CN109721066B

CN109721066B - Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method

Info

Publication number: CN109721066B
Application number: CN201711050925.7A
Authority: CN
Inventors: 史春风; 林民; 朱斌
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-10-31
Filing date: 2017-10-31
Publication date: 2021-02-09
Anticipated expiration: 2037-10-31
Also published as: CN109721066A

Abstract

The invention discloses a titanium-silicon molecular sieve and a production method thereof, and the method comprises the following steps: carrying out hydrolytic condensation reaction on a raw material mixture containing a template agent, a titanium source, an organic silicon source and water, leading out generated steam and condensing in the reaction process, wherein the ratio of the mass of a condensate to the total mass of the raw material mixture is 0.1-0.4: 1, sealing the reaction kettle, adjusting the conditions in the reaction kettle to hydrothermal crystallization conditions, and performing hydrothermal crystallization to obtain a hydrothermal crystallization mixture; optionally, the hydrothermal crystallization mixture is mixed with a complementary titanium silicalite molecular sieve and then spray-molded. The invention also discloses an ammoximation reaction method using the titanium silicalite molecular sieve as a catalyst. According to the method disclosed by the invention, the processes of solid-liquid separation and washing are omitted, and the amount of wastewater is greatly reduced; and the mixture obtained by hydrothermal crystallization can be directly used for spray forming without adopting extra adhesives, and the obtained titanium silicalite molecular sieve particles have better catalytic activity.

Description

Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method

Technical Field

The invention relates to the technical field of molecular sieve preparation, in particular to a production method of a titanium silicalite molecular sieve, the titanium silicalite molecular sieve produced by the method, and an ammoximation reaction method using the titanium silicalite molecular sieve as a catalyst.

Background

The titanium silicalite TS-1 is a novel titanium silicalite with excellent catalytic selective oxidation performance formed by introducing a transition metal element titanium into a molecular sieve framework with a ZSM-5 structure. TS-1 not only has the catalytic oxidation effect of titanium, but also has the shape-selective effect and excellent stability of ZSM-5 molecular sieve. As the TS-1 molecular sieve can adopt the pollution-free low-concentration hydrogen peroxide as the oxidant in the oxidation reaction of the organic matters, the problems of complex process and environmental pollution in the oxidation process are avoided, and the molecular sieve has the advantages of incomparable energy conservation, economy, environmental friendliness and the like of the traditional oxidation system and has good reaction selectivity, thereby having great industrial application prospect.

The synthesis of TS-1 was first disclosed in 1981 (USP 4410501). The method comprises the steps of firstly synthesizing a reaction mixture containing a silicon source, a titanium source and organic alkali and/or alkaline oxide serving as a template agent, carrying out hydrothermal crystallization on the reaction mixture in a high-pressure kettle at the temperature of 130-200 ℃ for 6-30 days, and then separating, washing, drying and roasting to obtain the product.

Despite intensive research efforts by researchers on the preparation of titanium silicalite molecular sieves, there are still some problems with the preparation of titanium silicalite molecular sieves, and improvements and optimizations to the existing methods of titanium silicalite molecular sieve production are needed.

Disclosure of Invention

The inventor of the invention finds that the existing titanium silicalite molecular sieve production process mainly has the following problems in the practical process:

(1) the titanium silicalite molecular sieve product obtained by the existing method through separation, washing, drying and roasting can generate a large amount of ammonia nitrogen wastewater in the separation and washing processes, the COD value of the ammonia nitrogen wastewater is extremely high, the requirement of emission and/or recycling can be met only after purification treatment is carried out, and the production burden of titanium silicalite molecular sieve manufacturers is increased by the purification treatment of the large amount of ammonia nitrogen wastewater;

(2) when the titanium silicalite molecular sieve prepared by the existing method is molded, not only an adhesive or a precursor thereof needs to be additionally introduced, but also the titanium silicalite molecular sieve and the adhesive or the precursor thereof need to be mixed, so that the raw material cost is increased, and the operation procedures are increased.

In view of the above problems, the inventors of the present invention have conducted intensive studies and found that: leading out steam generated in the hydrolysis condensation reaction process, condensing, finishing the hydrolysis condensation reaction and performing hydrothermal crystallization when the amount of formed condensate is controlled within a certain range, wherein the mixture obtained by the hydrothermal crystallization can be directly used for spray forming, the catalytic performance and the application performance of the titanium silicalite molecular sieve particles obtained by the spray forming are uniform and stable, the solid-liquid separation and washing process is omitted, and the generation of ammonia nitrogen wastewater is avoided. The present invention has been completed based on this finding.

According to a first aspect of the present invention, there is provided a process for producing a titanium silicalite molecular sieve, the process comprising:

(1) under the condition of hydrolysis condensation reaction, carrying out hydrolysis condensation reaction on a raw material mixture containing a template agent, a titanium source, an organic silicon source and water to obtain a hydrolysis condensation mixture, and carrying out hydrothermal crystallization on the obtained hydrolysis condensation mixture to obtain a hydrothermal crystallization mixture;

(2) optionally, mixing the hydrothermal crystallization mixture with a complementary titanium silicalite molecular sieve to obtain slurry;

(2) carrying out spray forming on the hydrothermal crystallization mixture or the slurry;

wherein, in the hydrolytic condensation reaction process, the generated steam is led out and condensed to obtain condensate, and the ratio of the mass of the condensate to the total mass of the raw material mixture is 0.1-0.4: 1, sealing the reaction kettle, adjusting the conditions in the reaction kettle to hydrothermal crystallization conditions, and carrying out hydrothermal crystallization.

According to a second aspect of the invention, there is provided a titanium silicalite molecular sieve produced by the process of the first aspect of the invention.

According to a third aspect of the present invention, there is provided a cyclohexanone ammoximation reaction method, which comprises contacting cyclohexanone, ammonia and hydrogen peroxide with a titanium silicalite molecular sieve under ammoximation reaction conditions, wherein the titanium silicalite molecular sieve is the titanium silicalite molecular sieve of the second aspect of the present invention.

The titanium silicalite molecular sieve produced by the method can omit the processes of solid-liquid separation and washing of the mixture obtained by hydrothermal crystallization on one hand, and greatly reduce the amount of wastewater generated in the production process; on the other hand, the mixture obtained by hydrothermal crystallization can be directly used for spray forming without adopting an additional adhesive or a precursor thereof, and the obtained titanium silicalite molecular sieve particles show good catalytic activity and selectivity when used as a catalyst, and particularly can obtain higher catalytic activity and selectivity when used as a catalyst for an ammoximation reaction.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

(3) and carrying out spray forming on the hydrothermal crystallization mixture or the slurry.

