pimelinketone, the method can obtain high cyclohexane conversion and pimelinketone selectivity.
HTS is the class hetero-atom molecular-sieve be made up of titanyl tetrahedron and silicon-oxy tetrahedron, has higher thermostability, resistance to acid and hydrophobicity, also has good catalytic activity and selectivity simultaneously.But using HTS as catalyzer, when carrying out oxidizing ethyle alkyl using hydrogen peroxide as oxygenant, be difficult to obtain gratifying cyclohexane conversion and pimelinketone selectivity, the effective rate of utilization of hydrogen peroxide is not high yet simultaneously.
The present inventor is through in depth studying, surprisingly find: in confined conditions, HTS is contacted at 80-200 DEG C with the solution containing organic bases, and product of contact is carried out drying and roasting, the product of roasting obtained is used as catalyzer when carrying out oxidizing ethyle alkyl using hydrogen peroxide as oxygenant, the transformation efficiency of hexanaphthene and the selectivity of pimelinketone can be significantly improved, and the effective rate of utilization of hydrogen peroxide can be significantly improved.This completes the present invention.
The invention provides a kind of method preparing pimelinketone, under the method is included in oxidation reaction condition, in the presence of a catalyst, hexanaphthene is contacted with hydrogen peroxide, wherein, described catalyzer is by confined conditions, HTS is contacted at 80-200 DEG C with modification liquid, and product of contact is successively carried out dry and roasting and obtain, described modification liquid is the aqueous solution containing organic bases, the mass ratio of described HTS and described modification liquid is 100: 10-150, in gram described HTS with in mole the ratio of organic bases for 100: 0.005-0.2.
Method according to the present invention has high cyclohexane conversion and pimelinketone selectivity.Further, according to stablizing of the catalyzer used in method of the present invention, even if long-time use also has high catalytic activity.In addition, method is simple and environmental friendliness according to of the present invention.
Embodiment
The invention provides a kind of method preparing pimelinketone, under the method is included in oxidation reaction condition, in the presence of a catalyst, hexanaphthene is contacted with hydrogen peroxide.
According to method of the present invention, described catalyzer is by confined conditions, HTS is contacted at 80-200 DEG C with modification liquid, and product of contact is successively carried out dry and roasting and obtain, described modification liquid is the aqueous solution containing organic bases, the mass ratio of described HTS and described modification liquid is 100: 10-150, in gram described HTS with in mole the ratio of organic bases for 100: 0.005-0.2.In such a situa-tion HTS is processed, water base of solvent as described modification liquid exists with the form of saturated steam, the solute (such as: organic bases) that this saturated steam carries in modification liquid exchanges with the commutative material in HTS in the gas phase, after HTS drying after above-mentioned process and roasting, as the catalyzer of oxidizing ethyle alkyl, the transformation efficiency of hexanaphthene can be significantly improved, the selectivity of oxidation products cyclohexanone, and there is high effective utilization ratio of hydrogen peroxide; In addition, the stability of catalytic activity of the catalyzer adopting aforesaid method to prepare is high, even if react for a long time, still has higher catalytic activity.
According to method of the present invention, the mass ratio of described HTS and described modification liquid is preferably 100: 10-120.Activity and the stability of the catalyzer finally obtained can not only be improved in such a situa-tion further, but also the amount of the water as solvent can be reduced further, and then improve the economy of method of the present invention further.Further preferably, the mass ratio of described HTS and described modification liquid is 100: 10-90.
According to method of the present invention, the activity of catalyzer finally obtained from further raising and the angle of stability, in gram HTS with in mole the ratio of organic bases be preferably 100: 0.01-0.15, be more preferably 100: 0.05-0.15.
According to the present invention, the various molecular sieve containing titaniums that described HTS can be commonly used for this area, such as, described HTS can be but be not limited to: the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, at least one in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.Preferably, described HTS is the HTS of MFI structure.
According to method of the present invention, the content of the titanium atom in described HTS can be the conventional content of this area, is not particularly limited.Usually, with oxide basis, in described HTS, the content of titanium atom is preferably 0.1-5 % by weight, is more preferably 1-4 % by weight, more preferably 2-3 % by weight.
According to method of the present invention, described modification liquid is the aqueous solution containing organic bases.
