CN111085264B - Monolithic modified TS-1 catalyst based on carbon porous ceramic, and preparation method and application thereof - Google Patents

Abstract

The invention discloses a preparation method of a carbon porous ceramic-based integral modified TS-1 catalyst, which comprises the following steps: soaking the carbon porous ceramic in the modified TS-1 glue solution according to the proportion that the modified TS-1 glue solution completely immerses the carbon porous ceramic, taking out the carbon porous ceramic after soaking, draining off surface liquid, placing the carbon porous ceramic on the liquid surface in a pressure reactor filled with ammonia or amine solution, heating for keeping reaction, cooling to room temperature, taking out the carbon porous ceramic, drying, heating for roasting, cooling to room temperature, and taking out to obtain the integral modified TS-1 catalyst. The catalyst is piled up to a certain height when in use, keeps good strength, cannot be cracked, and cannot be extruded and deformed mutually; the catalyst also has a good lifetime and catalytic activity and selectivity do not decay over long runs.

Description

Integral modified TS-1 catalyst based on carbon porous ceramics and its preparation method and application

technical field

The invention belongs to the technical field of catalyst preparation, and in particular relates to a monolithic modified TS-1 catalyst and its preparation method and application.

Background technique

Propylene oxide is an important chemical raw material, which is used in the synthesis of polyether polyol, propylene glycol, propylene glycol ether, dimethyl carbonate, polypropylene carbonate, nonionic surfactant, etc. It is an essential raw material for the polyurethane industry. It plays an important role in the chemical industry.

The demand for propylene oxide is increasing year by year, especially with the rapid development of my country's economy and technology, higher requirements are put forward for the safety, cleanliness and efficiency of propylene oxide production technology. For many years, the production method of propylene oxide in my country has been dominated by the highly polluting chlorohydrin method, which has brought great pressure on the environment. However, the use of the chlorohydrin method has been strictly prohibited in developed countries such as Europe and the United States. In recent years, my country has gradually banned the use of chlorohydrins to produce propylene oxide. Although the co-oxidation method is advanced in technology, it also has shortcomings such as a high proportion of co-production products, a large amount of organic sewage treatment, high energy consumption, high investment costs, and high transfer costs for technology mastered abroad. One-step direct oxidation of propylene to prepare propylene oxide is a clean and economical technological route, and my country also advocates the use of this method to produce propylene oxide. The catalyst used in the one-step direct oxidation method is mainly TS-1 catalyst. After years of research, TS-1 catalyst has made important progress, and its activity and selectivity have reached a good level. However, TS-1 has The extremely small particles of nanopores, in the process of industrialization, there is a bottleneck problem that it is extremely difficult to separate the tiny particles from the liquid. Although there are abundant literature reports on methods for TS-1 molding and synergizing, such as spray drying granulation method, extrusion molding granulation method, carrier surface coating method, hollow microsphere method, etc., all of them have decreased activity and selectivity. Obvious problems that slow down the process of industrialization. Although suitable reactors are also used to make up for the lack of catalysts for these shaped and synergized catalysts, such as semi-continuous tank reactors, continuous tank reactors, fixed-bed reactors, etc., but they cannot fundamentally solve the problem. .

Contents of the invention

The first object of the present invention is to provide a kind of monolithic modified TS-1 catalyst, solve the existing catalyst problem of one-step direct oxidation of propylene to prepare propylene oxide, use this catalyst to greatly improve the yield of main product propylene oxide Selectivity, greatly improving production efficiency and reducing production costs.

The second object of the present invention is to provide a method for preparing the monolithic modified TS-1 catalyst.

The third object of the present invention is to provide an application of the monolithic modified TS-1 catalyst in the preparation of propylene oxide by the direct oxidation of propylene, adopting the continuous operation of the fixed bed reactor to solve the problem of catalyst and reaction solution Separation issues.

In order to achieve the above object, the technical scheme adopted in the present invention is as follows:

The first aspect of the present invention provides a monolithic modified TS-1 catalyst. The structure of the catalyst is a cylindrical structure with a diameter of 3 mm to 100 mm and a height of 2 mm to 50 mm. The catalyst contains three-dimensional channels that communicate with each other. , the average pore diameter of the three-dimensional channel is 0.1μm~0.75mm; the micro-mesopore diameter of the TS-1 layer on the surface of the channel is 0.5~50nm, the BET specific surface area is 120~300m ² /g, and the pore volume is 0.1~15cm ³ /g .

A second aspect of the present invention provides a method for preparing the monolithic modified TS-1 catalyst, comprising the following steps:

Soak the carbon porous ceramics in the modified TS-1 glue solution. The ratio of the two is based on the fact that the modified TS-1 glue solution completely immerses the carbon porous ceramics. After soaking, take out the surface liquid and place it in a container filled with ammonia or amine The solution is above the liquid level in the pressure reactor, heated to maintain the reaction, lowered to room temperature, taken out the carbon porous ceramics, dried and then heated up for roasting, and taken out after lowered to room temperature to obtain the integrally modified TS-1 catalyst.

The carbon porous ceramic is soaked in the modified TS-1 glue solution at a temperature of 25° C. to 85° C. for 3 minutes to 60 minutes; preferably: a temperature of 45° C. to 65° C. and a time of 15 minutes to 40 minutes.

The amine solution is an aqueous solution of at least one of methylamine, ethylamine, ethylenediamine, n-propylamine, isopropylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, preferably trimethylamine, triethylamine An aqueous solution of at least one of amine, dimethylamine, and isopropylamine; the concentration of the ammonia or amine solution is 0.25% to 25%.

The ammonia solution is ammonia water.

The heating and maintaining reaction temperature is 125°C-195°C, and the time is 10h-80h.

After the drying, the temperature is raised for roasting, the drying temperature is 100-120°C, and the time is 1-10h, preferably, the temperature is 105°C, and the time is 5h; the roasting temperature is 450°C-650°C, and the time is 2h-8h .

The preparation method of the carbon porous ceramic comprises the following steps:

After cutting the cleaned porous ceramics, immerse them in the metal salt solution. The ratio of the porous ceramics to the metal salt solution is based on the solution that can immerse the porous ceramics. Take it out and dry it in the _N2 airflow. Keep it under the mixed air flow for a period of time, and cool down to room temperature to obtain the carbon porous ceramic.

