CN104556111B - A kind of Titanium Sieve Molecular Sieve and its synthetic method - Google Patents

Abstract

A titanium-silicon molecular sieve and a synthesis method thereof, wherein the titanium-silicon molecular sieve grain surface is rich in silicon, and the surface silicon-titanium ratio is higher than the bulk phase silicon-titanium ratio. The synthesis method of the titanium-silicon molecular sieve includes mixing a titanium source, a template agent, an organic silicon source, an inorganic ammonium source and water, hydrolyzing alcohol, aging, mixing with a solid silicon source, and then crystallizing in a closed reactor to recover titanium Silica Molecular Sieve. The titanium-silicon molecular sieve provided by the invention has higher oxidation activity, and the ineffective decomposition activity of side reaction hydrogen peroxide is obviously reduced.

Description

A kind of titanium silicon molecular sieve and its synthesis method

technical field

The invention relates to a titanium silicon molecular sieve and a synthesis method thereof.

Background technique

Titanium-silicon molecular sieve is a new type of heteroatom molecular sieve developed in the early 1980s. At present, TS-1 with MFI structure, TS-2 with MEL structure, MCM-22 with MWW structure and TS-48 with larger pore structure have been synthesized. Among them, TS-1 was first developed and synthesized by Italian EniChem Company. It is a new type of titanium-silicon molecular sieve with excellent catalytic selective oxidation performance formed by introducing transition metal element titanium into the molecular sieve framework with ZSM-5 structure. TS-1 It not only has the catalytic oxidation effect of titanium, but also has the shape-selective effect and excellent stability of ZSM-5 molecular sieve. Using this titanium-silicon molecular sieve as a catalyst can catalyze various types of organic oxidation reactions, such as epoxidation of alkenes, partial oxidation of alkanes, oxidation of alcohols, hydroxylation of phenols, ammoxidation of cyclic ketones, etc. Since TS-1 molecular sieve can use non-polluting low-concentration hydrogen peroxide as an oxidant in the oxidation reaction of organic matter, it avoids the problems of complex oxidation process and environmental pollution, and has incomparable energy saving, economy and environment in traditional oxidation systems. Friendly and other advantages, and has good reaction selectivity. As a catalyst for the selective oxidation of organic matter, titanium-silicon molecular sieve is considered a milestone in the field of molecular sieve catalysis. It can overcome the disadvantages of traditional catalytic oxidation system from the source, such as complex reaction process, harsh conditions and serious environmental pollution. Today, people pay extra attention to it.

In 1983, Taramasso first reported the method of synthesizing titanium-silicon molecular sieves by hydrothermal crystallization in the patent US 4410501. This method is a classic method for synthesizing TS-1. It is mainly divided into two steps: gel preparation and crystallization. The synthesis process is as follows: put tetraethyl orthosilicate (TEOS) into a container without CO ₂ under nitrogen protection, and slowly add TPAOH ( Template agent), then slowly drop tetraethyl titanate (TEOT), and stir for 1h to prepare a reaction mixture containing silicon source, titanium source and organic base, heat, remove alcohol, replenish water, 175 ° C under autogenous pressure Stir under the kettle, crystallize for 10 days, then separate, wash, dry, and roast to obtain TS-1 molecular sieve. However, there are many factors affecting the process of titanium insertion into the framework in this process, and the conditions for hydrolysis and nucleation are not easy to control. Therefore, the TS-1 molecular sieve synthesized by this method has disadvantages such as low catalytic activity, poor stability, and difficulty in synthesis and reproduction.

Chinese patent CN 98101357.0 (CN 1260241A) discloses the titanium-silicon molecular sieve rearrangement technology, and synthesizes a new type of titanium-silicon molecular sieve with a unique hollow structure, which not only greatly enhances the reproducibility of synthesizing TS-1, but also increases the pore volume of the molecular sieve, greatly The mass transfer diffusion rate of the reactant molecules in the molecular sieve channel is improved, and the catalytic performance is increased. The method disclosed in this patent mixes the titanium hydrolysis solution and the synthesized TS-1 molecular sieve uniformly according to the ratio of molecular sieve (g): Ti (mol) = 200-1500:1, and mixes the obtained mixture in a reaction kettle with 120- React at 200°C for 1-8 days, filter, wash and dry. At present, the application of HTS molecular sieves in catalytic oxidation of phenol hydroxylation and cyclohexanone ammoximation has been industrialized. It has the advantages of mild reaction conditions, high atom utilization, simple process, and clean and efficient water by-product.

The current direct hydrothermal synthesis method of titanium-silicon molecular sieves usually uses organosilicon source and/or inorganic silicon source. Organic silicon sources such as organosilicon ester TEOS are relatively expensive, and the content of active ingredients forming molecular sieves is also low. It is difficult to increase the solid content of molecular sieve crystallization products, and a large amount of ethanol is volatilized during the production of molecular sieves, and these ethanols are difficult to collect. Reuse. In order to reduce costs, researchers have used inorganic silicon sources to replace some or all of the organic silicon sources. However, the activity of titanium-silicon molecular sieves synthesized using inorganic silicon sources (solid silicon sources) is lower than that of titanium-silicon molecular sieves synthesized entirely using organic silicon sources. In addition, the prior art does not involve further improving the activity of titanium silicate molecular sieves.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new titanium-silicon molecular sieve for the deficiency of the existing titanium-silicon molecular sieve, and another technical problem to be solved by the present invention is to provide a synthesis method of the titanium-silicon molecular sieve.

The invention provides a kind of synthetic method of titanium silicon molecular sieve, comprises the steps:

(1) Mix titanium source, templating agent, organosilicon source, water and optional inorganic ammonium source, and hydrolyze alcohol;

(2) Aging the product obtained in step (1) at room temperature to 50°C;

(3) Mix the aging product obtained in step (2) with the solid silicon source evenly, and then crystallize in a closed reaction kettle to recover the titanium-silicon molecular sieve.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the molar ratio of the titanium source to the total silicon source is preferably 0.01-0.05:1. The molar ratio of the aging product obtained in step (2) to the solid silicon source in step (3) is 1:0.1-10; wherein in the molar ratio, the aging product obtained in step (2) is SiO ₂ is counted, and the solid silicon source is counted as SiO ₂ .