The organic silicon source may be any of various materials capable of forming silica under hydrolytic condensation conditions, and may be, for example, one or more selected from silicon-containing compounds represented by formula I,

in the formula I, R₁、R₂、R₃And R₄Each is C₁-C₄Alkyl group of (1). Said C is₁-C₄Alkyl of (2) includes C₁-C₄Straight chain alkyl of (2) and C₃-C₄Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

Preferably, the silicon source is one or more than two selected from methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, isopropyl orthosilicate and n-butyl orthosilicate.

The titanium source can be a titanium source commonly used in the technical field of molecular sieve preparation. In particular, the titanium source may be an organic titanium source (e.g. an organic titanate) and/or an inorganic titanium source (e.g. an inorganic titanium salt). The inorganic titanium source may be TiCl₄、Ti(SO₄)₂、TiOCl₂One or more of titanium hydroxide, titanium oxide, titanium nitrate and titanium phosphate. The organic titanium source can be one or more than two of fatty titanium alkoxide and organic titanate. The titanium source is preferably an organic titanium source, more preferably an organic titanate, and still more preferably of the formula M₄TiO₄The organic titanate shown, wherein 4M can be same or different, and each is preferably C₁-C₄Alkyl group of (1). The titanium source is particularly preferably one or two or more of tetraisopropyl titanate, tetra-n-propyl titanate, tetrabutyl titanate, and tetraethyl titanate.

The template agent can be a template agent commonly used in the technical field of molecular sieve preparation, and specifically can be one or more than two of urea, amine, alcohol amine and quaternary ammonium hydroxide.

The quaternary ammonium base may be various organic quaternary ammonium bases, the amine may be an organic compound having at least one amino group in a molecular structure, and the alcohol amine may be an organic compound having at least one amino group and at least one hydroxyl group in a molecular structure.

Specifically, the quaternary ammonium base can be a quaternary ammonium base shown in a formula II,

in the formula II, R₅、R₆、R₇And R₈Are the same or different and are each C₁-C₄Alkyl of (2) including C₁-C₄Straight chain alkyl of (2) and C₃-C₄Branched alkyl groups of (a), for example: r₅、R₆、R₇And R₈Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

The amine may be an aliphatic amine of formula III,

R⁹(NH₂)_n(formula III)

In the formula III, n is an integer of 1 or 2. When n is 1, R⁹Is C₁-C₆Alkyl of (2) including C₁-C₆Straight chain alkyl of (2) and C₃-C₆Such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl. When n is 2, R⁹Is C₁-C₆Alkylene of (2) including C₁-C₆Linear alkylene of (A) and (C)₃-C₆Such as methylene, ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene.

The alcohol amine may be an aliphatic alcohol amine represented by formula IV,

(HOR¹⁰)_mNH_(3-m)(formula IV)

In the formula IV, m are R¹⁰Are the same or different and are each C₁-C₄Alkylene of (2) including C₁-C₄Linear alkylene of (A) and (C)₃-C₄Branched alkylene groups of (a), such as methylene, ethylene, n-propylene and n-butylene; m is 1, 2 or 3. Preferably, the alcohol amine is one or more than two of monoethanolamine, diethanolamine and triethanolamine.

Specific examples of the templating agent may include, but are not limited to, one or more of urea, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, ethylamine, n-butylamine, butanediamine, hexamethylenediamine, monoethanolamine, diethanolamine, and triethanolamine.

Preferably, the templating agent is a quaternary ammonium base, more preferably tetraethylammonium hydroxide and/or tetrapropylammonium hydroxide.

According to the method of the present invention, in step (1), the amounts of the organic silicon source, the titanium source, the template and water can be selected conventionally. Generally, the molar ratio of the organic silicon source, the titanium source, the templating agent, and the water may be 100: (0.005-10): (0.005-40): (200-10000), preferably 100: (0.05-8): (0.5-30): (500- & ltSUB & gt 5000- & gt), more preferably 100: (0.2-6): (5-25): (800-4000), more preferably 100: (1-5): (10-20): (1500-3000), the organic silicon source is SiO₂The titanium source is calculated as TiO₂In terms of NH, the template agent₃And (6) counting.

In step (1), the aqueous solution containing the templating agent may be mixed with a mixture containing a titanium source and an organic silicon source to obtain the raw material mixture. The mixture containing the titanium source and the organic silicon source can be obtained by mixing the titanium source and the organic silicon source. Preferably, the mixture containing the titanium source and the organic silicon source can be obtained by a method comprising the following steps: the titanium source and the organic silicon source are mixed with stirring at 0 to 60 ℃, preferably 15 to 40 ℃, more preferably 20 to 30 ℃ for 1 to 2 hours.

The aqueous solution containing the templating agent may be obtained by dispersing the templating agent in water, the mixing may be performed at a temperature of 20-60 deg.C, preferably 15-40 deg.C, more preferably 20-30 deg.C, the mixing may be continued for 1-2 hours, and the templating agent may be provided in pure form or in the form of a concentrated solution.

The aqueous solution containing the templating agent and the mixture containing the titanium source and the organic silicon source may be mixed at a temperature of 15 to 60c, preferably 20 to 40 c, more preferably 20 to 30 c, for 1 to 2 hours to obtain the raw material mixture.

In the step (1), in the hydrolysis condensation reaction process, the titanium source and the organic silicon source undergo hydrolysis condensation reaction, and simultaneously release a small molecular compound, usually alcohol. These small molecule compounds volatilize to form vapor which escapes from the reaction system. According to the method of the invention, the escaping vapour is condensed and the condensate is collected.

In the step (1), the ratio of the mass of the condensate to the total mass of the raw material mixture is 0.1-0.4: 1, sealing the reaction kettle, adjusting the conditions in the reaction kettle to hydrothermal crystallization conditions, and carrying out hydrothermal crystallization. Preferably, the ratio of the mass of the condensate to the total mass of the raw mixture is from 0.14 to 0.3: 1, sealing the reaction kettle, adjusting the conditions in the reaction kettle to hydrothermal crystallization conditions, and carrying out hydrothermal crystallization. The quality of the condensate can be controlled by controlling the temperature and/or duration of the contact reaction. Preferably, the hydrolytic condensation reaction may be carried out at a temperature of 80 to 98 ℃. More preferably, the hydrolytic condensation reaction is carried out at a temperature of 85 to 95 deg.C (e.g., 89 to 95 deg.C). The duration of the hydrolytic condensation reaction may be 4 to 36 hours, preferably 6 to 28 hours, more preferably 10 to 24 hours, and further preferably 12 to 16 hours. The hydrolytic condensation reaction is usually carried out under normal pressure (i.e., 1 atm), and may be carried out under reduced pressure. Specifically, the hydrolytic condensation reaction may be carried out at a pressure of-0.2 MPa to 0MPa, which is a gauge pressure.