In one embodiment of the invention, described modification liquid is the aqueous solution of organic bases.That is, described modification liquid is obtained by the aqueous solution preparing organic bases.The method of the aqueous solution of preparation organic bases is known in those skilled in the art, repeats no more herein.When described modification liquid is the aqueous solution of organic bases, the present invention is not particularly limited for paper mill wastewater organic in described modification liquid, as long as when HTS contacts with previously described ratio with described modification liquid, the amount of organic bases can meet previously described requirement.
In the present invention, described organic bases can be the various organic compound for alkalescence.Preferably, described organic bases be selected from quaternary ammonium hydroxide, fatty amine and alkyl alcoholamine one or more.
In the present invention, described quaternary ammonium hydroxide can be the compound shown in formula I:
In formula I, R
1, R
2, R
3and R
4be C separately
1-C
20straight or branched alkyl, C
3-C
20cycloalkyl or C
6-C
20aryl.Preferably, R
1, R
2, R
3and R
4be C separately
1-C
10straight or branched alkyl and C
3-C
10cycloalkyl.Further preferably, R
1, R
2, R
3and R
4be C separately
1-C
6straight or branched alkyl.In the present invention, described C
1-C
20straight 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 NSC 62789 base.
In the present invention, the example of described quaternary ammonium hydroxide can be 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).
In the present invention, fatty amine can be replaced by amido at least two hydrogen atoms in the compound (comprising primary amine, secondary amine and tertiary amine) that the one or more hydrogen be selected from amino molecule are replaced by aliphatic alkyl and generate and aliphatic hydrocarbon and compound in the compound (such as: aliphatie diamine) formed.
In the present invention, the compound that the one or more hydrogen in described amino molecule are replaced by aliphatic alkyl and generate can be such as the compound shown in formula II:
In formula II, R
5, R
6and R
7can be H or C separately
1-C
16straight or branched alkyl, and R
5, R
6and R
7be asynchronously H; Preferably, R
5, R
6and R
7be H or C separately
1-C
6straight or branched alkyl, and R
5, R
6and R
7be asynchronously H.In the present invention, described C
1-C
16straight 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 n-hexadecyl.
Particularly, the example of the compound that the one or more hydrogen in described amino molecule are replaced by aliphatic alkyl and generate can be 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, tertiary 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.
In the present invention, the compound that at least two hydrogen atoms in described aliphatic hydrocarbon are replaced by amido and formed such as can one or more in quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine and decamethylene diamine.
In the present invention, described alkyl alcoholamine refers in molecular structure the alkyl hydrocarbon simultaneously with at least one amido and at least one hydroxyl.Such as, described alkyl alcoholamine can be the compound shown in formula III:
In formula III, R
8, R
9and R
10can be H, C separately
1-C
16straight or branched hydroxyalkyl or C
1-C
16straight or branched alkyl, and R
8, R
9and R
10be asynchronously H or C
1-C
16straight or branched alkyl; Preferably, R
8, R
9and R
10be H, C separately
1-C
5straight or branched hydroxyalkyl or C
1-C
5straight or branched alkyl, and R
8, R
9and R
10be asynchronously H or C
1-C
5straight or branched alkyl.In the present invention, C
1-C
16straight or branched hydroxyalkyl example can for but be not limited to: methylol, hydroxyethyl, hydroxypropyl, hydroxyl butyl and hydroxyl amyl group.
In the present invention, the example of described alkyl alcoholamine can be 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 that raw material is ready availability, 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 trolamine.
In another embodiment of the invention, described modification liquid is by the presence of an organic base, and mixed with water in silicon source and obtain, wherein, the mol ratio of silicon, organic bases and water in 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 described silicon source is preferably 1: 0.3-3: 20-50, and more preferably 1: 0.5-2: 20-40.The kind of described organic bases is described in detail above, 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 can be mixed with water.Preferably, the condition of described mixing comprises: temperature can be 25-90 DEG C, and the time can be 2-10 hour.
In the present invention, described silicon source refers to the silicon-containing compound that can provide element silicon, and such as, described silicon source can one or more for being selected from the silicon ester shown in silicon sol, silica gel and formula IV,
In formula IV, R
11, R
12, R
13and R
14be C separately
1-C
4straight or branched alkyl.
In the present invention, the example of the silicon ester shown in formula IV can be but be not limited to: methyl silicate, tetraethoxy, positive n-propyl silicate, positive isopropyl silicate and the positive positive butyl ester of silicic acid.