The synthetic method of titanium silicon molecular sieve provided by the present invention preferably comprises the following steps:

(1) Mix template agent, titanium source, organosilicon source, inorganic ammonium source and water to hydrolyze alcohol; the hydrolyzed alcohol is usually stirred at 0-150°C, such as 0-100°C, for at least 10 minutes; the stirring time of the stirring is, for example, 10 minutes to 50 hours; wherein, the molar ratio of inorganic ammonium source (calculated as NH ₄ ⁺ ): titanium source (calculated as TiO ₂ ) is 0 to 5:1;

(2) Aging the product obtained in step (1), the aging is standing the product obtained in step (1) at room temperature for 1-60 hours, such as 2-50 hours or 3-30 hours, further such as 3-15 hours;

(3) Mix the aging product obtained in step (2) with the solid silicon source according to a weight ratio of 1:0.1-10, and then crystallize in a closed reaction kettle to recover titanium-silicon molecular sieves; , the aging product and solid silicon source obtained in step (2) are both calculated as _SiO2 ; wherein, the molar ratio of titanium source to total silicon source is 0.005-0.05:1, and the molar ratio of water to total silicon source is 5-100 : 1; the molar ratio of the template agent to the total silicon source is not less than 0.05～0.5:1, such as 0.05～0.3:1; wherein, in the molar ratio, the total silicon source is calculated as SiO ₂ , and the total silicon source is the sum of the organic silicon source calculated as _SiO2 and the solid silicon source calculated as _SiO2 , the inorganic ammonium source is calculated as _NH4 ⁺ ; the inorganic ammonium source is inorganic ammonium salt and/or ammonia water, and the titanium source is calculated as _TiO2 Water is measured as H ₂ O.

The present invention also provides a titanium-silicon molecular sieve, which has the following characteristics: the surface of the titanium-silicon molecular sieve crystal grains is rich in silicon, and the ratio of the silicon-titanium molar ratio on the grain surface to the bulk phase silicon-titanium molar ratio is greater than 1.1, for example, 1.1- 5. The ratio of the surface silicon-titanium ratio to the bulk silicon-titanium ratio is, for example, 1.2˜4:1.

Among them, the surface silicon-titanium ratio can be measured by TEM-EDX or ion-induced corrosion XPS method, which is the silicon-titanium ratio of the atomic layer no more than 5nm away from the grain surface, such as 1-5nm, and the bulk phase silicon-titanium ratio can be determined by chemical analysis. method, or measured by TEM-EDX or XPS in the central region of the crystal grain, for example, the distance from the crystal grain surface is greater than 20nm.

According to the method for synthesizing the titanium-silicon molecular sieve provided by the invention, the grain surface of the prepared titanium-silicon molecular sieve is rich in silicon, and the silicon-to-titanium ratio on the grain surface is obviously higher than the bulk phase silicon-to-titanium ratio. In addition, the titanium-silicon molecular sieve synthesis method provided by the present invention uses relatively cheap and easily available solid silicon sources such as high-purity silica gel or/and white carbon black to partially replace expensive organic silicon sources, which can reduce waste emissions and save energy in the molecular sieve production process. High-performance titanium-silicon molecular sieves can be obtained while reducing the cost of raw materials. The method for synthesizing titanium-silicon molecular sieves provided by the present invention can synthesize titanium-silicon molecular sieves at a lower dosage of template agent and lower water-to-silicon ratio, reduce the synthesis cost of titanium-silicon molecular sieves, and increase the solid content of the crystallized products of synthetic molecular sieves , to increase the yield of single-pot molecular sieve.

The titanium-silicon molecular sieve provided by the present invention has a higher ratio of surface silicon-titanium ratio to bulk phase silicon-titanium ratio, and has higher oxidation activity. It can be used for the oxidation reaction in which hydrogen peroxide participates, and can reduce the decomposition of hydrogen peroxide by titanium in the surface layer. , which is beneficial to reduce the activity of the ineffective decomposition side reaction of hydrogen peroxide and improve the utilization rate of raw materials.

Description of drawings

Fig. 1 is the XRD spectrum of the titanium silicon TS-1 molecular sieve prepared in the embodiment of the present invention.

Fig. 2 is the XRD spectrum of the Ti-β molecular sieve prepared in the embodiment of the present invention.

Fig. 3 is a TEM image of the hollow titanium-silicon TS-1 molecular sieve obtained in step (4) of the embodiment of the present invention.

Fig. 4 is the hydrogen peroxide test of the titanium-silicon molecular sieve prepared in the prior art and Example 6, a graph showing the concentration of hydrogen peroxide changing with time.

Fig. 5 is a schematic diagram of measuring bulk silicon-titanium ratio and surface silicon-titanium ratio by TEM-EDX, in which box 1 shows the measurement of the silicon-titanium ratio in the particle edge region, and box 2 shows the measurement of the silicon-titanium ratio in the particle center region. Since the particle edge area has a higher external area per unit volume, and the corresponding external area per unit volume in the central area is lower, the EDX measurement results in Box 1 and Box 2 can reflect the difference in silicon-titanium ratio between the surface and the surface.

Detailed ways

The method for synthesizing titanium-silicon molecular sieves provided by the present invention can synthesize titanium-silicon molecular sieves at a lower dosage of template agent, so the dosage of template agent can be lower, for example, the molar ratio of template agent to total silicon source is 0.05-0.3:1 , further 0.05～0.25:1 or 0.05～0.2:1; in the method provided by the present invention, titanium-silicon molecular sieves can be synthesized under high solid content, thereby reducing the usage of water and increasing the single-pot output that is in the same More molecular sieves are synthesized under the volume of the synthesis reactor, so the molar ratio of water to total silicon source (silicon dioxide) can be 5-80:1 or 5-50:1, such as 5-30:1, such as 6-20 or 6-15:1. For example, the molar ratio of template agent to total silicon source is 0.05-0.2:1, and the molar ratio of water to total silicon source is 6-15:1.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the molar ratio of the titanium source to the total silicon source is 0.005-0.05:1, preferably 0.01-0.03:1, for example, 0.01-0.025:1.