The clean porous ceramics are washed with clean water for at least three times and dried to remove possible ash impurities and the like.

The porous ceramic is a channel containing an interpenetrating three-dimensional network-like open-pore structure inside, and the size of the channel is 0.1 μm to 0.75 mm, preferably 0.5 μm to 0.55 mm; the structure of the porous ceramic has a diameter of 3 mm to 100 mm, A cylindrical structure with a height of 2mm to 50mm.

_The porous ceramics are mainly made of corundum sand, silicon carbide, cordierite and other raw materials, which are obtained through molding, foaming, and sintering. They can be purchased from the market or customized from manufacturers. ₂ O ₃ , CaO, MgO, Na ₂ O, TiO ₂ , etc., the ratio among them is determined according to the production ratio of the porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the present invention.

The metal ion in the metal salt solution is at least one of Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Ni ²⁺ , and Cu ²⁺ , and the anion paired with the metal ion is formate (HCOO ^- ), acetic acid Root (CH ₃ COO ^- ), propionate (CH ₃ CH ₂ COO ^- ), citrate, lactate, PO ₄ ^3- , Cl ^- , Br ^- , NO ₃ ^- , SO ₄ ^2- ; concentration of metal salt solution 0.15%-20%; the solvent in the metal salt solution is water and acetic acid; the metal salt is preferably at least one of ferrous acetate, nickel nitrate, cobalt citrate, copper nitrate and copper phosphate.

The cleaned porous ceramics are cut and soaked in a metal salt solution at a temperature of 15° C. to 80° C. for 5 minutes to 12 hours.

The drying temperature in the N ₂ airflow is 100-120° C., and the drying time is 2-5 hours.

The temperature of the heating-up calcination is 180°C-550°C, and the time is 1h-7h.

The temperature for continuing to heat up is 325°C to 750°C.

Said keeping under the mixed gas flow for a period of time is: switch _N2 to _H2 and _N2 mixed gas, the flow ratio of _H2 to _N2 is 0.1-50, the feeding time is 30min-5h, switch the gas to N _2. Adjust the temperature to 350-900°C, the time is 1min-200min, switch _N2 to a mixture of small molecular substances containing C, H and O and _N2 , and the small molecular substances containing C, H and O and The flow ratio of N ₂ is 0.1-10, and the feeding time is 1 min-200 min.

The small molecular substances containing C, H and O are methane, ethane, acetylene, ethylene, propylene, propyne, methanol, ethanol, acetone, benzene, toluene, ethylbenzene, preferably ethane, propane, acetylene, ethylene , propylene, propyne, ethanol, benzene.

The preparation method of described modified TS-1 glue comprises the following steps:

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature to form a gel to obtain a modified TS-1 glue; the tetraalkyl silicate: functionalized trialkoxysilane: template agent: pH regulator: tetraalkyl titanate: alcohol: H The molar ratio of ₂ O is (0.5～1.5):(0.001～0.15):(0.15～0.55):(0.01～0.2):(0.01～0.15):(0.5～2.5):(15～25).

The templating agent is tetrapropylammonium hydroxide and tetrapropylammonium bromide.

The pH regulator is ammonia water, methylamine, ethylamine, ethylenediamine, trimethylamine, n-propylamine, isopropylamine.

The tetraalkyl silicate is tetramethyl silicate, tetraethyl silicate, tetraisopropyl silicate, tetra-n-propyl silicate.

The functionalized trialkoxysilane is vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-( β-aminoethyl) aminopropyl trimethoxysilane, γ-(β-aminoethyl) aminopropyl triethoxysilane, γ-semicarbazide propyl trimethoxysilane, γ-semicarbazide propyl trimethoxysilane Ethoxysilane.

The tetraalkyl titanate is tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate.

Described alcohol is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol.

The time for stirring at room temperature to form a gel is 2 hours to 10 hours.

The third aspect of the present invention provides an application of the monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene.

Said application includes the following steps:

Pack the prepared monolithic modified TS-1 catalyst in a fixed bed reactor, feed propylene, solvent, and hydrogen peroxide into the reactor, and the flow ratio of propylene, solvent, and hydrogen peroxide is 1:(1～11):( 0.5～2), the space velocity LHSV of the reactor is 200～1000h ^-1 , the temperature of the reactor is controlled at 30℃～90℃, the temperature of the fixed bed is controlled at 30℃～90℃, and the material reacts in the catalyst bed , the mixture generated by the reaction is discharged from the reactor, and the discharged mixture obtains pure propylene oxide through subsequent separation. During the reaction, sampling and analysis are taken from the outlet of the reactor, and the conversion rate (98.5～99.8%) of hydrogen peroxide is calculated to form a ring The selectivity of oxypropane (93.5～98.5%).

The solvent is at least one of acetonitrile, acetone, dioxane, methanol and ethanol.

The concentration of the hydrogen peroxide is 30%-70%.

Owing to adopting above-mentioned technical scheme, the present invention has following advantage and beneficial effect:

The monolithic modified TS-1 catalyst provided by the present invention is packed in a designed fixed-bed reactor through repeated experiments and comparative optimization, and the reactants propylene, hydrogen peroxide and solvent are respectively continuously Adding a fixed bed reactor, controlling the catalyst bed at a certain temperature, propylene is directly oxidized by hydrogen peroxide under the action of the catalyst in the fixed bed to generate propylene oxide. Due to the synergy of the catalyst, the change of the operation mode, and the optimization of the operating conditions, the liquid material flowing out of the fixed bed reactor has been separated from the catalyst, and only contains the product propylene oxide, unreacted propylene, hydrogen peroxide and solvent, and also contains a small amount The hydration of propylene oxide produces propylene glycol. The effluent mixture is first passed through a separation tower to separate low-boiling point propylene, propylene oxide from high-boiling point water, solvent, and by-product propylene glycol. Propylene is separated from propylene oxide to obtain propylene oxide with a purity that meets the requirements, and the separated propylene is returned to the feed port of the reactor for recycling. The solvent with higher boiling point, water and propylene glycol are rectified and separated, and the solvent with the required purity is returned to the reactor inlet for recycling, and the propylene glycol with the required purity is sold as a by-product, and the water with the required purity can be used as industrial water or recycled The heat therein will be discharged after reaching the standard, which solves the difficult problems in the existing propylene oxide production technology.