In the present invention, described silicon sol refers to water the colloidal solution of the silicon oxide being disperse phase, and wherein, the content of silicon oxide can be 10-40 % by weight.
In the present invention, described silica gel can be exist in solid form containing a small amount of moisture silicon oxide particle (wherein, water-content is generally 0.1-10 % by weight), also can be the silicon oxide powder existed with substantially moisture free solid (wherein, water-content is generally less than 0.1 % by weight) form.Described silica gel, such as can for 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 size of this area.Preferably, the median size of described silica gel is 20nm-2mm, is preferably 100-1000 micron.In the present invention, described median size adopts scanning electronic microscope (SEM) to measure.That is, when adopting scanning electronic microscope to measure, the graduated scale in the length of particle and scanning electronic microscope is compared, using the particle diameter of the maximum length of particle as particle.
Preferably, described silicon source is the silicon ester shown in formula IV.
In another embodiment of the present invention, described modification liquid is by the presence of an organic base, silicon source and titanium source are mixed with water and obtained, and the mol ratio of titanium, organic bases and water in the silicon in described silicon source, described titanium source is 1: 0.01-0.1: 0.05-5: 15-100.Preferably, the mol ratio of the silicon in described silicon source, titanium, organic bases and the water in described titanium source is 1: 0.01-0.05: 0.3-3: 20-50.Further preferably, the mol ratio of the silicon in described silicon source, titanium, organic bases and the water in described titanium source is 1: 0.01-0.03: 0.5-2: 20-40.The kind in described organic bases and silicon source is described in detail above, does not repeat them here.
According to the present invention, in the presence of an organic base, silicon source and titanium source are mixed with water and in the presence of an organic base, first described silicon source can be mixed with water, and then add titanium source and mix; Can also be in the presence of an organic base, silicon source and titanium source are mixed with water simultaneously.
In the present invention, described titanium source refers to the titanium-containing compound that can provide titanium elements, and such as, described titanium source can for being selected from TiCl
4, Ti (SO
4)
2, TiOCl
2with one or more in the titanic acid ester shown in formula V,
In formula V, R
15, R
16, R
17and R
18can be C separately
1-C
6straight or branched alkyl, be preferably C
2-C
4straight or branched alkyl, be more preferably ethyl, propyl group (comprising n-propyl and sec.-propyl) or butyl (comprising normal-butyl, sec-butyl, isobutyl-and the tertiary butyl).
In the present invention, the example of the titanic acid ester shown in formula V can be 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 formula V.
According to method of the present 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 DEG C, and the time can be 2-10 hour.
According to the present invention, from the optionally angle improving the transformation efficiency of hexanaphthene, the effective rate of utilization of hydrogen peroxide and pimelinketone further, described modification liquid is preferably the aqueous solution of organic bases; Or by the presence of an organic base, silicon source, titanium source are mixed with water and obtain, and the mol ratio of the silicon in described silicon source, titanium, organic bases and the water in described titanium source is 1: 0.01-0.1: 0.05-5: 15-100.More preferably, described modification liquid is by the presence of an organic base, silicon source, titanium source are mixed with water and obtained, and the mol ratio of the silicon in described silicon source, titanium, organic bases and the water in described titanium source is 1: 0.01-0.1: 0.05-5: 15-100; Further preferably, described modification liquid is by the presence of an organic base, titanic acid ester shown in silicon source, formula V mixed with water and obtains, and the mol ratio of the silicon in described silicon source, titanium, organic bases and the water in described titanium source is 1: 0.01-0.1: 0.05-5: 15-100.
According to method of the present invention, described catalyzer is by confined conditions, HTS is contacted at 80-200 DEG C with modification liquid, and product of contact is successively carried out dry and roasting and obtain.
According to method of the present invention, the Contact Temperature of described HTS and described modification liquid can be 80-200 DEG C, is preferably 135-180 DEG C.The duration of contact of described HTS and described modification liquid can carry out appropriate selection, is generally at least 2 hours, such as, can be 6-72 hour.
The present invention is not particularly limited for the method for described drying and roasting and condition, can be the ordinary method of this area.Usually, the condition of described drying comprises: temperature can be 25-200 DEG C, is preferably 70-160 DEG C; Time can be 2-12 hour, is preferably 2-6 hour.The condition of described roasting comprises: temperature can be 300-800 DEG C, is preferably 500-700 DEG C; Time can be 2-12 hour, is preferably 2-6 hour.