In the synthesis method of the titanium-silicon molecular sieve provided by the present invention, the molar ratio of the inorganic ammonium source to the titanium source is 0-5:1, for example, 0.01-4:1, preferably 0.01-0.5:1. Adding an inorganic ammonium source can increase the oxidation activity of the synthesized molecular sieve, increase the utilization rate of the titanium source (it can have a higher skeleton titanium-silicon ratio under the same amount of titanium source usage), and reduce the usage amount of the titanium source.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the molar ratio of the template agent to the total silicon source is not less than 0.05:1, preferably 0.05-0.3:1, for example 0.05-0.2:1.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the molar ratio of the organosilicon source to the solid silicon source is 1:0.1-10, preferably 1:1-9, for example 1:2-8 or 1:3-7 . The ratio of the aging product obtained in step (2) to the solid silicon source in terms of SiO ₂ is equal to the molar ratio of the organic silicon source to the solid silicon source. The solid silicon source is an inorganic silicon source.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the template agent described in step (1) is an organic base or a mixture of an organic base and an organic quaternary ammonium salt, and the organic base is one of an organic quaternary ammonium base and an organic amine One or more; For example, the template can be an organic quaternary ammonium base, a mixture of an organic quaternary ammonium base and an organic amine, a mixture of an organic quaternary ammonium base and an organic quaternary ammonium salt, a mixture of an organic amine and an organic quaternary ammonium salt, or Organic quaternary ammonium bases and mixtures of organic quaternary ammonium salts and organic amines. The organic amine is one or more of aliphatic amines, aromatic amines and alcohol amines. The general formula of the aliphatic amines (also known as fatty amine compounds) is R ³ (NH ₂ ) _n , where R ³ is an alkyl or alkylene group with 1 to 4 carbon atoms, n=1 or 2; the general formula of the alcohol amine (also called alcohol amine compound in the present invention) is (HOR ⁴ ) _m NH _{(3 -m)} , wherein R ⁴ is an alkyl group with 1 to 4 carbon atoms, m=1, 2 or 3. One or more of the aliphatic amines such as ethylamine, n-butylamine, butylenediamine or hexamethylenediamine; the aromatic amines refer to amines with an aromatic substituent, such as aniline, toluidine, One or more of p-phenylenediamine; one or more of said alcoholamines such as monoethanolamine, diethanolamine or triethanolamine. Described organic quaternary ammonium base such as one or more in tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide or tetraethyl ammonium hydroxide; Described organic quaternary ammonium salt such as tetrapropyl ammonium bromide, tetra One or more of butylammonium bromide, tetraethylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride.

In one embodiment, the template agent includes an organic base, including an organic quaternary ammonium compound, and the molar ratio of the organic base introduced into the template agent to the silicon source is not less than 0.05:1, for example, 0.05-0.45; 1, the The organic base is an organic quaternary ammonium base and/or an organic amine; the molar ratio of the organic quaternary ammonium compound to the silicon source is not less than 0.05:1, such as 0.05 to 0.45:1, and the organic quaternary ammonium compound is an organic quaternary ammonium compound. Ammonium bases and/or organic quaternary ammonium salts.

A kind of implementation method, described template agent, comprises organic quaternary ammonium base, can be organic quaternary ammonium base or the mixture that comprises organic quaternary ammonium base, for example described template agent is the mixture of organic quaternary ammonium base and organic amine, A mixture of an organic quaternary ammonium base and an organic quaternary ammonium salt, or a mixture of an organic quaternary ammonium base, an organic quaternary ammonium salt and an organic amine. Preferably, the molar ratio of organic quaternary ammonium base to organic ammonium is 1:0 to 10, such as 1:0 to 8, and the molar ratio of organic quaternary ammonium base to organic quaternary ammonium salt is 1:0 to 10, such as 1:0 to 8. The molar ratio of the organic quaternary ammonium base to the total silicon source is 0.05-0.45:1, for example 0.05-0.3:1, for example 0.05-0.2:1.

The method for synthesizing a titanium-silicon molecular sieve provided by the present invention, in one embodiment, the titanium-silicon molecular sieve is TS-1 molecular sieve, and the template agent is tetrapropylammonium hydroxide or tetrapropylammonium hydroxide and selected from A mixture of one or more of organic amines, tetrapropylammonium chloride, and tetrapropylammonium bromide. In one embodiment, the titanium-silicon molecular sieve is TS-2 molecular sieve, and the template agent is tetrabutylammonium hydroxide or tetrabutylammonium hydroxide and selected from organic amines, tetrabutylammonium chloride, tetrabutyl bromide A mixture of one or more of ammonium chlorides. .

The method for synthesizing a titanium-silicon molecular sieve provided by the present invention, in one embodiment, the titanium-silicon molecular sieve is a Ti-β molecular sieve, and the template agent is tetraethylammonium hydroxide or tetraethylammonium hydroxide and selected from A mixture of one or more of organic amines, tetraethylammonium chloride, and tetraethylammonium bromide.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the organosilicon source described in step (1) is organosilicon grease, and the general formula of the organosilicon ester is Si(OR ¹ ) ₄ , and R ¹ is selected from the group consisting of 1 An alkyl group with ~6 carbon atoms, for example, R ¹ is a C ₁ -C ₄ alkyl group, and the alkyl group may be a branched chain alkyl group or a straight chain alkyl group. Described organosilicon grease is for example one or more in tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate, dimethyl diethyl silicon ester; Wherein preferred tetramethyl silicate, silicon One or more of acid tetraethyl ester, dimethyl diethyl silicon ester. The solid silicon source mentioned in the present invention is high-purity silicon dioxide solid or powder, such as white carbon black and/or high-purity silica gel. Preferably, the _SiO2 content in the solid silicon source is not less than 99.99% by weight based on dry weight, and the total mass content of Fe, Al and Na impurities in terms of elements is less than 10ppm; for example, the _SiO2 content is 99.99% ~100% by weight, usually greater than 99.99 and less than 100% by weight. The solid silicon source can be high-purity silica gel and/or white carbon black, preferably white carbon black, wherein the _SiO content in the silica gel is preferably greater than or equal to 99.99% by weight, such as greater than 99.99% by weight and less than 100% by weight, and The total mass content of Fe, Al and Na impurities is less than 10 ppm. The specific surface area of the white carbon black is preferably between 50-400m ² /g, based on the dry weight of the white carbon black, the SiO ₂ content in the white carbon black is preferably greater than or equal to 99.99% by weight, for example, 99.99- 100% by weight is, for example, greater than 99.99% by weight and less than 100% by weight, and the total mass content of Fe, Al and Na impurities in the white carbon black is less than 10 ppm. The white carbon black can be purchased commercially, or prepared according to existing methods, for example, according to the method provided by the patent CN200910227646.2. One preparation method is to obtain by combustion reaction of silicon tetrachloride with hydrogen and oxygen.

The titanium source is an organic titanium compound or an inorganic titanium compound, such as one or more of tetraalkyl titanate (Ti(alkoxy) ₄ , TiCl ₄ , Ti(SO ₄ ) ₂ and their hydrolysis products The number of carbon atoms in the alkyl group in the tetraalkyl titanate molecule is 1 to 6, for example, the number of carbon atoms is 1, 2, 3, 4, 5 or 6. Titanium source and total silicon source (also known as silicon source) molar ratio is, for example, 0.008˜0.035:1, eg, 0.01˜0.03:1 or 0.01˜0.025:1, or 0.015˜0.025:1.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the inorganic ammonium source described in step (1) is inorganic ammonium salt and/or ammonia water, and one of the inorganic ammonium salts such as ammonium chloride, ammonium nitrate and ammonium sulfate is obtained. or more. The inorganic ammonium source is preferably ammonia water, and the molar ratio of the ammonia water calculated as NH ₄ ⁺ to the titanium source calculated as TiO ₂ is 0-5:1, such as 0.01-4:1, such as 0.01-0.5:1 . Adding the inorganic quaternary ammonium salt can increase the content of titanium in the skeleton of the synthesized molecular sieve and improve the activity of the molecular sieve.