When the titanium silicalite molecular sieve is prepared by adopting the existing method, the template agent is easy to decompose in the hydrothermal crystallization process, the quality of the titanium silicalite molecular sieve is influenced, the template agent is a raw material with higher value in the production process of the titanium silicalite molecular sieve, the template agent is difficult to recycle due to ineffective decomposition, and the feeding amount of the template agent is required to be increased for ensuring the quality of the molecular sieve, so that the production cost of the titanium silicalite molecular sieve is obviously increased; in addition, the decomposed template agent forms an oil phase, which not only influences the crystallization of the molecular sieve, but also floats on the upper layer of the hydrothermal crystallization slurry after standing, and partial oil phase substances are attached to the inner surface of the reaction kettle, so that the reaction kettle is polluted, and the cleaning difficulty of the reaction kettle is increased. The inventor of the present invention found in the research process that if the hydrolysis condensation mixture is mixed with at least part of the condensate liquid and then is subjected to hydrothermal crystallization, the decomposition of the template agent in the hydrothermal crystallization process can be effectively inhibited.

Thus, according to the process of the present invention, in a preferred embodiment, it is preferred to further comprise mixing at least part of the condensate with said hydrolytic condensation mixture before sealing the reaction vessel.

According to this preferred embodiment, the condensate contains water and alcohol, the alcohol may be present in an amount of 80 to 96 wt.%, preferably 83 to 95 wt.%, more preferably 88 to 92 wt.%, and the water may be present in an amount of 4 to 20 wt.%, preferably 5 to 17 wt.%, more preferably 8 to 12 wt.%, based on the total amount of the condensate. In addition to water and alcohol, the condensate also contains nitrogen, which is typically derived from the templating agent. The concentration of nitrogen element in the condensate may be 0.01 to 50mmol/L, preferably 0.02 to 20mmol/L, more preferably 0.04 to 5mmol/L, and still more preferably 0.05 to 3 mmol/L. Particularly preferably, the concentration of nitrogen element in the condensate is 0.5-1.5mmol/L, so that the decomposition of the template agent in the hydrothermal crystallization process can be better inhibited.

According to this preferred embodiment, the entire condensate can be mixed with the hydrolytic condensation mixture, or part of the condensate can be mixed with the hydrolytic condensation mixture. Preferably, the condensate may be used in an amount of 1 to 50 parts by weight, preferably 1.5 to 40 parts by weight, relative to 100 parts by weight of the hydrolytic condensation mixture. More preferably, the condensate is used in an amount of 5 to 30 parts by weight with respect to 100 parts by weight of the hydrolytic condensation mixture. Further preferably, the condensate is used in an amount of 10 to 25 parts by weight relative to 100 parts by weight of the hydrolytic condensation mixture, so that the decomposition of the template agent during hydrothermal crystallization can be inhibited and the quality of the molecular sieve obtained by hydrothermal crystallization can be further improved.

According to this preferred embodiment, the hydrolytic condensation mixture can be mixed with the condensate at a temperature of 20 to 80 ℃, preferably 40 to 60 ℃, for 1 to 6 hours, preferably 1 to 3 hours. The mixing may be carried out by means of stirring.

According to this preferred embodiment, it is possible to obtain a condensate having a mass ratio of 0.1 to 0.4: 1. preferably 0.14 to 0.3: 1, mixing at least part of the condensate with the hydrolytic condensation mixture, and then sealing the reaction kettle for hydrothermal crystallization.

In the step (1), the hydrothermal crystallization may be performed under conventional conditions. According to the method of the present invention, a titanium silicalite molecular sieve having a desired crystal form can be obtained even if hydrothermal crystallization is performed at a lower temperature for a shorter time than existing hydrothermal crystallization conditions under the same remaining conditions. According to the method of the present invention, in the step (2), the hydrothermal crystallization is preferably performed at a temperature of 120-. The duration of the hydrothermal crystallization is preferably 6 to 48 hours, more preferably 8 to 36 hours, and further preferably 10 to 24 hours. The hydrothermal crystallization is usually carried out under autogenous pressure, and pressure may be additionally applied during the hydrothermal crystallization. Preferably, the hydrothermal crystallization is performed under autogenous pressure. The hydrothermal crystallization can be carried out in a conventional reaction vessel.

According to the method of the present invention, step (2) is an optional operation, and step (2) may or may not be performed.

In one embodiment, the ratio of the mass of the condensate to the total mass of the feed mixture is from 0.1 to 0.4: 1. preferably 0.14 to 0.3: 1, directly sealing the reaction kettle, adjusting the conditions in the reaction kettle to hydrothermal crystallization conditions (namely, hydrothermal crystallization is not carried out in the presence of condensate), carrying out hydrothermal crystallization, and directly feeding the obtained hydrothermal crystallization mixture into the step (3) for spray forming. According to this embodiment, there is no need to add supplemental titanium silicalite molecular sieves, nor to add additional binders or precursors thereof. According to the embodiment, the hydrolysis condensation mixture is preferably directly subjected to hydrothermal crystallization, and the hydrothermal crystallization mixture is subjected to spray forming without solid-liquid separation and washing, so that the amount of the generated ammonia nitrogen wastewater is greatly reduced.

In a more preferred embodiment, the ratio of the mass of the condensate to the total mass of the starting mixture is from 0.1 to 0.4: 1. preferably 0.14 to 0.3: 1, mixing the hydrolytic condensation mixture with at least part of the condensate, sealing the reaction kettle, adjusting the conditions in the reaction kettle to hydrothermal crystallization conditions, carrying out hydrothermal crystallization, mixing the hydrothermal crystallization mixture with the supplementary titanium-silicon molecular sieve to obtain slurry, and carrying out spray forming on the slurry.

According to the more preferable embodiment, the decomposition of the template agent in the hydrothermal crystallization process can be effectively inhibited, meanwhile, the hydrothermal crystallization mixture can be directly sprayed and formed after being mixed with the complementary titanium silicalite molecular sieve without solid-liquid separation and washing, the amount of the generated ammonia nitrogen wastewater is greatly reduced, and the prepared titanium silicalite molecular sieve particles show more uniform and stable catalytic activity when being used as a catalyst.

According to this more preferred embodiment, the complementary titanium silicalite added may be a titanium silicalite that conforms to the topology of the titanium silicalite prepared by step (1) or a titanium silicalite that differs from the topology of the titanium silicalite prepared by step (1). Preferably, the topology structure of the titanium silicalite molecular sieve prepared by the step (1) is consistent with that of the complementary titanium silicalite molecular sieve, and more preferably, the topology structure of the titanium silicalite molecular sieve prepared by the step (1) and that of the complementary titanium silicalite molecular sieve are both titanium silicalite molecular sieves with MFI structures, such as titanium silicalite TS-1.