The monolithic modified TS-1 catalyst provided by the present invention has a certain dimension and can be used to pack into a fixed bed to form a bed of a certain height. When carrying out catalytic reactions, propylene, hydrogen peroxide and solvents, etc. Materials can flow through the catalyst bed smoothly without large pressure drop. When the material flows through the catalyst bed, the reaction materials such as propylene and hydrogen peroxide can easily enter the pores of the catalyst, and undergo adsorption-activation-reaction on the surface of the pores, and the products can be desorbed in time and diffuse to the outside of the catalyst, and are fixed with the main flow In addition, the catalyst is piled up to a certain height and maintains good strength without being broken or squeezed and deformed; the catalyst also has a good lifespan. After a long period of operation, the catalytic activity and selectivity will not decay. .

detailed description

In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

Example 1

Cut the porous ceramics with a pore size of 0.1 μm into a cylindrical structure with a diameter of 3 mm and a height of 5 mm, rinse the porous ceramics with clean water at least three times, and dry them to remove possible ash impurities, etc. The porous ceramics contain an interpenetrating three-dimensional network The channels of the open-pore structure are made of corundum sand, silicon carbide, cordierite and other raw materials, which are obtained through molding, foaming, and sintering. They can be purchased from the market or customized from manufacturers. The main chemical composition is SiO _2. Al ₂ O ₃ , CaO, MgO, Na ₂ O, TiO ₂ , etc. The ratio among them is determined according to the production ratio of the porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the present invention. Soak in 0.15% ferrous acetate aqueous solution, the soaking temperature is 15°C, and the soaking time is 5min. Take it out, dry it in the air, put it in a tube-type high-temperature furnace, dry it at 105°C in _N2 flow for 2h, raise the temperature to 180°C, and roast it for 1h; raise the temperature to 375°C, switch _N2 to _H2 and mix _N2 Gas, the flow rate ratio of _H2 and _N2 is 0.1, and the feeding time is 30 minutes; the gas is switched to _N2 , the temperature is adjusted to 350 ° C, and the time is 45 minutes, so that the metal is reduced to fine particles and attached to the porous ceramic surface; Switch _N2 to a mixture of methane and _N2 , the flow ratio of methane to _N2 is 0.1, and the feeding time is 1min; a layer of carbon substance is formed and attached to the surface of the porous ceramic channel. After analysis, the carbon substance is graphene A mixture of carbon nanofibers, carbon nanotubes, and graphene sheets in the structure is cooled to obtain carbon porous ceramics.

Example 2

Cut the porous ceramics with a channel size of 0.75 mm into a cylindrical structure with a diameter of 5 mm and a height of 5 mm, rinse the porous ceramics with clean water at least three times, and dry them to remove possible ash impurities, etc. The porous ceramics contain an interpenetrating three-dimensional network The channels of the open-pore structure are made of corundum sand, silicon carbide, cordierite and other raw materials, which are obtained through molding, foaming, and sintering. They can be purchased from the market or customized from manufacturers. The main chemical composition is SiO _2. Al ₂ O ₃ , CaO, MgO, Na ₂ O, TiO ₂ , etc. The ratio among them is determined according to the production ratio of the porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the present invention. Soak in 20% nickel nitrate aqueous solution, the soaking temperature is 75°C, and the soaking time is 12h. Take it out, dry it in the air, put it in a tube-type high-temperature furnace, dry it at 105°C in _N2 flow for 5h, raise the temperature to 350°C, and roast it for 7h; raise the temperature to 750°C, switch _N2 to _H2 and mix _N2 Gas, the flow ratio of _H2 and _N2 is 50, and the feeding time is 5h; the gas is switched to _N2 , the temperature is adjusted to 900°C, and the time is 50min, so that the metal is reduced to fine particles and attached to the porous ceramic surface; Switch _N2 to a mixture of acetylene and _N2 , the flow ratio of acetylene to _N2 is 10, and the feeding time is 200 minutes; a layer of carbon substance is formed and attached to the surface of the porous ceramic channel. After analysis, the carbon substance is graphene A mixture of carbon nanofibers, carbon nanotubes, and graphene sheets in the structure is cooled to obtain carbon porous ceramics.

Example 3

Cut the porous ceramics with a channel size of 0.55 mm into a cylindrical structure with a diameter of 5 mm and a height of 5 mm, rinse the porous ceramics with clean water at least three times, and dry them to remove possible ash impurities, etc. The porous ceramics contain an interpenetrating three-dimensional network The channels of the open-pore structure are made of corundum sand, silicon carbide, cordierite and other raw materials, which are obtained through molding, foaming, and sintering. They can be purchased from the market or customized from manufacturers. The main chemical composition is SiO _2. Al ₂ O ₃ , CaO, MgO, Na ₂ O, TiO ₂ , etc. The ratio among them is determined according to the production ratio of the porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the present invention. Soak in 5% cobalt citrate aqueous solution, the soaking temperature is 45°C, and the soaking time is 1h. Take it out, dry it in the air, put it in a tube-type high-temperature furnace, dry it at 105°C in _N2 flow for 3h, raise the temperature to 450°C, and bake it for 3h; raise the temperature to 550°C, switch _N2 to _H2 and mix _N2 Gas, the flow ratio of _H2 and _N2 is 25, and the feeding time is 2.5h; switch the gas to _N2 , adjust the temperature to 480°C, and the time is 65min, so that the metal is reduced to fine particles and attached to the porous ceramic surface ;Switch _N2 to the mixed gas of ethylene and _N2 , the flow ratio of ethylene and _N2 is 0.5, and the feeding time is 40min; a layer of carbon substance is formed and attached to the surface of the porous ceramic channel. After analysis, the carbon substance is graphite Carbon nanofibers, carbon nanotubes, and graphene sheet mixtures of ene structures are cooled to obtain carbon porous ceramics.