In addition, can also with reference to the preparation of method disclosed in the Chinese patent application 201010213601.2 of the applicant and Chinese patent application 201010213605.0 about the catalyzer used in method of the present invention.
According to method of the present invention, described oxygenant is hydrogen peroxide.According to method of the present invention, the hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.From the angle improved further according to the security of method of the present invention, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.According to method of the present invention, when described hydrogen peroxide provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.The hydrogen peroxide used in the embodiment of the present invention and comparative example for concentration be the hydrogen peroxide of 30 % by weight.
According to method of the present invention, the contact of hexanaphthene and hydrogen peroxide is preferably carried out in the presence of solvent, can regulate more easily so on the one hand, thus make method according to the present invention have higher security to the severe degree of reaction; The contact of each reactant can also be made more abundant on the other hand.The present invention is not particularly limited for the kind of described solvent, all kinds of SOLVENTS can commonly used for this area.Preferably, described solvent is C
1-C
10alcohol, C
3-C
10ketone and C
2-C
10nitrile in one or more, such as: described solvent can be one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.More preferably, described solvent is C
1-C
5fatty alcohol and C
3-C
5aliphatic ketone in one or more, such as: described solvent can be one or more in acetone, methyl alcohol and the trimethyl carbinol.
According to method of the present 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.
According to method of the present invention, the contact of hexanaphthene and hydrogen peroxide can be carried out under oxygen-containing atmosphere (such as: air atmosphere or oxygen atmosphere), also can carry out under anoxic condition.In embodiments of the invention and comparative example, the contact of hexanaphthene and hydrogen peroxide is carried out all in air atmosphere.
Method according to the present invention is not particularly limited for described oxidation reaction condition.Usually, described oxidation reaction condition comprises: temperature can be 0-150 DEG C, is preferably 30-120 DEG C, is more preferably 30-70 DEG C; Pressure can be 0.1-3MPa, is preferably 0.1-2.5MPa, is 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, is more preferably 1: 1-8; The mass ratio of hexanaphthene and described catalyzer can be 2-100: 1, is preferably 2-50: 1, is more preferably 10-50: 1.
According to method of the present invention, can adopt periodical operation, also can adopt operate continuously etc., the present invention is not particularly limited this.According to method of the present 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 after solvent and catalyzer be added reactor, add hexanaphthene and oxygenant continuously, to react; When carrying out rhythmic reaction in the tank reactor closed, catalyzer, hexanaphthene and hydrogen peroxide and optional solvent can be added in reactor, to react simultaneously.When carrying out in a continuous manner, the reactor that fixed-bed reactor or slurry bed reactor etc. are conventional can be adopted.Wherein, when implementing method of the present invention in fixed-bed reactor, feed way can for load catalyzer after in fixed-bed reactor, hexanaphthene and hydrogen peroxide and optional solvent added continuously; When implementing method of the present invention in slurry bed reactor, after catalysts and solvents can being pulled an oar in the reactor, add hexanaphthene and hydrogen peroxide continuously, to react.
The ordinary method of this area can be adopted to be separated from the product of contact of hexanaphthene and hydrogen peroxide by pimelinketone according to method of the present invention, such as: by product of contact being distilled, thus can be separated from reaction product by pimelinketone.The method of described distillation and condition are known in the field, repeat no more herein.
The invention will be further described for following embodiment, but therefore do not limit content of the present invention.
In following examples and comparative example, if not otherwise specified, used reagent is commercially available analytical reagent.
In following examples, titanium-silicon molecular sieve TS-1 used is according to Zeolites, and the 1992,12nd volume, prepared by the method described in 943-950 page.
In following examples, HTS Ti-MCM-41 used is that prepared by the method described in 1994,147-148, with oxide basis, the titanium content in this HTS is 3 % by weight according to Corma etc. at Chem.Commun..
In following examples, HTS Ti-Beta used is that according to Takashi Tatsumi etc. at J.Chem.Soc.Chem.Commun. prepared by the method described in 1997,677-678, with oxide basis, the titanium content in this HTS is 2.6 % by weight.