According to this embodiment, the weight ratio of the supplemental titanium silicalite molecular sieve to the hydrothermal crystallization mixture is preferably 0.01 to 10: 1, more preferably 0.05 to 8: 1. further preferably, the weight ratio of the supplementary titanium silicalite molecular sieve to the hydrothermal crystallization mixture is 0.2-5: 1. still more preferably, the weight ratio of the supplementary titanium silicalite molecular sieve to the hydrothermal crystallization mixture is 0.4-3: 1, the particle size distribution of the finally prepared titanium silicalite molecular sieve particles can be further improved, and titanium silicalite molecular sieve particles with narrower particle size distribution can be obtained. The hydrothermal crystallization mixture is on a dry basis. In the present invention, the dry basis means the mass of the hydrothermal crystallization mixture after drying at 120 ℃ for 8 hours.

According to this embodiment, the hydrothermal crystallization mixture and the complementary titanium silicalite molecular sieves can be uniformly mixed by a conventional method. For example, the hydrothermal crystallization mixture and the complementary titanium silicalite molecular sieve can be uniformly mixed by stirring.

According to this embodiment, the conditions for mixing the hydrothermal crystallization mixture and the complementary titanium silicalite molecular sieve are not particularly limited, and may be performed under conventional conditions. For example, the hydrothermal crystallization mixture may be mixed with the supplemental titanium silicalite molecular sieves uniformly at a temperature of 20 to 100 ℃, preferably 30 to 60 ℃, more preferably 30 to 40 ℃. The mixing duration is based on the capability of uniformly mixing the hydrothermal crystallization mixture and the supplementary titanium silicalite molecular sieve. In general, the duration of the mixing may be from 0.1 to 12 hours, preferably from 0.5 to 6 hours, more preferably from 1 to 3 hours.

According to the method of the present invention, in the step (3), the conditions for spray forming may be conventionally selected, and the present invention is not particularly limited thereto. Generally, the inlet temperature for spray forming may be 200-450 deg.C, preferably 250-400 deg.C.

According to the method of the present invention, the molecular sieve particles obtained by spray forming can be used directly, for example, as a catalyst; the catalyst may be used after calcination, for example, as a catalyst after calcination. The conditions for the calcination in the present invention are not particularly limited, and the calcination may be carried out under conventional conditions. Specifically, the calcination may be carried out at a temperature of 300-800 ℃, preferably at a temperature of 450-600 ℃. The duration of the calcination may be from 2 to 12 hours, preferably from 2 to 4 hours. The calcination may be performed in an air atmosphere or an inert atmosphere.

The bulk density of the titanium silicalite molecular sieve produced by the process of the first aspect of the invention is in the range of 0.3 to 0.6g/mL, preferably in the range of 0.35 to 0.55 g/mL. The bulk density of titanium silicalite molecular sieves prepared by conventional methods is typically in the range of 0.62 to 0.8 g/mL. The titanium silicalite molecular sieves produced by the process of the first aspect of the invention typically have a D50 of from 15 to 80 microns, preferably from 25 to 70 microns, more preferably from 30 to 60 microns. In the invention, D50 is measured by a laser particle size analyzer, and is a value obtained by directly measuring the titanium silicalite molecular sieve obtained by spray forming without screening and separating.

According to a third aspect of the present invention, there is provided an ammoximation reaction method, comprising contacting cyclohexanone, ammonia and hydrogen peroxide with a titanium silicalite molecular sieve under ammoximation reaction conditions, wherein the titanium silicalite molecular sieve is the titanium silicalite molecular sieve of the second aspect of the present invention.

According to the ammoximation reaction method of the present invention, the ammoximation reaction conditions are not particularly limited, and may be carried out under conventional conditions.

In general, the molar ratio of cyclohexanone, ammonia and hydrogen peroxide may be 1: 0.2-5: 0.5-2, preferably 1: 1-3: 0.8-1.5.

The contacting may be carried out in a solvent or in the absence of a solvent. The solvent may be one or more of alcohol, nitrile, ether, ester and water. Specific examples of the solvent may include, but are not limited to, one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, methyl t-butyl ether, acetonitrile, acrylonitrile, and water. Preferably, the solvent is tert-butanol. The amount of the solvent used in the present invention is not particularly limited, and may be selected conventionally. Generally, the solvent may be used in an amount of 10 to 5000 parts by weight, preferably 100-4000 parts by weight, more preferably 1000-3000 parts by weight, relative to 100 parts by weight of cyclohexanone.

According to the cyclohexanone ammoximation reaction process of the present invention, the contact of cyclohexanone, ammonia and hydrogen peroxide may be carried out at a temperature of 40 to 100 deg.C, preferably 60 to 95 deg.C, more preferably 70 to 90 deg.C. The pressure in the reactor may be 0 to 3MPa, preferably 0.2 to 2MPa, said pressure being a gauge pressure. The contacting can be carried out in a fixed bed reactor or in a slurry bed reactor. When the cyclohexanone is contacted in a fixed bed reactor, the liquid hourly volume space velocity of the cyclohexanone can be 0.1-50h^-1Preferably 0.2 to 25h^-1More preferably 1-20h^-1More preferably 2 to 15 hours^-1. When the slurry bed reactor is used for contact, the weight ratio of cyclohexanone to titanium silicalite molecular sieve can be 100: 1-50, preferably 100: 2-20.

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

In the following production examples and production comparative examples, X-ray diffraction analysis (XRD) was carried out on a Siemens D5005 type X-ray diffractometer.

In the following preparation examples and comparative preparations, infrared spectroscopic analysis was performed on a Nicolet 8210 type Fourier infrared spectrometer.

In the following preparation examples and preparation comparative examples, the molar composition of the molecular sieve was measured on an X-ray fluorescence spectrometer of model 3271E, manufactured by Nippon chemical mechanical Co., Ltd.

In the following preparation examples and preparation comparative examples, the D50 of titanium silicalite particles was measured using a laser particle size distribution instrument of malvern instruments ltd.

In the following preparation examples and comparative preparations, the bulk density was measured by the method specified in GB/T6286-1986.

In the following preparation examples and preparation comparative examples, the total specific surface area and pore volume were measured by the BET method.

In the following production examples and production comparative examples, the radial crush strength was measured by the method specified in RIPP 25-90.

In the following preparation examples and comparative preparations, the decomposition rate of the template agent in the hydrothermal crystallization process was calculated by the following method:

the decomposition rate (%) of the template (1-the weight of the oil phase separated after hydrothermal crystallization/the total weight of the template added before crystallization) × 100%, wherein the weight of the oil phase separated after hydrothermal crystallization and the total weight of the template added before crystallization are both calculated as N element.

In the following experimental examples and experimental comparative examples, the content of each component in the obtained reaction solution was analyzed by gas chromatography, and on the basis, the conversion of cyclohexanone and the selectivity of caprolactam were calculated by the following formulas, respectively:

cyclohexanone conversion (%) × 100 [ (% by mole of added cyclohexanone-by mole of unreacted cyclohexanone)/mole of added cyclohexanone ];

caprolactam selectivity (%) × 100% in terms of molar amount of caprolactam produced by the reaction/(molar amount of cyclohexanone added-molar amount of unreacted cyclohexanone).