Example 4

Cut the porous ceramics with a channel size of 0.15 mm into a cylindrical structure with a diameter of 5 mm and a height of 5 mm, rinse the porous ceramics with clean water at least three times, and dry them to remove possible ash impurities, etc. The porous ceramics contain an interpenetrating three-dimensional network The channels of the open-pore structure are made of corundum sand, silicon carbide, cordierite and other raw materials, which are obtained through molding, foaming, and sintering. They can be purchased from the market or customized from manufacturers. The main chemical composition is SiO _2. Al ₂ O ₃ , CaO, MgO, Na ₂ O, TiO ₂ , etc. The ratio among them is determined according to the production ratio of the porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the present invention. Soak in 7.5% copper nitrate aqueous solution, the soaking temperature is 50°C, and the soaking time is 2h. Take it out, dry it in the air, put it in a tube-type high-temperature furnace, dry it at 105°C in _N2 flow for 3h, raise the temperature to 475°C, and roast it for 2.5h; raise the temperature to 600°C, switch _N2 to _H2 and _N2 Mixed gas, the flow ratio of _H2 and _N2 is 5, and the feeding time is 1.5h; the gas is switched to _N2 , the temperature is adjusted to 520°C, and the time is 105min, so that the metal is reduced to fine particles and attached to the porous ceramics surface; switch N ₂ to the mixed gas of ethanol and N ₂ , the flow ratio of ethanol and N ₂ is 0.25, and the feeding time is 60 minutes; a layer of carbon substance is formed and attached to the surface of the porous ceramic channel. After analysis, the carbon substance is A mixture of carbon nanofibers, carbon nanotubes, and graphene sheets with a graphene structure is cooled to obtain carbon porous ceramics.

Example 5

Cut the porous ceramics with a channel size of 0.35 mm into a cylindrical structure with a diameter of 5 mm and a height of 5 mm, rinse the porous ceramics with clean water at least three times, and dry them to remove possible ash impurities, etc. The porous ceramics contain an interpenetrating three-dimensional network The channels of the open-pore structure are made of corundum sand, silicon carbide, cordierite and other raw materials, which are obtained through molding, foaming, and sintering. They can be purchased from the market or customized from manufacturers. The main chemical composition is SiO _2. Al ₂ O ₃ , CaO, MgO, Na ₂ O, TiO ₂ , etc. The ratio among them is determined according to the production ratio of the porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the present invention. Soak in acetic acid solution with a concentration of 17.5% copper phosphate, the soaking temperature is 80°C, and the soaking time is 6h. Take it out, dry it in the air, put it in a tube high-temperature furnace, dry it at 105°C for 3h in _N2 flow, raise the temperature to 515°C, and bake it for 3.5h; raise the temperature to 625°C, switch _N2 to _H2 and _N2 Mixed gas, the flow ratio of H ₂ and N ₂ is 10, and the feeding time is 3 hours; the gas is switched to N ₂ , the temperature is adjusted to 625°C, and the time is 85 minutes, so that the metal is reduced to fine particles and attached to the porous ceramic surface ;Switch _N2 to the mixed gas of benzene and _N2 , the flow ratio of benzene and _N2 is 0.15, and the feeding time is 60min; a layer of carbon substance is formed and attached to the surface of the porous ceramic channel. After analysis, the carbon substance is graphite Carbon nanofibers, carbon nanotubes, and graphene sheet mixtures of ene structures are cooled to obtain carbon porous ceramics.

Example 6

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature for 2 hours to form a gel to obtain a modified TS-1 glue; tetramethyl silicate: vinyltriethoxysilane: tetrapropylammonium hydroxide: methylamine: tetramethyl titanate: ethanol: H ₂ The molar ratio of O is 0.5:0.001:0.15:0.01:0.01:0.5:25.

Example 7

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature for 10 hours to form a gel to obtain a modified TS-1 glue; tetraethyl silicate: vinyltriethoxysilane: tetrapropylammonium bromide: trimethylamine: tetraethyl titanate: n-propanol: The molar ratio of H ₂ O is 1.5:0.15:0.55:0.15:0.15:2.0:15.

Example 8

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature for 7 hours to form a gel to obtain a modified TS-1 glue; tetraisopropyl silicate: γ-aminopropyltrimethoxysilane: tetrapropylammonium bromide: ethylenediamine: tetra-n-propyl titanate The molar ratio of :isopropanol:H ₂ O is 1.1:0.01:0.25:0.05:0.08:1.1:20.

Example 9

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature for 5 hours to form a gel to obtain a modified TS-1 glue; tetra-n-propyl silicate: γ-aminopropyltriethoxysilane: tetrapropylammonium hydroxide: ammonia water: tetraisopropyl titanate: The molar ratio of n-butanol:H ₂ O is 0.8:0.02:0.45:0.015:0.03:1.5:22.

Example 10

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature for 6 hours to form a gel to obtain a modified TS-1 glue; tetraethyl silicate: γ-(β-aminoethyl) aminopropyltrimethoxysilane: tetrapropylammonium hydroxide: isopropylamine: titanium The molar ratio of tetra-n-butyl acid:isobutanol:H ₂ O is 0.65:0.15:0.30:0.015:0.025:2.5:16.

Example 11

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature for 5h to form a gel to obtain a modified TS-1 glue; tetraethyl silicate: γ-(β-aminoethyl) aminopropyltriethoxysilane: tetrapropylammonium bromide: methylamine: The molar ratio of tetraisopropyl titanate:n-propanol:H ₂ O is 0.75:0.025:0.25:0.05:0.022:2.0:18.

Example 12

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature for 4 hours to form a gel to obtain a modified TS-1 glue; tetramethyl silicate: γ-semicarbazide propyl trimethoxysilane: tetrapropyl ammonium hydroxide: isopropylamine: tetraisopropyl titanate: The molar ratio of ethanol:H ₂ O is 0.95:0.1:0.22:0.15:0.025:1.5:22.