In the present invention, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate cyclohexane conversion, effective utilization ratio of hydrogen peroxide and pimelinketone selectivity on this basis respectively:
Embodiment 1
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
By 10 grams of TS-1 HTS (with oxide basis, titanium content in this HTS is 2.5 % by weight), 4.8 grams of concentration is that the aqueous solution of the tetraethyl ammonium hydroxide of 28 quality % is placed in the autoclave that liner is tetrafluoroethylene, and 2mL deionized water is added again in above-mentioned autoclave, then autoclave is closed, temperature in reactor is elevated to 145 DEG C, and reacts 12 hours at such a temperature.By reaction product 100 DEG C of dryings 180 minutes, then by desciccate roasting 3 hours under 650 DEG C of air atmospheres, thus obtain catalyst A.
Hexanaphthene, hydrogen peroxide, acetone and catalyst A are placed in autoclave, react 12 hours under temperature is 30 DEG C and pressure is the condition of 1.5MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 36%, and effective utilization ratio of hydrogen peroxide is 61%, and 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 pimelinketone selectivity is 57%.
Comparative example 1
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 1 is adopted to prepare pimelinketone, unlike, do not use catalyzer.Adopt gas-chromatography to carry out the composition of the assaying reaction reaction solution of 2 hours, test result is: cyclohexane conversion is 0.3%, and pimelinketone selectivity is 0%.
Comparative example 2
The method identical with embodiment 1 is adopted to prepare pimelinketone, unlike, use TS-1 HTS as catalyzer.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 27%, and effective utilization ratio of hydrogen peroxide is 32%, and 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 pimelinketone selectivity is 42%.
Comparative example 3
The method identical with embodiment 1 is adopted to prepare pimelinketone, unlike, when Kaolinite Preparation of Catalyst, in above-mentioned autoclave, add 20mL deionized water again, thus obtain catalyzer.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 31%, and effective utilization ratio of hydrogen peroxide is 45%, and 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 pimelinketone selectivity is 41%.
Embodiment 2
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
By 12 grams of TS-1 HTS (with oxide basis, titanium content in this HTS is 1.2 % by weight), 1 gram of trolamine and 5 grams of concentration is that the aqueous solution of the four n-propyl ammonium hydroxide of 16.3 quality % is placed in the autoclave that liner is tetrafluoroethylene, and 3mL deionized water is added again in above-mentioned autoclave, then autoclave is closed, temperature in reactor is elevated to 160 DEG C, and reacts 56 hours at such a temperature.By reaction product 150 DEG C of dryings 120 minutes, then by desciccate roasting 6 hours under 540 DEG C of air atmospheres, thus obtain catalyst B.
Hexanaphthene, hydrogen peroxide, the trimethyl carbinol and catalyst B are placed in autoclave, react 12 hours under temperature is 70 DEG C and pressure is the condition of 2.5MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 33%, and effective utilization ratio of hydrogen peroxide is 55%, and 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 pimelinketone selectivity is 60%.
Embodiment 3
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
By 12 grams of TS-1 HTS (with oxide basis, titanium content in this HTS is 3.2 % by weight), 0.5 gram of Tri N-Propyl Amine and 7.5 grams of concentration is that the aqueous solution of the four n-propyl ammonium hydroxide of 16.3 quality % is placed in the autoclave that liner is tetrafluoroethylene, then autoclave is closed, temperature in reactor is elevated to 175 DEG C, and reacts 48 hours at such a temperature.By reaction product 90 DEG C of dryings 240 minutes, then by desciccate roasting 2 hours under 700 DEG C of air atmospheres, thus obtain catalyzer C.
Hexanaphthene, hydrogen peroxide, methyl alcohol and catalyzer C are placed in autoclave, react 12 hours under temperature is 50 DEG C and pressure is the condition of 0.5MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 48%, and effective utilization ratio of hydrogen peroxide is 71%, and 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 pimelinketone selectivity is 66%.
Embodiment 4
The present embodiment is used for illustrating according to the method preparing pimelinketone 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 in autoclave, react 12 hours under temperature is 40 DEG C and pressure is the condition of 1.5MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 65%, and effective utilization ratio of hydrogen peroxide is 57%, and 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 pimelinketone selectivity is 81%.