Preparative examples 1-10 are illustrative of the titanium silicalite molecular sieves of the present invention and methods for their production.

Reference example 1

This reference is made to the preparation of molecular sieves TS-1 by the method described in Zeolite, 1992, Vol.12, pp.943-950, which is used to illustrate the synthesis of titanium silicalite TS-1 by conventional hydrothermal crystallization.

At room temperature (20 ℃), 22.5 g of ethyl orthosilicate (silicon ester 28, available from xirkat chemical trade ltd, yokkang) was mixed with 7.0 g of tetrapropylammonium hydroxide, and 59.8 g of distilled water was added, and after stirring and mixing, hydrolysis was carried out at normal pressure and 60 ℃ for 1.0 hour to obtain a hydrolyzed solution of ethyl orthosilicate, a solution consisting of 1.1 g of tetrabutyl titanate and 5.0 g of anhydrous isopropyl alcohol was slowly added under vigorous stirring, and the resulting mixture was stirred at 75 ℃ for 3 hours to obtain a clear transparent colloid. Placing the colloid in a stainless steel sealed reaction kettle, and standing at a constant temperature of 170 ℃ for 3 days to obtain a mixture of crystallized products; the mixture was filtered, washed with water, and dried at 110 ℃ for 60 minutes to obtain a molecular sieve raw powder. The molecular sieve raw powder is roasted for 3 hours at the temperature of 550 ℃ in the air atmosphere to obtain the molecular sieve.

Through detection, in an XRD spectrogram of the obtained molecular sieve, a five-finger diffraction characteristic peak which is specific to an MFI structure exists between 22.5-25.0 degrees of 2 theta, and the molecular sieve is shown to have the MFI structure similar to TS-1. Fourier infrared spectrum at 960cm^-1The characteristic absorption peak which the all-silicon molecular sieve does not have appears in the vicinity, and the titanium enters the sample framework. The above characterization results show that the prepared molecular sieve is a titanium silicalite TS-1. The molecular sieve property parameters are listed in table 4.

Preparation of example 1

(1) A50 wt% concentrated solution of tetrapropylammonium hydroxide (the solvent for this concentrated solution is water) was added to deionized water at 20 ℃ under 1 atm with stirring, and mixed for 1 hour to obtain an aqueous solution containing a template.

Tetrabutyl titanate as a titanium source and ethyl orthosilicate (silicon ester 28, same as in reference example 1) as an organic silicon source were mixed at 20 ℃ and 1 atm with stirring for 1 hour to obtain a mixture containing the titanium source and the organic silicon source.

Feeding an aqueous solution containing a template agent and a mixture containing a titanium source and an organic silicon source into a reaction kettle according to the proportion listed in Table 1, and carrying out hydrolytic condensation reaction with stirring according to the reaction conditions listed in Table 1 to obtain a hydrolytic condensation mixture, wherein the end point of the hydrolytic condensation reaction is determined by the mass ratio of a condensate to the total amount of the raw material mixture (namely, the mass ratio of the condensate to the total amount of the aqueous solution containing the template agent and the mixture containing the titanium source and the organic silicon source), and the specific numerical values are listed in Table 1.

In the hydrolysis condensation reaction process, nitrogen is used for auxiliary purging, steam in the reaction kettle is taken out, the taken steam is condensed by adopting condensed water, the condensate enters a condensate storage tank, and the composition of the condensate is listed in table 2.

(2) After the hydrolysis condensation reaction is completed, the condensate collected in the step (1) is added into the reaction kettle and stirred for 3 hours at the temperature of 40 ℃. The amounts of condensate used relative to 100 parts by weight of the hydrolytic condensation mixture (on a dry basis) are listed in Table 3. Next, the reaction vessel was sealed, the temperature in the reaction vessel was raised to the hydrothermal crystallization temperature, and hydrothermal crystallization was carried out under autogenous pressure, and the conditions of hydrothermal crystallization and the decomposition rate of the template agent during hydrothermal crystallization are shown in table 3.

After the hydrothermal crystallization is finished, after the temperature in the reaction kettle naturally drops to 30 ℃, the reaction kettle is opened, the titanium silicalite TS-1 (prepared by the same method as in reference example 1) is added into the reaction kettle, and after stirring for 2 hours, the obtained slurry is output. The addition amount of the titanium silicalite TS-1 is shown in Table 3.

(3) The resulting slurry was spray molded and the resulting particles were calcined at 550 ℃ for 3 hours in air atmosphere to give molecular sieve particles, the spray molding conditions being listed in table 3.

Through detection, in the XRD spectrogram of the obtained molecular sieve, a five-finger diffraction characteristic peak which is special for an MFI structure exists between 22.5-25.0 degrees of 2 theta,indicating that the molecular sieve has an MFI structure similar to TS-1. Fourier infrared spectrum at 960cm^-1The characteristic absorption peak which the all-silicon molecular sieve does not have appears in the vicinity, and the titanium enters the sample framework. The above characterization results show that the prepared molecular sieve is a titanium silicalite TS-1. The properties of the resulting molecular sieve particles are set forth in table 4.

Preparation of example 2

The titanium silicalite molecular sieve is produced by adopting the same method as the preparation example 1, except that in the step (2), the condensate collected in the step (1) is not added into the reaction kettle, but the reaction kettle is directly sealed for hydrothermal crystallization after the hydrolysis condensation reaction is finished; and in the step (2), the titanium silicalite TS-1 is not added into the mixture obtained by hydrothermal crystallization.

Through detection, in an XRD spectrogram of the obtained molecular sieve, a five-finger diffraction characteristic peak which is specific to an MFI structure exists between 22.5-25.0 degrees of 2 theta, and the molecular sieve is shown to have the MFI structure similar to TS-1. Fourier infrared spectrum at 960cm^-1The characteristic absorption peak which the all-silicon molecular sieve does not have appears in the vicinity, and the titanium enters the sample framework. The above characterization results show that the prepared molecular sieve is a titanium silicalite TS-1.

Preparation of comparative example 1

A titanium silicalite molecular sieve was produced in the same manner as in preparation example 1, except that in step (2), the condensate collected in step (1) was replaced with an equal weight of deionized water.

Through detection, five-finger diffraction characteristic peaks which are special for an MFI structure exist in the XRD crystal phase of the obtained molecular sieve between 22.5-25.0 degrees of 2 theta, and the molecular sieve is shown to have the MFI structure similar to TS-1. Fourier infrared spectrum at 960cm^-1The characteristic absorption peak which the all-silicon molecular sieve does not have appears in the vicinity, and the titanium enters the sample framework. The above characterization results show that the prepared molecular sieve is a titanium silicalite TS-1.