Example 13

Mix the templating agent with water to form a solution, add a pH regulator and stir, then add tetraalkyl silicate and functionalized trialkoxysilane to continue stirring, and finally add the alcohol solution of tetraalkyl titanate to continue stirring, Stir at room temperature for 10 hours to form a gel to obtain a modified TS-1 glue; tetraethyl silicate: γ-semicarbazide propyl triethoxysilane: tetrapropyl ammonium hydroxide: ammonia water: tetra-n-propyl titanate: The molar ratio of n-propanol:H ₂ O is 0.75:0.12:0.17:0.20:0.02:1.25:21.

Preparation Example of Monolithic Modified TS-1 Catalyst

The preparation of the monolithic modified TS-1 catalyst is obtained by immersing the above-mentioned carbon porous ceramics in the above-mentioned modified TS-1 glue and recrystallizing. The following examples only list part of the carbon porous ceramics and modified TS-1. 1. The combination of glue solutions, but not limited to the combination and conditions of the following examples.

The structure of the monolithic modified TS-1 catalyst obtained below is a cylindrical structure with a diameter of 3 mm to 100 mm and a height of 2 mm to 50 mm. The catalyst contains three-dimensional channels interconnected with each other, and the average pore diameter of the three-dimensional channels is 0.1 μm to 0.75 mm. ; The micro-mesopore diameter of the TS-1 layer on the channel surface is 0.5-50nm, the BET specific surface area is 120-300m ² /g, and the pore volume is 0.1-15cm ³ /g.

Example 14

Soak the carbon porous ceramics obtained in Example 1 in the modified TS-1 glue solution obtained in Example 6, the soaking temperature is 35°C, and the soaking time is 3min, take out the carbon porous ceramics, drain the surface liquid, place in On the upper grid frame in the autoclave filled with 0.25% ammonia solution, raise the temperature of the autoclave to 125°C, keep it for 10h, lower the autoclave to room temperature, take out the carbon porous ceramics, place them in a high-temperature furnace, and heat them at 105°C Drying at low temperature for 5 hours, then raising the temperature to 450°C and roasting for 2 hours, taking it out after cooling down to room temperature, and obtaining the monolithic modified TS-1 catalyst.

Example 15

Soak the carbon porous ceramic obtained in Example 5 in the modified TS-1 glue solution obtained in Example 13, the immersion temperature is 85°C, and the immersion time is 60min, take out the carbon porous ceramic, drain the surface liquid, and place On the upper grid frame in the autoclave equipped with 25% triethylamine solution, raise the temperature of the autoclave to 195°C, keep it for 80h, lower the autoclave to room temperature, take out the carbon porous ceramics, place them in a high-temperature furnace, and Dry at 105°C for 5 hours, then raise the temperature to 650°C and calcinate for 8 hours, take it out after cooling down to room temperature, and obtain the monolithic modified TS-1 catalyst.

Example 16

Soak the carbon porous ceramics obtained in Example 3 in the modified TS-1 glue solution obtained in Example 7, the soaking temperature is 65°C, and the soaking time is 20 minutes, take out the carbon porous ceramics, drain the surface liquid, and place On the upper grid frame in the autoclave filled with 7.5% trimethylamine solution, raise the temperature of the autoclave to 165°C and keep it for 50h, then lower the autoclave to room temperature, take out the carbon porous ceramics, and place them in a high-temperature furnace. It was dried at ℃ for 5 hours, then raised to 560℃ and calcined for 4.5 hours, and then taken out after cooling down to room temperature to obtain the monolithic modified TS-1 catalyst.

Example 17

Soak the carbon porous ceramics obtained in Example 2 in the modified TS-1 glue solution obtained in Example 11, the soaking temperature is 40°C, and the soaking time is 35 minutes, take out the carbon porous ceramics, drain the surface liquid, and place in On the upper grid frame in the autoclave equipped with 11% isopropylamine solution, raise the temperature of the autoclave to 175 °C and keep it for 65 hours, then lower the autoclave to room temperature, take out the carbon porous ceramics, place them in a high-temperature furnace, and first heat the autoclave at 105 It was dried at ℃ for 5 hours, then raised to 490℃ and calcined for 6.5 hours, and then taken out after cooling down to room temperature to obtain the monolithic modified TS-1 catalyst.

Example 18

Soak the carbon porous ceramic obtained in Example 4 in the modified TS-1 glue solution obtained in Example 9, the immersion temperature is 32.5°C, and the immersion time is 50min, take out the carbon porous ceramic, drain the surface liquid, and place On the upper grid frame in the autoclave equipped with 20% dimethylamine solution, the autoclave was heated to 170°C, kept for 70h, the autoclave was lowered to room temperature, the carbon porous ceramic was taken out, placed in a high-temperature furnace, and first Dry at 105°C for 5 hours, then raise the temperature to 650°C and calcinate for 7.5 hours, take it out after cooling down to room temperature, and obtain the monolithic modified TS-1 catalyst.

Example 19

Soak the carbon porous ceramic obtained in Example 2 in the modified TS-1 glue solution obtained in Example 8, the immersion temperature is 70°C, and the immersion time is 45min, take out the carbon porous ceramic, drain the surface liquid, and place On the upper grid frame in the autoclave equipped with 17.5% dimethylamine solution, raise the temperature of the autoclave to 155 °C and keep it for 48 hours, then lower the autoclave to room temperature, take out the carbon porous ceramics, place them in a high-temperature furnace, and Dry at 105°C for 5 hours, then raise the temperature to 625°C and calcinate for 7 hours, take it out after cooling down to room temperature, and obtain the monolithic modified TS-1 catalyst.

Example 20

Soak the carbon porous ceramic obtained in Example 5 in the modified TS-1 glue solution obtained in Example 12, the immersion temperature is 52.5°C, and the immersion time is 48min, take out the carbon porous ceramic, drain the surface liquid, and place On the upper grid frame in the autoclave equipped with 12.5% isopropylamine solution, raise the temperature of the autoclave to 155°C and keep it for 40h, then lower the autoclave to room temperature, take out the carbon porous ceramics, place them in a high-temperature furnace, and first heat the autoclave at 105 It was dried at ℃ for 5 hours, then raised to 635℃ and calcined for 6.8 hours, and then taken out after cooling down to room temperature to obtain the monolithic modified TS-1 catalyst.