In the method for synthesizing titanium-silicon molecular sieve provided by the present invention, in step (1), titanium source, template agent, organosilicon source, inorganic ammonium source and water are mixed, and alcohol is hydrolyzed. The hydrolyzed alcohol can be stirred at 0-150°C, preferably 0-100°C, such as 50-95°C, for at least 10 minutes, so as to hydrolyze the organic silicon source and titanium source, and reduce the organic silicon source and organic titanium source in the resulting mixture. The content of alcohol (usually monohydric alcohol) produced by hydrolysis, that is, to catch alcohol after hydrolysis. Usually, the stirring time is 10 to 3000 minutes, for example, 2 to 30 hours. By hydrolyzing the alcohol, a clear and transparent organosilicon source and titanium source hydrolyzate can be obtained. Preferably, the mass content of the monohydric alcohol produced by the hydrolysis of the organic silicon source and the organic titanium source in the product obtained in step (1) does not exceed 10 ppm, preferably, the content of the monohydric alcohol in the mixture obtained in step (1) does not exceed 10 ppm ( quality).

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, in step (2), the product obtained in step (1) is aged, and the aging is to allow the product obtained in step (1) to stand at room temperature to 50° C. for 1 to 60 hours. The room temperature is 15-40°C; the aging time is 1-60 hours, such as 2-50 hours, preferably 3-30 hours, such as 3-15 hours, and no stirring is carried out during the aging process, and the material that is step (1 ) The resulting product was allowed to stand.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, in step (3), the aging product obtained in step (2) is mixed with the solid silicon source, and the molar ratio of the product obtained in step ( ₂ ) to the solid silicon source in terms of SiO is: 1:0.1~10 (that is, the molar ratio of the organosilicon source to the solid silicon source is 1:0.1~10, for example, it can be 1:1~9, 1:2~8, 1:1~7 or 1:3 ~ 6. The method provided by the present invention can use a relatively high proportion of solid silicon source, can increase the solid content of the synthesis product, thereby increasing the output of a single synthesis without changing the synthesis reactor.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the crystallization described in step (3), the crystallization temperature is 110-200°C, the crystallization pressure is autogenous pressure, and the crystallization time is 2 hours to 20 days, usually described The crystallization time is 0.5 to 20 days, for example, the crystallization time is 0.5 to 10 days, and the crystallization temperature in the further step (3) is 140 to 180°C, for example, 160 to 180°C, and the crystallization time is preferably 0.5 -10 days, for example, 1 to 6 days, further, for example, 1 to 3 days. The crystallization pressure is an autogenous pressure. The crystallization can be carried out in a stainless steel stirred tank. The crystallization temperature can be raised in one stage or in multiple stages. The heating rate can be carried out according to the existing heating method for crystallization, for example, 0.5-1° C./min. The crystallization can be carried out in a stainless steel stirred tank. In one embodiment, the crystallization temperature of the crystallization is 160-180° C., the crystallization time is 0.5-6 days, for example, 1-3 days, and the crystallization pressure is autogenous pressure. One embodiment, the crystallization described in step (3) is: crystallization at 100-130°C, for example, 110-130°C for 0.5-1.5 days, then crystallization at 160-180°C for 1-3 days, and crystallization The pressure is autogenous.

In the method for synthesizing titanium-silicon molecular sieves provided by the present invention, the recovery of titanium-silicon molecular sieves in step (3) is an existing method, including filtering, washing and roasting the crystallized product or filtering, washing, drying and roasting the crystallized product. The purpose of filtration is to separate the crystallized titanium-silicon molecular sieve from the crystallization mother liquor. The purpose of washing is to wash away the silicon-containing template agent adsorbed on the surface of the molecular sieve particles. Mix and wash at a weight ratio of 1:1-20, such as 1:(1-15), and then filter or rinse with water. The purpose of drying is to remove most of the moisture in the molecular sieve, so as to reduce the evaporation of moisture during calcination, and the drying temperature can be 100-200°C. The purpose of calcination is to remove the template agent in the molecular sieve, for example, the calcination temperature is 350-650° C., and the calcination time is 2-10 hours. The titanium-silicon molecular sieve product provided by the invention is obtained through recycling.

In the synthesis method of titanium-silicon molecular sieve provided by the present invention, the titanium-silicon molecular sieve recovered in step (3) can be further processed, that is, the synthesis method of titanium-silicon molecular sieve provided by the present invention can also include step (4):

(4) Crystallize the titanium-silicon molecular sieve obtained in step (3) in an organic alkali solution, and then recover the titanium-silicon molecular sieve. The titanium-silicon molecular sieve obtained in this process has a hollow structure, which is called molecular sieve rearrangement in the present invention. Among them _, the molar ratio of titanium silicon molecular sieve (calculated as _SiO2 ) to organic base is 1:0.02～0.5, for example, 1:0.02～0.2; the molar ratio of molecular sieve and water calculated as SiO2 is 1:2～50, such as 1 :2～30 or 1:2～20, or 1:5～10; the crystallization temperature is 120～200°C, and the time is 0.5～10 days, such as 0.5～8 days; the crystallization pressure is autogenous pressure, wherein the Described organic base is preferably organic quaternary ammonium base. Preferably, the crystallization temperature in step (4) is 150-200°C, the crystallization time is 0.5-10 days or 1-6 days, and the molar ratio of molecular sieve to water is 1:2-30. The recovery method is an existing method, which generally includes filtering, washing, drying and roasting the crystallized product, and can refer to the recovery method described in step (3). Described organic base is organic amine and/or organic quaternary ammonium base; Described organic amine is one or more in fatty amine, aromatic amine and alcohol amine, and described fatty amine (also known as fatty amine compound ), whose general formula is R ³ (NH ₂ ) _n , wherein R ³ is an alkyl or alkylene group having 1 to 4 carbon atoms, and n=1 or 2; the alcohol amine (also called alcohol in the present invention Amine compounds) whose general formula is (HOR ⁴ ) _m NH _(3-m) , wherein R ⁴ is an alkyl group with 1 to 4 carbon atoms, and m=1, 2 or 3. One or more of the aliphatic amines such as ethylamine, n-butylamine, butylenediamine or hexamethylenediamine; the aromatic amines refer to amines with an aromatic substituent, such as aniline, toluidine, One or more of p-phenylenediamine; one or more of said alcoholamines such as monoethanolamine, diethanolamine or triethanolamine. One or more of the organic quaternary ammonium bases such as tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or tetraethylammonium hydroxide. In one embodiment, the titanium-silicon molecular sieve is TS-1 molecular sieve, and the organic quaternary ammonium base is tetrapropylammonium hydroxide. In one embodiment, the titanium-silicon molecular sieve is TS-2 molecular sieve, and the organic quaternary ammonium base is tetrabutylammonium hydroxide. In one embodiment, the titanium-silicon molecular sieve is titanium-silicon beta molecular sieve (titanium-silicon β molecular sieve), and the organic quaternary ammonium base is tetraethylammonium hydroxide.