Preparation of comparative example 2

A titanium silicalite molecular sieve was produced in the same manner as in preparative example 1, except that in step (2), the condensate collected in step (1) was replaced with an equal weight of ethanol.

Preparation of comparative example 3

A titanium silicalite molecular sieve was produced in the same manner as in preparation example 1, except that in step (2), the condensate collected in step (1) was replaced with an equal weight of a mixture of water and ethanol (composition listed in table 2).

Preparation of comparative example 4

A titanium silicalite molecular sieve was produced in the same manner as in preparation example 1, except that in step (2), the condensate collected in step (1) was replaced with a mixed solution of water, ethanol and tetrapropylammonium hydroxide (composition shown in table 2) in equal weight.

Preparation of example 3

A titanium silicalite molecular sieve was produced in the same manner as in preparation example 1, except that, in step (1), the hydrolytic condensation reaction was carried out under the reaction conditions as listed in table 1.

Preparation of example 4

Preparation of example 5

(1) Tetrapropylammonium hydroxide was mixed with deionized water at 25 ℃ and 1 atm under stirring for 1.5 hours to obtain an aqueous solution containing a template.

Tetraisopropyl titanate as a titanium source and ethyl orthosilicate (silicone ester 40, available from xirkat chemical trade co., york, hong kong) as an organosilicon source were mixed at 25 c under 1 atm for 1.5 hours with stirring to obtain a mixture containing the titanium source and the organosilicon source.

Feeding an aqueous solution containing a template agent and a mixture containing a titanium source and an organic silicon source into a reaction kettle according to the proportion listed in Table 1, and carrying out hydrolytic condensation reaction with stirring according to the reaction conditions listed in Table 1 to obtain a hydrolytic condensation mixture, wherein the end point of the hydrolytic condensation reaction is determined by the mass percentage of a condensate to the total amount of the raw material mixture (namely, the mass percentage of the condensate to the total amount of the aqueous solution containing the template agent and the mixture containing the titanium source and the organic silicon source), and the specific numerical values are listed in Table 1.

(2) After the hydrolysis condensation reaction is completed, the condensate collected in the step (1) is added into the reaction kettle and stirred for 2 hours at the temperature of 50 ℃. The amounts of condensate used relative to 100 parts by weight of the hydrolytic condensation mixture (on a dry basis) are listed in Table 3.

Next, the reaction vessel was sealed, the temperature in the reaction vessel was raised to the hydrothermal crystallization temperature, and hydrothermal crystallization was carried out under autogenous pressure, and the conditions of hydrothermal crystallization and the decomposition rate of the template agent during hydrothermal crystallization are shown in table 3.

After the hydrothermal crystallization is completed, the temperature in the reaction kettle is naturally reduced to 40 ℃, the reaction kettle is opened, the titanium silicalite TS-1 (prepared by the same method as in reference example 1) is added into the reaction kettle, and after stirring for 1 hour, the obtained slurry is output. The addition amount of the titanium silicalite TS-1 is shown in Table 3.

(3) The resulting slurry was spray molded and the resulting particles were calcined at 500 ℃ for 4 hours in air atmosphere to give molecular sieve particles, the spray molding conditions being listed in table 3.

Through detection, in an XRD spectrogram of the obtained molecular sieve, a five-finger diffraction characteristic peak which is specific to an MFI structure exists between 22.5-25.0 degrees of 2 theta, and the molecular sieve is shown to have the MFI structure similar to TS-1. Fourier infrared spectrum at 960cm^-1The characteristic absorption peak which the all-silicon molecular sieve does not have appears in the vicinity, and the titanium enters the sample framework. The above characterization results show that the prepared molecular sieve is a titanium silicalite TS-1. The properties of the resulting molecular sieve particles are set forth in table 4.

Preparation of example 6

The titanium silicalite molecular sieve is produced by adopting the same method as the preparation example 5, except that in the step (2), the condensate collected in the step (1) is not added into the reaction kettle, but the reaction kettle is directly sealed for hydrothermal crystallization after the hydrolysis condensation reaction is finished; and in the step (2), the titanium silicalite TS-1 is not added into the mixture obtained by hydrothermal crystallization.

Preparation of comparative example 5

A titanium silicalite molecular sieve was produced in the same manner as in preparation example 5, except that in step (2), the condensate collected in step (1) was replaced with a mixed solution of water, ethanol and tetrapropylammonium hydroxide (composition shown in table 2) of equal weight.

Preparation of example 7

Titanium silicalite molecular sieves were produced in the same manner as in preparative example 5 except that the condensate was used in the amounts shown in Table 3 relative to 100 parts by weight of the hydrolytic condensation mixture (on a dry basis).

Preparation of example 8

(1) Tetrapropylammonium hydroxide was mixed with deionized water at 30 ℃ and 1 atm under stirring for 1 hour to obtain an aqueous solution containing a template.

Tetrabutyl titanate as a titanium source and ethyl orthosilicate (silicon ester 40, available from xiekatt chemical trade co., yokohong) as an organosilicon source were mixed at 30 ℃ and 1 atm under stirring for 1 hour to obtain a mixture containing the titanium source and the organosilicon source.

(2) After the hydrolysis condensation reaction is completed, the condensate collected in the step (1) is added into the reaction kettle and stirred for 1 hour at the temperature of 60 ℃. The amounts of condensate used relative to 100 parts by weight of the hydrolytic condensation mixture (on a dry basis) are listed in Table 3. Next, the reaction vessel was sealed, the temperature in the reaction vessel was raised to the hydrothermal crystallization temperature, and hydrothermal crystallization was carried out under autogenous pressure, and the conditions of hydrothermal crystallization and the decomposition rate of the template agent during hydrothermal crystallization are shown in table 3.

After the hydrothermal crystallization is finished, after the temperature in the reaction kettle naturally drops to 40 ℃, the reaction kettle is opened, the titanium silicalite TS-1 (prepared by the same method as in reference example 1) is added into the reaction kettle, and after stirring for 3 hours, the obtained slurry is output. The addition amount of the titanium silicalite TS-1 is shown in Table 3.

(3) The resulting slurry was spray molded and the resulting particles were calcined at 480 ℃ for 6 hours in air atmosphere to give molecular sieve particles, the spray molding conditions being listed in table 3.

Preparation of example 9

The titanium silicalite molecular sieve is produced by the same method as the preparation example 8, except that in the step (2), the condensate collected in the step (1) is not added into the reaction kettle, but the reaction kettle is directly sealed for hydrothermal crystallization after the hydrolysis condensation reaction is finished; and in the step (2), the titanium silicalite TS-1 is not added into the mixture obtained by hydrothermal crystallization.

Preparation of comparative example 6

A titanium silicalite molecular sieve was produced in the same manner as in preparative example 8, except that in step (2), the condensate collected in step (1) was replaced with a mixed solution of water, ethanol and tetrapropylammonium hydroxide (composition shown in table 2) of equal weight.