One-step direct epoxidation embodiment of propylene

The monolithic modified TS-1 catalyst prepared in Examples 14 to 20 was used to catalyze the direct oxidation of propylene with hydrogen peroxide in a fixed-bed reactor to prepare propylene oxide. The following examples only list some combinations of catalysts and reaction conditions thereof, but are not limited to the catalysts and reaction conditions listed in the following examples.

In the following examples, the diameter of the monolithic catalyst is 50 mm, and the height of the catalyst bed is 1500 mm.

Example 21

A kind of application of said monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene comprises the following steps:

The monolithic modified TS-1 catalyst prepared in Example 14 was packed in a fixed-bed reactor, propylene was metered into the reactor at a pressure of 0.4 MPa, dioxane and hydrogen peroxide were passed into the reactor respectively, and propylene, di The flow ratio of hexane and hydrogen peroxide is 1:2:1.5, the space velocity of the reactor is 200h ^-1 , the concentration of hydrogen peroxide is 30%, the temperature of the reactor bed is controlled at 30°C, and the materials react in the catalyst bed. The reaction mixture is discharged from the reactor. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analysis were taken from the outlet of the reactor during the reaction, and the conversion rate (99.8%) of hydrogen peroxide was calculated. The selectivity of generating propylene oxide was 95%, and there was about 5% 1,2-propanediol at the same time. The unreacted propylene is returned to the reactor for recycling, the separated solvent is returned to the reactor for recycling, and the separated water is used as industrial water or discharged as up-to-standard water. The isolated by-product 1,2-propanediol is sold as a by-product. According to the different types of solvents, if alcohol solvents are used, a small amount of side reaction between propylene oxide and alcohol will produce propylene glycol ether as a by-product, and the propylene glycol ether will be sold as a by-product after separation.

Example 22

A kind of application of said monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene comprises the following steps:

The monolithic modified TS-1 catalyst prepared in Example 20 was packed in a fixed-bed reactor, propylene was metered into the reactor at a pressure of 0.4 MPa, acetone and hydrogen peroxide were passed into the reactor respectively, and the proportions of propylene, acetone and hydrogen peroxide were The flow ratio is 1:5:0.75, the space velocity of the reactor is 1000h ^-1 , the concentration of hydrogen peroxide is 70%, the temperature of the reactor bed is controlled at 90°C, the material reacts in the catalyst bed, and the mixture generated from the reaction device discharge. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analysis were taken from the outlet of the reactor during the reaction, and the conversion rate (99.8%) of hydrogen peroxide was calculated. The selectivity of generating propylene oxide was 93.5%, and there was about 6.5% of 1,2-propanediol at the same time. The unreacted propylene is returned to the reactor for recycling, the separated solvent is returned to the reactor for recycling, and the separated water is used as industrial water or discharged as up-to-standard water. The isolated by-product 1,2-propanediol is sold as a by-product. According to the different types of solvents, if alcohol solvents are used, a small amount of side reaction between propylene oxide and alcohol will produce propylene glycol ether as a by-product, and the propylene glycol ether will be sold as a by-product after separation.

Example 23

A kind of application of said monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene comprises the following steps:

The monolithic modified TS-1 catalyst prepared in Example 15 was packed in a fixed-bed reactor, propylene was metered into the reactor at a pressure of 0.4 MPa, and acetonitrile and hydrogen peroxide were passed into the reactor respectively. The flow ratio is 1:7:1.4, the space velocity of the reactor is 500h ^-1 , the concentration of hydrogen peroxide is 50%, the temperature of the reactor bed is controlled at 50°C, the materials react in the catalyst bed, and the reaction mixture is produced from the reaction device discharge. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analysis were taken from the outlet of the reactor during the reaction, and the conversion rate (99.5%) of hydrogen peroxide was calculated. The selectivity of producing propylene oxide was 96.5%, and there was about 3.5% of 1,2-propanediol at the same time. The unreacted propylene is returned to the reactor for recycling, the separated solvent is returned to the reactor for recycling, and the separated water is used as industrial water or discharged as up-to-standard water. The isolated by-product 1,2-propanediol is sold as a by-product. According to the different types of solvents, if alcohol solvents are used, a small amount of side reaction between propylene oxide and alcohol will produce propylene glycol ether as a by-product, and the propylene glycol ether will be sold as a by-product after separation.

Example 24

A kind of application of said monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene comprises the following steps:

The monolithic modified TS-1 catalyst prepared in Example 16 was packed in a fixed-bed reactor, propylene was metered into the reactor at a pressure of 0.4 MPa, methanol and hydrogen peroxide were passed into the reactor respectively, and the propylene, methanol and hydrogen peroxide The flow ratio is 1:4.5:1.0, the space velocity of the reactor is 350h ^-1 , the concentration of hydrogen peroxide is 45%, the temperature of the reactor bed is controlled at 40°C, the materials react in the catalyst bed, and the reaction mixture is produced from the reaction device discharge. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analysis from the outlet of the reactor during the reaction, and calculating the conversion rate (98.5%) of hydrogen peroxide, the selectivity of generating propylene oxide is 93.5%, and there are about 4.5% of 1,2-propanediol and 2% of propylene glycol methyl simultaneously ether. The unreacted propylene is returned to the reactor for recycling, the separated solvent is returned to the reactor for recycling, and the separated water is used as industrial water or discharged as up-to-standard water. The isolated by-product 1,2-propanediol is sold as a by-product. According to the different types of solvents, if alcohol solvents are used, a small amount of side reaction between propylene oxide and alcohol will produce propylene glycol ether as a by-product, and the propylene glycol ether will be sold as a by-product after separation.