Embodiment 5
The present embodiment is used for illustrating according to the method preparing pimelinketone 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 in autoclave, react 12 hours under temperature is 60 DEG C and pressure is the condition of 0.5MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 46%, and effective utilization ratio of hydrogen peroxide is 55%, and 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 pimelinketone selectivity is 54%.
Embodiment 6
The present embodiment is used for illustrating according to the method preparing pimelinketone 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 in autoclave, react 12 hours under temperature is 30 DEG C and pressure is the condition of 1.5MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 53%, and effective utilization ratio of hydrogen peroxide is 58%, and 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 pimelinketone selectivity is 57%.
Embodiment 7
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
By tetraethyl orthosilicate, tetraethyl ammonium hydroxide and deionized water (wherein, in the mol ratio of the silicon source of silicon, tetraethyl ammonium hydroxide and water for 1: 0.85: 20) be placed in the autoclave that liner is tetrafluoroethylene, stir 1 hour at 25 DEG C, then the temperature in autoclave is increased to 75 DEG C, and stir 3 hours more at such a temperature, thus obtain modification liquid A.
By 10 grams of modification liquid A and 12 gram TS-1 HTS (with oxide basis, titanium content in this HTS is 4.5 % by weight) be placed in another autoclave, then autoclave is closed, the temperature of autoclave is elevated to 175 DEG C, and reacts 12 hours at such a temperature.By reaction product directly 150 DEG C of dryings 120 minutes, and then roasting 5 hours under 580 DEG C of air atmospheres, thus obtain catalyzer D.
Hexanaphthene, hydrogen peroxide, acetone and catalyzer D are placed in autoclave, react 12 hours under temperature is 40 DEG C and pressure is the condition of 1MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 44%, and effective utilization ratio of hydrogen peroxide is 56%, and 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 pimelinketone selectivity is 52%.
Embodiment 8
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
By tetraethyl orthosilicate, tetraethyl titanate, tetraethyl ammonium hydroxide and deionized water (wherein, in the tetraethyl orthosilicate of silicon, in the mol ratio of the tetraethyl titanate of titanium, tetraethyl ammonium hydroxide and water for 1: 0.02: 0.75: 35) be placed in the autoclave that liner is tetrafluoroethylene, stir 1 hour at 25 DEG C, then the temperature in autoclave is increased to 80 DEG C, and stir 3 hours more at such a temperature, thus obtain modification liquid B.
By 13 grams of above-mentioned modification liquid B and 15 gram TS-1 HTS (with oxide basis, titanium content in this HTS is 2.8 % by weight) be placed in another autoclave, then autoclave is closed, the temperature of autoclave is elevated to 160 DEG C, and reacts 62 hours at such a temperature.By reaction product directly 135 DEG C of dryings 240 minutes, and then roasting 3 hours under 560 DEG C of air atmospheres, thus obtain catalyzer E.
Hexanaphthene, hydrogen peroxide, acetone and catalyzer E are placed in autoclave, react 12 hours under temperature is 40 DEG C and pressure is the condition of 1MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 73%, and effective utilization ratio of hydrogen peroxide is 65%, and 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 pimelinketone selectivity is 75%.
Embodiment 9
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
Silica gel (is purchased from Qingdao silica gel factory, spheroidal particle, 180-830 micron), di-n-propylamine, four n-propyl ammonium hydroxide and deionized water are (wherein, in the silica gel of silicon, di-n-propylamine, the mol ratio of four n-propyl ammonium hydroxide and water is 1: 0.35: 1.2: 30) be placed in the autoclave that liner is tetrafluoroethylene, stir 1.5 hours at 25 DEG C, then in autoclave, tetraethyl titanate is added (wherein, in the silica gel of silicon with in the mol ratio of the tetraethyl titanate of titanium for 1: 0.025), the temperature of autoclave is increased to 65 DEG C, and stir 5 hours at such a temperature, thus obtain modification liquid C.
By 5 grams of above-mentioned modification liquid C and 10 gram TS-1 HTS (with oxide basis, titanium content in this HTS is 3.1 % by weight) be placed in another autoclave, then autoclave is closed, the temperature of autoclave is elevated to 150 DEG C, and reacts 65 hours at such a temperature.By reaction product directly 135 DEG C of dryings 240 minutes, and then roasting 3 hours under 560 DEG C of air atmospheres, thus obtain catalyzer F.