Step (4) The present invention is called molecular sieve rearrangement. This process can be carried out once or repeated one or more times. The repetition means that the titanium-silicon molecular sieve obtained by the treatment replaces the molecular sieve obtained in step (3). (4) Processing. Through rearrangement treatment, titanium-silicon molecular sieve with secondary pore structure can be obtained, and the gained titanium-silicon molecular sieve has a hollow structure, that is, the crystal grains of the titanium-silicon molecular sieve are hollow structures, and the radial length of the cavity part of the hollow crystal grains is 5-300nm, at 25°C, P/P ₀ =0.10, adsorption time 1 hour, the measured benzene adsorption amount is at least 70 mg/g, the adsorption isotherm and desorption isotherm of the low-temperature nitrogen adsorption of the molecular sieve There is a hysteresis loop between them. Molecular sieves have larger pore volume and specific surface area after rearrangement.

The following examples will further illustrate the present invention, but do not limit the present invention thereby.

The measurement method of grain size and surface silicon-titanium ratio and bulk phase silicon-titanium ratio in the embodiment adopts TEM-EDX, and TEM electron microscope experiment is carried out on the Tecnai F20G2S-TWIN type transmission electron microscope of FEI company, is equipped with Gatan company's energy filter System GIF2001, the accessory is equipped with X-ray energy spectrometer. Electron microscopy samples were prepared on microgrids with a diameter of 3 mm by means of suspension dispersion. In the embodiment, each sample randomly selects 20 particles to measure its surface silicon-titanium ratio and bulk phase silicon-titanium ratio, calculates the ratio of the surface silicon-titanium ratio and bulk phase silicon-titanium ratio, and then takes the average value of its 20 samples as the The ratio of the surface silicon-titanium ratio to the bulk silicon-titanium ratio of the sample.

XRD measurement method: The X-ray diffraction (XRD) crystal phase diagram of the sample is determined on a Siemens D5005 X-ray diffractometer, and the radiation source is CuKα (λ=1.5418 ), tube voltage 40kV, tube current 40mA, scanning speed 0.5°/min, scanning range 2θ=4°～40°.

The test method of the BET specific surface area adopts the nitrogen adsorption capacity method, and is calculated according to the BJH method. (See Petrochemical Analysis Methods (RIPP Test Method), RIPP151-90, Science Press, published in 1990)

The raw material properties used in embodiment and comparative example are as follows:

Tetrabutyl titanate, analytically pure, Sinopharm Chemical Reagent Co., Ltd.

Titanyl sulfate, analytically pure, Sinopharm Chemical Reagent Co., Ltd.

Tetrapropylammonium hydroxide, Guangdong Dayou Chemical Factory.

Tetraethyl silicate, analytically pure, Sinopharm Chemical Reagent Co., Ltd.

Ammonia water, analytically pure, concentration 20% by weight.

White carbon black, product of Zhejiang Juhua Group, model AS-150; solid content greater than 95% by weight, silicon dioxide content in dry basis greater than 99.99% by weight, total content of iron, sodium and Al less than 10ppm, specific surface area of 195m ² /g.

Other reagents that are not further specified are commercially available and analytically pure.

Comparative example 1

This comparative example illustrates the preparation of conventional titanium silicate molecular sieves according to the method of Thangaraj et al. (Zeolites, 1992, Vol. 12, pp. 943-950).

Mix 22.5g tetraethyl silicate with 7.0g tetrapropylammonium hydroxide, add 59.8g deionized water and mix evenly; then hydrolyze at 60°C for 1.0h to obtain a hydrolysis solution of tetraethyl silicate. Under the action of vigorous stirring, a solution consisting of 1.1 g of tetrabutyl titanate and 5.0 g of isopropanol was slowly dropped into the above solution, and the mixture was stirred at 75° C. for 3 h to obtain a clear and transparent colloid. Then move the colloid into a closed stainless steel reaction kettle, and crystallize at a constant temperature at 170°C for 3 days to obtain a conventional TS-1 molecular sieve. Its XRD analysis spectrum is shown in Figure 1.

Comparative example 2

The HTS molecular sieve used in this comparative example was prepared according to the patent CN98101357.0.

Mix 22.5 g of tetraethyl silicate with 9.0 g of tetrapropylammonium hydroxide, add 64.5 g of deionized water and mix evenly; then hydrolyze at 60° C. for 1.0 h to obtain a hydrolysis solution of tetraethyl silicate. Under the action of vigorous stirring, a solution consisting of 0.6 g of tetrabutyl titanate and 7.0 g of isopropanol was slowly dropped into the above solution, and the mixture was stirred at 75° C. for 7 h to obtain a clear and transparent colloid. Then move the colloid into a closed stainless steel reaction kettle, and crystallize at a constant temperature at 170°C for 3 days to obtain a conventional TS-1 molecular sieve.

Then tetrabutyl titanate, anhydrous isopropanol, tetrapropylammonium hydroxide and deionized water are uniformly mixed according to the molar ratio of 1:15:2.4:350, and hydrolyzed at 45°C for 30 minutes under normal pressure to obtain Hydrolyzed solution of tetrabutyl titanate. Take the TS-1 molecular sieve prepared above, mix it uniformly with the hydrolysis solution of tetrabutyl titanate above according to the ratio of molecular sieve (g):Ti(mol)=600:1, stir evenly at room temperature for 12 hours, and finally mix the dispersed Put the suspension into a stainless steel reaction kettle and place it at 165°C for 3 days to obtain the HTS molecular sieve. Its XRD analysis spectrum is shown in Figure 1.

Example 1

(1) 15g of tetrapropylammonium hydroxide (TPAOH) aqueous solution with a concentration of 25.05% by weight, 2.04g of tetrabutyl titanate, 8.5g of tetraethyl silicate, 2g of ammonia water with a concentration of 20% by weight and 38g of water in sequence Add it into a 500ml beaker, put it into a magnetic stirrer with heating and stirring functions, mix evenly, and stir at 80°C for 4 hours, replenish the evaporated water at any time, and obtain a colorless transparent hydrolyzate;

(2) Aging the obtained hydrolyzate at room temperature (26°C) for 12 hours to obtain an aging product;

(3) Add 9.6g of white carbon black powder to the above aging product under stirring, and stir for 1 hour after adding to form a "viscous body". After 2 days, the TS-1 sample was obtained. The obtained TS-1 sample was filtered, washed, dried at 120°C for 24 hours, and roasted at 550°C for 6 hours to obtain the titanium silicon TS-1 molecular sieve product described in the present invention. It is TS-1F1; its BET specific surface area is 426m ² /g, external area is 60m ² /g; micropore volume is 0.166mL/g, and mesopore volume is 0.086mL/g. According to XRD analysis, it has a MFI. structure, and the XRD spectrum is shown in Figure 1;

(4) Evenly mix 6 g of the TS-1F1 sample with a TPAOH aqueous solution with a concentration of 22.05% by weight. The weight ratio of the TS-1F1 to the TPAOH aqueous solution is 1:5, and crystallize in a closed reaction kettle at 150°C for 3 day, filter, wash, dry at 120°C for 24 hours, and bake at 550°C for 6 hours to obtain the rearranged TS-1 product, which is designated as TS-1P1. Its XRD analysis spectrum is shown in Figure 1. Its BET specific surface area is 457m ² /g, external area is 68m ² /g, micropore volume is 0.152mL/g, and mesopore volume is 0.168mL/g. It is a hollow structure (see Figure 3).