Example 25

A kind of application of said monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene comprises the following steps:

The monolithic modified TS-1 catalyst prepared in Example 15 was packed in a fixed-bed reactor, and propylene was metered into the reactor at a pressure of 0.4 MPa, and ethanol and hydrogen peroxide were passed into the reactor respectively, and propylene, ethanol, and hydrogen peroxide were added into the reactor. The flow ratio is 1:10:1.0, the space velocity of the reactor is 600h ^-1 , the concentration of hydrogen peroxide is 50%, the temperature of the reactor bed is controlled at 55°C, the materials react in the catalyst bed, and the reaction mixture is produced from the reaction device discharge. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analysis from the outlet of the reactor during the reaction, and calculating the conversion rate (99.2%) of hydrogen peroxide, the selectivity of generating propylene oxide is 94.5%, and there are about 3.5% 1,2-propanediol and 2% propylene glycol ethyl ether simultaneously . The unreacted propylene is returned to the reactor for recycling, the separated solvent is returned to the reactor for recycling, and the separated water is used as industrial water or discharged as up-to-standard water. The isolated by-product 1,2-propanediol is sold as a by-product. According to the different types of solvents, if alcohol solvents are used, a small amount of side reaction between propylene oxide and alcohol will produce propylene glycol ether as a by-product, and the propylene glycol ether will be sold as a by-product after separation.

Example 26

A kind of application of said monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene comprises the following steps:

The monolithic modified TS-1 catalyst prepared in Example 16 was packed in a fixed-bed reactor, propylene was metered into the reactor at a pressure of 0.4 MPa, dioxane, acetonitrile and hydrogen peroxide were respectively fed into the reactor, and the propylene The flow ratio of dioxane, acetonitrile and hydrogen peroxide is 1:4.2:5.8:1.35, the reactor space velocity is 800h ^-1 , the concentration of hydrogen peroxide is 45%, the temperature of the control reactor bed is 62°C, and the material is The catalyst bed reacts and the resulting mixture is discharged from the reactor. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analysis were taken from the outlet of the reactor during the reaction, and the conversion rate (99.3%) of hydrogen peroxide was calculated. The selectivity of generating propylene oxide was 97.5%, and there was about 2.5% of 1,2-propanediol at the same time. The unreacted propylene is returned to the reactor for recycling, the separated solvent is returned to the reactor for recycling, and the separated water is used as industrial water or discharged as up-to-standard water. The isolated by-product 1,2-propanediol is sold as a by-product. According to the different types of solvents, if alcohol solvents are used, a small amount of side reaction between propylene oxide and alcohol will produce propylene glycol ether as a by-product, and the propylene glycol ether will be sold as a by-product after separation.

Example 27

A kind of application of said monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene comprises the following steps:

The monolithic modified TS-1 catalyst prepared in Example 17 was packed in a fixed bed reactor, propylene was metered into the reactor at a pressure of 0.4 MPa, acetone, acetonitrile and hydrogen peroxide were passed into the reactor respectively, and propylene, acetone, The flow ratio of acetonitrile and hydrogen peroxide is 1:6.3:4.6:1.45, the space velocity of the reactor is 560h ^-1 , the concentration of hydrogen peroxide is 50%, the temperature of the reactor bed is controlled at 47.5°C, and the materials react in the catalyst bed, The reaction mixture is discharged from the reactor. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analysis were taken from the outlet of the reactor during the reaction, and the conversion rate (99.7%) of hydrogen peroxide was calculated. The selectivity of generating propylene oxide was 98.5%, and there was about 1.5% of 1,2-propanediol at the same time. The unreacted propylene is returned to the reactor for recycling, the separated solvent is returned to the reactor for recycling, and the separated water is used as industrial water or discharged as up-to-standard water. The isolated by-product 1,2-propanediol is sold as a by-product. According to the different types of solvents, if alcohol solvents are used, a small amount of side reaction between propylene oxide and alcohol will produce propylene glycol ether as a by-product, and the propylene glycol ether will be sold as a by-product after separation.

Example 28

A kind of application of said monolithic modified TS-1 catalyst in the preparation of propylene oxide by direct oxidation of propylene comprises the following steps:

The monolithic modified TS-1 catalyst prepared in Example 18 was packed in a fixed-bed reactor, propylene was metered into the reactor at a pressure of 0.4 MPa, methanol, acetonitrile and hydrogen peroxide were respectively fed into the reactor, and propylene, methanol, The flow ratio of acetonitrile and hydrogen peroxide is 1:4.8:3.9:1.8, the space velocity of the reactor is 680h ^-1 , the concentration of hydrogen peroxide is 35%, the temperature of the reactor bed is controlled at 55°C, and the materials react in the catalyst bed, The reaction mixture is discharged from the reactor. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analysis from the reactor outlet during the reaction process, and calculating the conversion rate (99.5%) of hydrogen peroxide, the selectivity of generating propylene oxide is 97.5%, and there are about 1.5% 1,2-propylene glycol and 1% propylene glycol ether simultaneously . The unreacted propylene is returned to the reactor for recycling, the separated solvent is returned to the reactor for recycling, and the separated water is used as industrial water or discharged as up-to-standard water. The isolated by-product 1,2-propanediol is sold as a by-product. According to the different types of solvents, if alcohol solvents are used, a small amount of side reaction between propylene oxide and alcohol will produce propylene glycol ether as a by-product, and the propylene glycol ether will be sold as a by-product after separation.

The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the present invention is not limited by the above-mentioned embodiments, and that described in the above-mentioned embodiments and the description only illustrates the principles of the present invention, and the present invention also has various aspects without departing from the spirit and scope of the present invention. Variations and improvements all fall within the scope of the claimed invention. The protection scope of the present invention is defined by the appended claims and their equivalents.