Hexanaphthene, hydrogen peroxide, acetone and catalyzer F are placed in autoclave, react 12 hours under temperature is 40 DEG C and pressure is the condition of 1MPa.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.Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 68%, and effective utilization ratio of hydrogen peroxide is 65%, and 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 pimelinketone selectivity is 68%.
Embodiment 10
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 8 is adopted to prepare pimelinketone, unlike, during Kaolinite Preparation of Catalyst, use Ti-MCM-41 HTS to replace TS-1 HTS.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 60%, and effective utilization ratio of hydrogen peroxide is 53%, and 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 pimelinketone selectivity is 68%.
Embodiment 11
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 8 is adopted to prepare pimelinketone, unlike, during Kaolinite Preparation of Catalyst, use Ti-Beta HTS to replace TS-1 HTS.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 62%, and effective utilization ratio of hydrogen peroxide is 61%, and 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 pimelinketone selectivity is 55%.
Embodiment 12
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 3 is adopted to prepare pimelinketone, unlike, catalyzer is adopted and is prepared with the following method:
Silica gel (is purchased from Qingdao silica gel factory, spheroidal particle, 180-830 micron), Tri N-Propyl Amine, four n-propyl ammonium hydroxide and deionized water (wherein, in the mol ratio of the silica gel of silicon, Tri N-Propyl Amine, four n-propyl ammonium hydroxide and water for 1: 0.3: 1.5: 20) be placed in the autoclave that liner is tetrafluoroethylene, stir 1 hour at 25 DEG C, the temperature of autoclave is increased to 65 DEG C, and stirs 5 hours more at such a temperature, thus obtain modification liquid D.
By 5 grams of above-mentioned modification liquid D and 12 gram TS-1 HTS (with oxide basis, titanium content in this HTS is 0.8 % by weight) be placed in another autoclave, then autoclave is closed, the temperature of autoclave is elevated to 150 DEG C, and reacts 65 hours at such a temperature.By reaction product directly 95 DEG C of dryings 240 minutes, and then roasting 2 hours under 700 DEG C of air atmospheres, thus obtain catalyzer G.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 43%, and effective utilization ratio of hydrogen peroxide is 62%, and 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 pimelinketone selectivity is 61%.
Embodiment 13
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 3 is adopted to prepare pimelinketone, unlike, catalyzer is adopted and is prepared with the following method:
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, in the mol ratio of the silicon sol of silicon, di-n-propylamine, four n-propyl ammonium hydroxide and water for 1: 0.3: 1.5: 20) be placed in the autoclave that liner is tetrafluoroethylene, stir 1 hour at 25 DEG C; Tetra-n-butyl titanate is added (wherein in autoclave, in the silicon sol of silicon with in the mol ratio of the tetra-n-butyl titanate of titanium for 1: 0.02) temperature of autoclave is increased to 65 DEG C, and stir 5 hours more at such a temperature, thus obtain modification liquid E.
By 5 grams of above-mentioned modification liquid E and 12 gram TS-1 HTS (with oxide basis, titanium content in this HTS is 3.5 % by weight) be placed in another autoclave, then autoclave is closed, the temperature of autoclave is elevated to 150 DEG C, and reacts 65 hours at such a temperature.By reaction product directly 95 DEG C of dryings 240 minutes, and then roasting 2 hours under 700 DEG C of air atmospheres, thus obtain catalyzer G.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 68%, and effective utilization ratio of hydrogen peroxide is 84%, and 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 pimelinketone selectivity is 66%.
Embodiment 14
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 7 is adopted to prepare pimelinketone, unlike, when preparing modification liquid, replace silica gel with positive silicic acid four n-propyl.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 41%, and effective utilization ratio of hydrogen peroxide is 56%, and 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 pimelinketone selectivity is 58%.
Embodiment 15
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 7 is adopted to prepare pimelinketone, unlike, when preparing modification liquid, replace silica gel with white carbon black (be purchased from Qingdao silica gel factory, prepared by vapour deposition process, median size is 100nm).
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 36%, and effective utilization ratio of hydrogen peroxide is 52%, and 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 pimelinketone selectivity is 47%.
Embodiment 16
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 8 is adopted to prepare pimelinketone, unlike, when preparing modification liquid, use titanium tetrachloride to replace tetraethyl titanate.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 68%, and effective utilization ratio of hydrogen peroxide is 62%, and 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 pimelinketone selectivity is 63%.