Example 2

(1) 7.4g of tetrapropylammonium hydroxide with a concentration of 25.05% by weight, 1.23g of tetrabutyl titanate, 4.16g of tetraethyl silicate, 0.67g of aqueous ammonia with a concentration of 20% by weight and 14g of water were added to the Put it into a 500ml beaker, put it on a magnetic stirrer with heating and stirring functions, mix evenly, and stir at 90°C for 1 hour, replenish the evaporated water at any time, and obtain a colorless transparent alkaline hydrolyzate.

(2) standing the obtained hydrolyzate at room temperature for 3 hours to obtain an aging product;

(3) Slowly add 9.6g of white carbon black powder to the obtained aging product under stirring, stir for 1.5 hours after the addition, transfer it to a stainless steel airtight reaction kettle, crystallize at a constant temperature of 145°C for 6 days, filter and wash , dried at 120°C for 24 hours and calcined at 550°C for 6 hours to obtain a TS-1 molecular sieve sample, denoted as TS-1F2, with a specific surface area of 435m ² /g, an external area of 61m ² /g, and a micropore volume of 0.159mL /g, the mesopore volume is 0.083mL/g; the XRD analysis spectrum has the characteristics as shown in Figure 1

(4) Mix 6g of TS-1F2 sample with 36g of 22.05% TPAOH aqueous solution evenly, crystallize in a closed reaction kettle at 150°C for 3 days, filter, wash, dry at 120°C for 24 hours, and roast at 550°C for 6 hours , to obtain TS-1 molecular sieve products, denoted as TS-1P2. Its XRD analysis spectrum has the characteristics shown in Figure 1. The BET specific surface area is 429m ² /g, the external area is 60m ² /g, the micropore volume is 0.150mL/g, and the mesopore volume is 0.177mL/g; it is a hollow structure in the transmission electron micrograph.

Example 3

(1) 43g of 25.05% tetrapropylammonium bromide (TPABr) aqueous solution, 1.68g of titanyl sulfate, 2.4g of triethylamine, 33.3g of tetraethyl silicate, and 0.05g of 20% by weight ammonia water and 26g of water were sequentially added to a 500ml beaker, put into a magnetic stirrer with heating and stirring functions to mix evenly, and stirred at 65°C for 3 hours, replenishing evaporated water at any time to obtain an alkaline hydrolyzate.

(2) The obtained hydrolyzate was left to stand at room temperature for 9 hours to obtain an aged product.

(3) In the beaker containing the aging product, slowly add 9.6g of white carbon black powder under stirring, and stir for one hour to form a relatively uniform "viscous body". Crystallize at constant temperature for 2 days, filter, wash, dry at 120°C for 24 hours, and calcine at 550°C for 6 hours to obtain the TS-1 molecular sieve product provided by the present invention, denoted as TS-1F3, with a specific surface area of 427m ² /g , the external area is 60m ² /g, the micropore volume is 0.173mL/g, and the mesopore volume is 0.079mL/g

(4) Mix 6g of TS-1F3 sample with 40g of 22.05% TPAOH aqueous solution, stir evenly, crystallize in a closed reaction kettle at 150°C for 3 days, filter, wash, dry at 120°C for 24 hours, and roast at 550°C for 6 Hours, the hollow TS-1 sample can be obtained, denoted as TS-1P3, its BET specific surface area is 438m ² /g, external area is 59m ² /g, micropore volume is 0.162mL/g, mesopore volume is 0.183mL/g . It is a hollow structure in the transmission electron micrograph.

Embodiment 4～7

Titanium-silicon molecular sieves were prepared according to the method of Example 1, and their proportions, synthesis conditions and results are shown in Table 1. Refer to Example 1 for other conditions.

Example 8

According to the method of Example 1, the difference is that no ammonium source is added.

Example 9

According to the method of Example 1, the difference is that in step (3), first crystallize at 120° C. for 1 day, and then crystallize at 170° C. for 2 days. See Table 1 for the ratio, synthesis conditions and results.

Example 10

Prepare TS-2 molecular sieve. Referring to the method in Example 1, the ratio and template were changed. The template used was tetrabutylammonium hydroxide (TBAOH). The ratio, synthesis conditions and results are shown in Table 1.

Example 11

Preparation of Ti-β molecular sieves. Referring to the method of Example 1, the proportion and template were changed. The template used was tetrabutylammonium hydroxide (TEAOH). The proportion, synthesis conditions and results are shown in Table 1. Its SEM picture is shown in Figure 4

Comparative example 1

According to the method of embodiment 1, the difference is that ammonia water is not added, and aging is not carried out.

Comparative example 2

According to the method of Example 1, the difference is that the aging temperature is 75°C.

Comparative example 3

According to the method of Example 1, the difference is that the solid silicon source is added in step (1).

Example 12

This example illustrates the reaction effect of the example sample provided by the present invention and the sample prepared in the comparative example for the preparation of hydroquinone by oxidative phenol hydroxylation and the preparation of cyclohexanone oxime by ammoximation of cyclohexanone.

The reagents used in this example are commercially available chemically pure reagents, and the concentration of each substance after the reaction is quantitatively analyzed by gas chromatography. The 6890 type gas chromatograph produced by Agilent Company used; the analytical chromatographic column used is FFAP column.

The conversion rate of phenol, the conversion rate of cyclohexanone, the selectivity of cyclohexanone oxime are calculated according to the following formula respectively in the embodiment:

Take 1.25g of the samples (unrearranged) prepared in the above-mentioned Examples 1-9 and Comparative Example respectively and add them to a three-neck flask reaction vessel containing 25g of phenol and 20ml of acetone. After the temperature stabilizes to the set value, add hydrogen peroxide 9.81 g (concentration 30% by weight), (phenol:hydrogen peroxide (H ₂ O ₂ ) molar ratio is 3), at a temperature of 80°C and a pressure of 0.1MPa (atmospheric pressure), sampling after 2 hours of reaction, phenol undergoes hydroxylation reaction to generate benzene diphenols.