Through detection, in an XRD spectrogram of the obtained molecular sieve, a five-finger diffraction characteristic peak which is specific to an MFI structure exists between 22.5-25.0 degrees of 2 theta, and the molecular sieve is shown to have the MFI structure similar to TS-1. Fourier infrared spectrum at 960cm^-1The characteristic absorption peak which is not existed in the all-silicon molecular sieve appears in the vicinity, which indicates that the titanium is already existedAnd entering a sample skeleton. The above characterization results show that the prepared molecular sieve is a titanium silicalite TS-1.

Preparation of comparative example 7

The titanium silicalite molecular sieve was produced in the same manner as in preparation example 8, except that in step (1), the hydrolysis condensation reaction was carried out without purging with nitrogen, and the vapor generated by the reaction was condensed and refluxed back to the reaction vessel. In the step (2), the condensate is not added into the reaction kettle, but the hydrolysis condensation mixture obtained in the step (1) is fed into the reaction kettle, stirred for 1 hour at the temperature of 60 ℃, and then the reaction kettle is sealed for hydrothermal crystallization.

Preparation of example 10

Titanium silicalite molecular sieves were produced in the same manner as in preparative example 8, except that the condensate was used in the amounts shown in Table 3 relative to 100 parts by weight of the hydrolytic condensation mixture (on a dry basis).

TABLE 1

TABLE 2

Numbering	Alcohol content (% by weight)	Nitrogen content (mmol/L)
			Preparation of example 1	91	1.25
Preparation of comparative example 3	91	0
			Preparation of comparative example 4	91	1.25
Preparation of example 3	83	2.32
			Preparation of example 4	94	0.08
Preparation of example 5	88	0.87
			Preparation of comparative example 5	88	0.88
Preparation ofExample 8	92	0.53
			Preparation of comparative example 6	92	0.55

TABLE 3

¹: the hydrothermal crystallization mixture is calculated by dry basis relative to the addition amount of 1 weight part of hydrothermal crystallization mixture, and the dry basis refers to the mass of the hydrothermal crystallization mixture after being dried at 120 ℃ for 8 hours.

TABLE 4

The results of preparation examples 2, 6 and 9 confirmed that, by using the method of the present invention, the amount of the condensate discharged from the system during the hydrolytic condensation reaction was controlled, and the hydrothermal crystallization mixture obtained by hydrothermal crystallization was directly spray-molded without adding additional titanium silicalite molecular sieves and binders or their precursors.

The results of preparation examples 1, 5 and 8 demonstrate that, by using the method of the present invention to produce a titanium silicalite molecular sieve, and mixing at least a part of the condensate generated in the hydrolysis condensation reaction process with the hydrolysis condensation mixture for hydrothermal crystallization, the invalid decomposition of the template agent in the hydrothermal crystallization process can be effectively inhibited, the amount of the template agent recycled is increased, the consumption of the template agent is reduced, and the production cost of the titanium silicalite molecular sieve is further reduced.

Experimental examples 1-10 are provided to illustrate the cyclohexanone ammoximation reaction method of the present invention.

Experimental examples 1 to 10

Experimental examples 1 to 10 the cyclohexanone ammoximation reaction was carried out by using the titanium silicalite molecular sieves prepared in preparation examples 1 to 10 as catalysts for the cyclohexanone ammoximation reaction, respectively, in the following manner.

The titanium silicalite molecular sieves prepared in preparation examples 1 to 10 were respectively loaded in a fixed bed reactor to form a catalyst bed (the aspect ratio of the catalyst bed was 5), cyclohexanone, ammonia, hydrogen peroxide (the concentration of hydrogen peroxide was 30 wt%) and a solvent were fed into the fixed bed reactor in the proportions shown in table 5, and the reaction was carried out under the reaction conditions shown in table 5 (the pressure in table 5 was gauge pressure). The reaction was continued for 80 hours. And collecting the reaction product output from the fixed bed reactor, measuring the composition of the reaction product, and calculating the conversion rate of cyclohexanone and the selectivity of caprolactam.

Each preparation example was repeated to prepare 3 batches of titanium silicalite molecular sieves, each batch of titanium silicalite molecular sieves was subjected to 3 sets of parallel experiments, each preparation example was subjected to 9 sets of experiments in total, and average values of cyclohexanone conversion and caprolactam selectivity obtained in the 9 sets of experiments were taken as the evaluation results of the catalytic performance of the titanium silicalite molecular sieves prepared in the preparation examples, and the specific results are listed in table 5.

Experimental comparative examples 1 to 7

The cyclohexanone ammoximation reaction was carried out in the same manner as in examples 1 to 10, except that the titanium silicalite molecular sieves prepared in comparative examples 1 to 7 were each used as a catalyst. The results of the experiment are listed in table 5.

Reference Experimental example 1

The cyclohexanone ammoximation reaction was carried out in the same manner as in examples 1 to 10, except that the titanium silicalite molecular sieves prepared in reference example 1 were each used as a catalyst. The results of the experiment are listed in table 5.

TABLE 5

The results of experimental examples 1-10 confirm that the titanium silicalite molecular sieve prepared by the method of the invention can obtain more excellent catalytic performance as the catalyst of cyclohexanone ammoximation reaction.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A method for producing a titanium silicalite molecular sieve, the method comprising:

(3) carrying out spray forming on the hydrothermal crystallization mixture or the slurry;

the method is characterized in that in the hydrolytic condensation reaction process, generated steam is led out and condensed to obtain condensate, and the ratio of the mass of the condensate to the total mass of the raw material mixture is 0.1-0.4: 1, sealing the reaction kettle, adjusting the conditions in the reaction kettle to hydrothermal crystallization conditions, and carrying out hydrothermal crystallization, wherein before the reaction kettle is sealed, at least part of the condensate is mixed with the hydrolysis condensation mixture.

2. The method of claim 1The method comprises the following steps of (1), wherein the molar ratio of the organic silicon source to the titanium source to the template to water is 100: (0.005-10): (0.005-40): (200-10000), the organic silicon source is SiO₂The titanium source is calculated as TiO₂In terms of NH, the template agent₃And (6) counting.

3. The method according to claim 2, wherein in the step (1), the molar ratio of the organic silicon source, the titanium source, the template and the water is 100: (0.05-8): (0.5-30): (500-5000), the organic silicon source is SiO₂The titanium source is calculated as TiO₂In terms of NH, the template agent₃And (6) counting.

4. The method of claim 3, wherein in step (1), the molar ratio of the organic silicon source, the titanium source, the templating agent, and the water is 100: (0.2-6): (5-25): (800-4000), the organic silicon source is SiO₂The titanium source is calculated as TiO₂In terms of NH, the template agent₃And (6) counting.