Embodiment 17
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 8 is adopted to prepare pimelinketone, unlike, when preparing modification liquid, use Ti (SO
4)
2replace tetraethyl titanate.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 62%, and effective utilization ratio of hydrogen peroxide is 64%, and 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 pimelinketone selectivity is 56%.
Embodiment 18
The present embodiment is used for illustrating according to the method preparing pimelinketone of the present invention.
The method identical with embodiment 8 is adopted to prepare pimelinketone, unlike, when preparing modification liquid, use TiOCl
2replace tetraethyl titanate.
Gas-chromatography is adopted to come the composition of the assaying reaction reaction solution of 2 hours and the composition of the reaction reaction solution of 12 hours.Wherein, the test result of reacting 2 hours is: cyclohexane conversion is 65%, and effective utilization ratio of hydrogen peroxide is 63%, and 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 pimelinketone selectivity is 59%.
Claims (15)
1. prepare the method for pimelinketone for one kind, under the method is included in oxidation reaction condition, in the presence of a catalyst, hexanaphthene is contacted with hydrogen peroxide, it is characterized in that, described catalyzer is by confined conditions, HTS is contacted at 80-200 DEG C with modification liquid, and product of contact is successively carried out dry and roasting and obtain, described modification liquid is by the presence of an organic base, by silicon source, titanium source mixes with water and obtains, silicon in described silicon source, titanium in described titanium source, the mol ratio of organic bases and water is 1:0.01-0.1:0.05-5:15-100, the mass ratio of described HTS and described modification liquid is 100:10-150, in gram described HTS with in mole the ratio of organic bases for 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 gram described HTS with in mole the ratio of organic bases for 100:0.01-0.15.
4. method according to claim 1, wherein, the mol ratio of titanium, organic bases and water in the silicon in described silicon source, described titanium source is 1:0.01-0.05:0.3-3:20-50.
5. the method according to claim 1 or 4, wherein, described titanium source is for being selected from TiCl
4, Ti (SO
4)
2, TiOCl
2with one or more in the titanic acid ester shown in formula V,
In formula V, R
15, R
16, R
17and R
18be C separately
1-C
6alkyl.
6. method according to claim 1, wherein, the condition of described mixing comprises: temperature is 25-90 DEG C, and the time is 2-10 hour.
7. the method according to claim 1 or 4, wherein, one or more for being selected from the silicon ester shown in silicon sol, silica gel and formula IV of described silicon source,
In formula IV, R
11, R
12, R
13and R
14be C separately
1-C
4alkyl.
8. according to the method in claim 1 and 3-4 described in any one, wherein, described organic bases be selected from quaternary ammonium hydroxide, fatty amine and alkyl alcoholamine one or more.
9. method according to claim 8, 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 trolamine.
10. method according to claim 1, wherein, described HTS and described modification liquid carry out the contact of 6-72 hour at 135-180 DEG C.
11. according to the method in claim 1-3 and 10 described in any one, wherein, described HTS is at least one in the HTS of the HTS of MFI structure, the HTS of MEL structure, the HTS of BEA structure, the HTS of MWW structure, the HTS of MOR structure, the HTS of TUN structure and two-dimentional hexagonal structure.
12. methods according to claim 1, wherein, the condition of described roasting comprises: temperature is 300-800 DEG C, and the time is 2-12 hour.
13. methods according to claim 1, wherein, the contact of hexanaphthene and oxygenant is carried out in the presence of solvent, and the mol ratio of hexanaphthene and described solvent is 1:1-100.
14. methods according to claim 13, wherein, described solvent is C
1-C
10alcohol, C
3-C
10ketone and C
2-C
10nitrile in one or more.
15. methods according to claim 1, wherein, described oxidation reaction condition comprises: temperature is 0-150 DEG C, and pressure is 0.1-3MPa, and the mol ratio of hexanaphthene and described oxygenant is 1:0.1-10, and the mass ratio of hexanaphthene and described catalyzer is 2-100:1.
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| 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 |
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| CN1328878A (en) * | 2000-06-15 | 2002-01-02 | 中国石油化工集团公司 | Method for synthesizing titanium silicone molecular sieve |
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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 |
| CN1328878A (en) * | 2000-06-15 | 2002-01-02 | 中国石油化工集团公司 | Method for synthesizing titanium silicone molecular sieve |
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