Take the titanium-silicon molecular sieves in the above-mentioned comparative examples and examples to prepare samples, and uniformly stir and mix in the slurry bed according to the mass ratio of TS-1 molecular sieve: tert-butanol: 25% by weight ammonia water = 1:7.5:7.5, TS-1 The consumption of 1 molecular sieve is 3.2g. Warm up to 75°C, then add 30% by weight hydrogen peroxide at a rate of 6ml/h at this temperature, and add a mixture of cyclohexanone and tert-butanol at a rate of 8.6ml/h (the volume ratio of cyclohexanone and tert-butanol 1:2.5), while adding 25% by weight ammonia solution at a rate of 6ml/h, the volumetric space velocity is 6.4h ^-1 . The above three stocks of materials were added at the same time, and the materials were continuously discharged at the corresponding speed at the same time. The reaction was stable for 4 hours, and the samples were analyzed. The results are shown in Table 2.

Hydrogen peroxide decomposition test

Take 15 grams of hydrogen peroxide with an H ₂ O ₂ concentration of 30% by weight, add 2 grams of titanium-silicon molecular sieve, stir at 80° C. for 1 hour, and analyze the concentration of hydrogen peroxide. The results are shown in Table 2.

It can be seen from Table 2 that under the same conditions, the molecular sieve provided by the present invention has a lower hydrogen peroxide decomposition rate, thereby improving the utilization rate of hydrogen peroxide in the oxidation reaction in which hydrogen peroxide participates, and improving the conversion rate of reactants.

Fig. 4 is the curve of the concentration of hydrogen peroxide in the hydrogen peroxide decomposition test of the TS-1 molecular sieve synthesized in Example 6 and the existing method (the unrearranged molecular sieve obtained in step 3) as a function of time.

It can be seen from Table 1 that the phenol hydroxylation and cyclohexanone activities of the sample obtained in the present invention are significantly higher than those of the conventional TS-1 molecular sieve of the comparative sample.

It should be noted that any combination of various implementations of the present invention can also be made, as long as they do not violate the idea of the present invention, they should also be regarded as the content disclosed in the present invention.

Claims (47)