5. The method of claim 4, wherein in step (1), the molar ratio of the organic silicon source, the titanium source, the template agent and the water is 100: (1-5): (10-20): (1500-3000), the organic silicon source is SiO₂The titanium source is calculated as TiO₂In terms of NH, the template agent₃And (6) counting.

6. The method according to any one of claims 1 to 5, wherein the organic silicon source is selected from silicon-containing compounds of formula I,

in the formula I, R₁、R₂、R₃And R₄Each is C₁-C₄Alkyl group of (1).

7. The method according to claim 6, wherein the organic silicon source is one or more selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, isopropyl orthosilicate, and n-butyl orthosilicate.

8. The method of any one of claims 1-5, wherein the titanium source is TiCl₄、Ti(SO₄)₂、TiOCl₂One or more than two of titanium hydroxide, titanium oxide, titanium nitrate, titanium phosphate, tetraisopropyl titanate, tetra-n-propyl titanate, tetrabutyl titanate and tetraethyl titanate

9. The method of any one of claims 1-5, wherein the templating agent is one or more of urea, amine, alcohol amine, and quaternary ammonium base.

10. The method of claim 9, wherein the templating agent is a quaternary ammonium base represented by formula II,

in the formula II, R₅、R₆、R₇And R₈Are the same or different and are each C₁-C₄Alkyl group of (1).

11. The method of claim 10, wherein the templating agent is tetraethylammonium hydroxide and/or tetrapropylammonium hydroxide.

12. The process according to claim 1, wherein the condensate is used in an amount of 1 to 50 parts by weight relative to 100 parts by weight of the hydrolytic condensation mixture.

13. The process according to claim 12, wherein the condensate is used in an amount of 1.5 to 40 parts by weight relative to 100 parts by weight of the hydrolytic condensation mixture.

14. The process according to claim 13, wherein the condensate is used in an amount of 2 to 30 parts by weight with respect to 100 parts by weight of the hydrolytic condensation mixture.

15. The process according to claim 14, wherein the condensate is used in an amount of 10 to 25 parts by weight with respect to 100 parts by weight of the hydrolytic condensation mixture.

16. A process according to any one of claims 12 to 15, wherein the hydrolytic condensation mixture is mixed with the condensate at 20 to 80 ℃ for 1 to 6 hours with stirring.

17. The method according to claim 16, wherein the hydrolytic condensation mixture is mixed with the condensate at 40-60 ℃ with stirring.

18. A method according to any one of claims 1 and 12 to 15, wherein the condensate comprises water and alcohol, the alcohol being present in an amount of 80 to 96 wt% and the water being present in an amount of 4 to 20 wt%, based on the total amount of the condensate.

19. A method according to claim 18, wherein the condensate comprises water and alcohol, the alcohol being present in an amount of 83-95 wt% and the water being present in an amount of 5-17 wt%, based on the total amount of the condensate.

20. A method according to claim 19, wherein the condensate comprises water and alcohol, the alcohol being present in an amount of 88-92% by weight and the water being present in an amount of 8-12% by weight, based on the total amount of the condensate.

21. The method according to any one of claims 1 and 12-15, wherein the condensate contains nitrogen.

22. The method of claim 21, wherein the concentration of elemental nitrogen in the condensate is 0.01 to 50 mmol/L.

23. The method of claim 22, wherein the concentration of elemental nitrogen in the condensate is 0.02 to 20 mmol/L.

24. The method of claim 23, wherein the concentration of elemental nitrogen in the condensate is 0.04 to 5 mmol/L.

25. The method of claim 24, wherein the concentration of elemental nitrogen in the condensate is 0.05 to 3 mmol/L.

26. The method of claim 25, wherein the concentration of elemental nitrogen in the condensate is 0.5 to 1.5 mmol/L.

27. The process of any one of claims 12 to 15, wherein the process comprises step (2) and the weight ratio of the supplemental titanium silicalite molecular sieve to the hydrothermal crystallization mixture is from 0.01 to 10: 1, the hydrothermal crystallization mixture is on a dry basis.

28. The process of claim 27, wherein the process comprises step (2), the weight ratio of the supplemental titanium silicalite molecular sieve to the hydrothermal crystallization mixture is from 0.05 to 8: 1, the hydrothermal crystallization mixture is on a dry basis.

29. The method of claim 28, wherein the method comprises a step (2) in which the weight ratio of the supplemental titanium silicalite molecular sieve to the hydrothermal crystallization mixture is from 0.2 to 5: 1, the hydrothermal crystallization mixture is on a dry basis.

30. The method of claim 29, wherein the method comprises a step (2) in which the weight ratio of the supplemental titanium silicalite molecular sieve to the hydrothermal crystallization mixture is from 0.4 to 3: 1, the hydrothermal crystallization mixture is on a dry basis.

31. The method according to claim 1, wherein, in the step (1), the hydrolytic condensation reaction is performed at a temperature of 80-98 ℃.

32. The process according to claim 31, wherein in step (1), the hydrolytic condensation reaction is carried out at a temperature of 85-95 ℃.

33. The process according to any one of claims 1, 31 and 32, wherein in step (1), the duration of the hydrolytic condensation reaction is 4 to 36 hours.

34. The process according to claim 33, wherein in step (1), the duration of the hydrolytic condensation reaction is 6 to 28 hours.

35. The process according to claim 34, wherein in step (1), the duration of the hydrolytic condensation reaction is 12 to 16 hours.

36. The method as claimed in any one of claims 1, 31 and 32, wherein, in the step (1), the hydrothermal crystallization is performed at a temperature of 120-180 ℃.

37. The method as claimed in claim 36, wherein, in the step (1), the hydrothermal crystallization is performed at a temperature of 140 ℃ to 175 ℃.

38. The method as claimed in claim 37, wherein, in the step (1), the hydrothermal crystallization is performed at a temperature of 160-175 ℃.

39. The method according to any one of claims 1, 31 and 32, wherein in step (1), the duration of the hydrothermal crystallization is 6-48 hours.

40. The method of claim 39, wherein in step (1), the duration of the hydrothermal crystallization is 8-36 hours.

41. The method according to claim 40, wherein in step (1), the duration of the hydrothermal crystallization is 10-24 hours.

42. The method according to claim 1, wherein the ratio of the mass of the condensate to the total mass of the raw mixture is 0.14-0.3: 1, sealing the reaction kettle, adjusting the conditions in the reaction kettle to hydrothermal crystallization conditions, and carrying out hydrothermal crystallization.

43. A titanium silicalite molecular sieve produced by the method of any one of claims 1 to 42.

44. A cyclohexanone ammoximation reaction method, which comprises contacting cyclohexanone, ammonia and hydrogen peroxide with a titanium silicalite molecular sieve under ammoximation reaction conditions, wherein the titanium silicalite molecular sieve is the titanium silicalite molecular sieve of claim 43.