1. A titanium-silicon molecular sieve, characterized in that, the ratio of the surface silicon-titanium ratio of the titanium-silicon molecular sieve grain to the bulk phase silicon-titanium ratio is 1.2 ~ 5, and the surface silicon-titanium ratio is no more than The silicon-titanium ratio of 5nm atomic layer; The preparation method of described titanium-silicon molecular sieve comprises the steps: (1) Mix titanium source, templating agent, organosilicon source, water and optional inorganic ammonium source, and hydrolyze alcohol; (2) Aging the product obtained in step (1) at room temperature to 50°C; (3) Mix the aging product obtained in step (2) with the solid silicon source evenly, and then crystallize in a closed reactor to recover titanium-silicon molecular sieves; the weight ratio of the aging product obtained in step (2) to the solid silicon source 1:0.1~10, wherein in the weight ratio, the aging product obtained in the step (2) is calculated as SiO ₂ , and the solid silicon source is calculated as SiO ₂ . 2. The titanium-silicon molecular sieve according to claim 1, wherein the ratio of the surface silicon-titanium ratio to the bulk silicon-titanium ratio is 1.2 to 4:1. 3. according to the described titanium-silicon molecular sieve of claim 1, it is characterized in that, the titanium-silicon ratio molar ratio of described titanium-silicon molecular sieve is 0.005～0.03:1. 4. The titanium-silicon molecular sieve according to claim 1, wherein the titanium-silicon molecular sieve is TS-1 molecular sieve, TS-2 molecular sieve or Ti-β molecular sieve. 5. According to the titanium-silicon molecular sieve according to any one of claims 1 to 4, it is characterized in that the crystal grain of the titanium-silicon molecular sieve is a hollow structure, and the radial length of the cavity part of the hollow crystal grain is 5-300nm , at 25°C, P/P ₀ =0.10, and the adsorption time of 1 hour, the measured benzene adsorption amount is at least 70 mg/g. hysteresis loop. 6. The titanium-silicon molecular sieve according to claim 1, wherein the titanium-silicon molar ratio of the titanium-silicon molecular sieve is 0.01˜0.025:1. 7. a synthetic method of titanium silicon molecular sieve, comprises the following steps: (1) Mix titanium source, templating agent, organosilicon source, water and optional inorganic ammonium source, and hydrolyze alcohol; (2) Aging the product obtained in step (1) at room temperature to 50°C; (3) Mix the aging product obtained in step (2) with the solid silicon source evenly, and then crystallize in a closed reactor to recover titanium-silicon molecular sieves; the weight ratio of the aging product obtained in step (2) to the solid silicon source 1:0.1~10, wherein in the weight ratio, the aging product obtained in the step (2) is calculated as SiO ₂ , and the solid silicon source is calculated as SiO ₂ . 8. The method according to claim 7, wherein the aging in step (2) is to leave the product obtained in step (1) at room temperature to 50°C for 1 to 60 hours; The weight ratio of the aging product obtained in the step (2) in the step (3) to the solid silicon source is 1:0.1~10, wherein in the weight ratio, the aging product obtained in the step (2) is _SiO2 , the solid silicon source is _SiO2 ; Inorganic ammonium source: the molar ratio of titanium source is 0~5:1; the molar ratio of water to total silicon source is 5~100:1; the molar ratio of template agent to total silicon source is 0.05~0.5:1; The molar ratio of the total silicon source is 0.005~0.05:1; Wherein, the total silicon source is the sum of the organic silicon source calculated as _SiO2 and the solid silicon source calculated as _SiO2 , and the inorganic ammonium source is calculated as _NH4 ⁺ ; The titanium source is calculated as TiO ₂ ; the inorganic ammonium source is inorganic ammonium salt and/or ammonia water. 9. according to the described method of claim 8, it is characterized in that, the molar ratio of described titanium source and total silicon source is 0.005～0.04:1. 10. according to the described method of claim 8, it is characterized in that, the molar ratio of described templating agent and described total silicon source is 0.05～0.3:1. 11. according to the described method of claim 8, it is characterized in that, the molar ratio of water and total silicon source is 5～50. 12. according to the described method of claim 8, it is characterized in that, the molar ratio of inorganic ammonium source and titanium source is 0.01～4:1. 13. The method according to claim 8, wherein the molar ratio of the organosilicon source to the solid silicon source is 1:1-9. 14. The method according to claim 7, characterized in that, in step (3), the crystallization temperature is 110-200°C, the crystallization pressure is autogenous pressure, and the crystallization time is 2 hours-20 sky. 15. The method according to claim 14, characterized in that the crystallization temperature of the crystallization in step (3) is 140-180°C. 16. The method according to claim 7, wherein the crystallization in step (3) is: crystallization at 100-130°C for 0.5-1.5 days, and then crystallization at 160-180°C for 1-3 days Day, crystallization pressure is autogenous pressure. 17. according to the described method of claim 7, it is characterized in that, described templating agent is organic base or is organic base and organic quaternary ammonium salt; Described organosilicon source is organosilicon grease, and described organosilicon ester , whose general formula is Si(OR ¹ ) ₄ , R ¹ is selected from alkyl groups with 1 to 6 carbon atoms, and the alkyl groups are branched or linear; the solid silicon source is high-purity Silica granules or silica powder, based on dry weight, the _SiO2 content of the solid silicon source is greater than 99.99% by weight, the total content of Fe, Al and Na in atomic terms is less than 10ppm, and the titanium The source is an organic titanium source and/or an inorganic titanium source. 18. The method according to claim 7, characterized in that, in step (1), the templating agent includes an organic quaternary ammonium base and an optional organic amine and/or an organic quaternary ammonium salt, wherein the organic quaternary ammonium The molar ratio of base to organic amine is 1:0~10, and the molar ratio of organic quaternary ammonium base to organic quaternary ammonium salt is 1:0~10. 19. according to the described method of claim 17, it is characterized in that, described organic silicon ester is tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate, dimethyl diethyl silicon ester one or more. 20. The method according to claim 7, wherein the solid silicon source is white carbon black, and the specific surface area of the white carbon black is 50-400m ² /g. 21. according to the described method of claim 18, it is characterized in that, described organic amine is one or more in aliphatic amine, aromatic amine and alcohol amine; The general formula of described aliphatic amine is R ³ (NH ₂ ) _n , wherein R ³ is an alkyl or alkylene group having 1 to 4 carbon atoms, n=1 or 2; the general formula of the alcohol amine is (HOR ⁴ ) _m NH _(3-m) , Wherein R is an alkyl group with 1 to 4 carbon atoms, m=1, 2 or 3; the aromatic amine is an amine with an aromatic substituent, and the organic quaternary ammonium base ^is tetrapropylhydrogen One or more of ammonium oxide, tetrabutylammonium hydroxide or tetraethylammonium hydroxide. 22. according to the described method of claim 21, it is characterized in that, described aliphatic amine is one or more in ethylamine, n-butylamine, butanediamine or hexamethylenediamine; Described alcohol amine is mono One or more of ethanolamine, diethanolamine or triethanolamine; the aromatic amine is one or more of aniline, toluidine, p-phenylenediamine. 23. according to the described method of claim 7, it is characterized in that, described titanium silicon molecular sieve is TS-1 molecular sieve, and described templating agent is tetrapropyl ammonium hydroxide or is tetrapropyl ammonium hydroxide and is selected from A mixture of one or more of organic amines, tetrapropylammonium chloride, and tetrapropylammonium bromide; or, the titanium-silicon molecular sieve is TS-2 molecular sieve, and the template agent is tetrabutylhydrogen Ammonium oxide is either a mixture of tetrabutylammonium hydroxide and one or more selected from organic amines, tetrabutylammonium chloride, and tetrabutylammonium bromide; or, the titanium silicon molecular sieve is Ti- β molecular sieve, the template agent is tetraethylammonium hydroxide or tetraethylammonium hydroxide and one or more selected from organic amines, tetraethylammonium chloride, tetraethylammonium bromide mixture. 24. The method according to claim 7, characterized in that the hydrolysis of alcohol in step (1) is carried out by stirring at 0-150°C for at least 10 minutes. 25. The method according to claim 7, characterized in that, in step (1), the alcohol is hydrolyzed, the stirring temperature is 50-95°C, and the stirring time is 2-30 hours. 26. The method according to claim 7, characterized in that the mass content of the alcohol produced by the hydrolysis of the organic silicon source and the organic titanium source in the product obtained in step (1) does not exceed 10 ppm. 27. The method according to claim 7, characterized in that the aging time in step (2) is 2-50 hours. 28. The method according to any one of claims 7-27, characterized in that the method further comprises step (4): crystallizing the titanium-silicon molecular sieve obtained in step (3) in an organic alkali aqueous solution for 0.5- 10 days, _{the crystallization temperature is 110~200°C; wherein the molar ratio of the titanium-silicon molecular sieve to the organic base is 1:0.02-0.5 in terms of SiO 2 ,} and the titanium-silicon molecular sieve is in the The molar ratio of water is 1:2~50; the organic base is organic quaternary ammonium base and/or organic amine. 29. The method according to claim 28, wherein the crystallization temperature in step (4) is 150-200°C, the molar ratio of titanium-silicon molecular sieve to water is 1:2-30, and the pressure is autogenous pressure . 30. The method according to claim 7, wherein the titanium source is one of tetraalkyl titanate Ti(alkoxy) ₄ , TiCl ₄ , Ti(SO ₄ ) ₂ and their hydrolysis products One or more, wherein the number of carbon atoms in the alkyl group in the tetraalkyl titanate is 1, 2, 3, 4, 5 or 6. 31. The method according to claim 7, characterized in that the mass content of monohydric alcohol in the product obtained by hydrolyzing alcohol in step (1) does not exceed 10 ppm. 32. The method according to claim 7, characterized in that the aging in step (2) is standing at room temperature ~50°C for 1~60 hours. 33. The method according to claim 32, wherein the standing time is 2 to 50 hours. 34. The method according to claim 8, wherein the molar ratio of the titanium source to the total silicon source is 0.01-0.03:1. 35. The method according to claim 8, wherein the molar ratio of the titanium source to the total silicon source is 0.01-0.025:1. 36. The method according to claim 8, wherein the molar ratio of the template agent to the total silicon source is 0.05-0.25:1. 37. The method according to claim 8, wherein the molar ratio of the template agent to the total silicon source is 0.05-0.2:1. 38. The method according to claim 11, wherein the molar ratio of water to the total silicon source is 6-30:1. 39. The method according to claim 8, wherein the molar ratio of the inorganic ammonium source to the titanium source is 0.05-0.5:1. 40. The method according to claim 8, wherein the molar ratio of the organosilicon source to the solid silicon source is 1:2-8. 41. The method according to claim 14, characterized in that the crystallization in step (3) takes 0.5-10 days. 42. The method according to claim 14, characterized in that the crystallization temperature of the crystallization in step (3) is 160-180°C. 43. The method according to claim 7, characterized in that the aging time in step (2) is 3-30 hours. 44. The method according to claim 7, wherein the aging time of step (2) is 3-15 hours. 45. The method according to claim 32, wherein the standing time is 3 to 30 hours. 46. The method according to claim 32, wherein the standing time is 3 to 15 hours. 47. The method according to claim 8, wherein the molar ratio of water to the total silicon source is 6-15:1.