Claims (7)

1. A monolithic modified TS-1 catalyst is prepared by a preparation method comprising the following steps:

soaking the carbon porous ceramic in the modified TS-1 glue solution according to the proportion of the modified TS-1 glue solution to the carbon porous ceramic completely, taking out the carbon porous ceramic after soaking, draining off surface liquid, placing the carbon porous ceramic on the liquid level in a pressure reactor filled with ammonia or amine solution, heating for keeping reaction, cooling to room temperature, taking out the carbon porous ceramic, drying, heating for roasting, cooling to room temperature, and taking out to obtain an integral modified TS-1 catalyst;

the carbon porous ceramic is prepared by a preparation method comprising the following steps:

cutting the cleaned porous ceramic, soaking in metal salt solution, taking out the porous ceramic and the metal salt solution according to the ratio of the porous ceramic to the metal salt solution that the porous ceramic can be soaked in the solution, drying, and soaking in N ₂ Drying in air flow, heating and roasting, continuously heating, keeping for a period of time under mixed air flow, and cooling to room temperature to obtain the carbon porous ceramic;

the modified TS-1 glue solution is prepared by a preparation method comprising the following steps:

mixing a template agent and water to prepare a solution, adding a pH regulator, stirring, adding tetraalkyl silicate and functionalized trialkoxysilane, continuously stirring, finally adding an alcoholic solution of tetraalkyl titanate, continuously stirring, and stirring at room temperature to form gel, thereby obtaining a modified TS-1 glue solution; the tetraalkyl silicate is functionalized trialkoxysilane, the template is pH regulator, the tetraalkyl titanate is alcohol, H ₂ The molar ratio of O is (0.5-1.5), (0.001-0.15), (0.15-0.55), (0.01-0.2), (0.01-0.15), (0.5-2.5) and (15-25);

the structure of the integral modified TS-1 catalyst is a cylindrical structure with the diameter of 3-100 mm and the height of 2-50 mm, the catalyst contains three-dimensional pore channels which are communicated with each other, and the average pore diameter of the three-dimensional pore channels is 0.1-0.75 mm; the diameter of the micro-mesoporous channel of the TS-1 layer on the surface of the pore channel is 0.5-50nm, the BET specific surface area is 120-300 m ² Per g, pore volume of 0.1-15 cm ³ /g；

Wherein the metal ion in the metal salt solution is Fe ²⁺ 、Fe ³⁺ 、Co ²⁺ 、Ni ²⁺ 、Cu ²⁺ The anion paired with the metal ion is at least one of formate, acetate, propionate, citrate, lactate, and PO ₄ ^3- 、Cl ^- 、Br ^- 、NO ₃ ^- 、SO ₄ ^2- (ii) a The concentration of the metal salt solution is 0.15-20%; the solvent in the metal salt solution adopts water and acetic acid; the metal salt is at least one of ferrous acetate, nickel nitrate, cobalt citrate, copper nitrate and copper phosphate;

cutting the cleaned porous ceramic, and soaking the cut porous ceramic in a metal salt solution at the temperature of 15-80 ℃ for 5 min-12 h;

said is in N ₂ Drying in air flow at 100-120 deg.c for 2-5 hr;

the temperature of the temperature rising roasting is 180-550 ℃, and the time is 1-7 h;

the temperature for continuously increasing the temperature is 325-750 ℃;

the keeping time under the mixed gas flow is as follows: n is to be ₂ Switch to H ₂ And N ₂ Mixed gas of H ₂ And N ₂ The flow ratio of (1) to (50) is 0.1 to (5) min to (30) h, and the gas is switched to N ₂ Regulating the temperature to 350-900 ℃ for 1-200 min, and adding N ₂ Switching to C, H, O-containing small molecule substance and N ₂ The mixed gas of (1), containing C, H, O micromolecule substance and N ₂ The flow ratio of (1) to (10) and the introduction time of (1) to (200) min;

the functionalized trialkoxysilane is vinyl trimethoxy silane, vinyl triethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma- (beta-aminoethyl) aminopropyl trimethoxy silane, gamma- (beta-aminoethyl) aminopropyl triethoxy silane, gamma-aminoureido propyl trimethoxy silane or gamma-aminoureido propyl triethoxy silane.

2. The integrally modified TS-1 catalyst of claim 1, wherein: wherein the temperature of soaking the carbon porous ceramic in the modified TS-1 glue solution is 25-85 ℃, and the time is 3-60 min;

the amine solution is at least one aqueous solution of methylamine, ethylamine, ethylenediamine, n-propylamine, isopropylamine, dimethylamine, trimethylamine, diethylamine and triethylamine, and the concentration of the ammonia or the amine solution is 0.25 to 25 percent;

the heating is carried out to keep the reaction temperature at 125-195 ℃ for 10-80 h;

and after drying, heating for roasting at the drying temperature of 100-120 ℃ for 1-10 h, at the roasting temperature of 450-650 ℃ for 2-8 h.

3. The integrally modified TS-1 catalyst of claim 1, wherein: wherein, the cleaned porous ceramic is obtained by washing the porous ceramic with clear water for at least three times and drying;

the porous ceramic is a pore canal with a three-dimensional network-shaped open pore structure, the pore canal is communicated with each other, the size of the pore canal is 0.1-0.75 mm, and the structure of the porous ceramic is a cylindrical structure with the diameter of 3-100 mm and the height of 2-50 mm.

4. The integrally modified TS-1 catalyst of claim 1, wherein: wherein the template agent is tetrapropylammonium hydroxide and tetrapropylammonium bromide;

the pH regulator is ammonia water, methylamine, ethylamine, ethylenediamine, trimethylamine, n-propylamine and isopropylamine;

the tetraalkyl silicate is tetramethyl silicate, tetraethyl silicate, tetra-isopropyl silicate and tetra-n-propyl silicate;

the tetra-alkyl titanate is tetra-methyl titanate, tetra-ethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate and tetra-n-butyl titanate;

the alcohol is methanol, ethanol, n-propanol, isopropanol, n-butanol, or isobutanol;

the stirring and gelling time at room temperature is 2-10 h.

5. Use of a structurally modified TS-1 catalyst according to any one of claims 1 to 4 in the preparation of propylene oxide by the direct oxidation of propylene.

6. Use according to claim 5, characterized in that: the application comprises the following steps:

filling the prepared integral modified TS-1 catalyst in a fixed bed reactor, introducing propylene, a solvent and hydrogen peroxide into the reactor, wherein the flow ratio of the propylene, the solvent and the hydrogen peroxide is 1 (1-11) to 0.5-2, and the space velocity LHSV of the reactor is 200-1000 h ^-1 Controlling the temperature of the reactor to be 30-90 ℃, controlling the temperature of the fixed bed layer to be 30-90 ℃, reacting the materials in the catalyst bed layer, discharging the mixture generated by the reaction from the reactor, carrying out subsequent separation on the discharged mixture to obtain pure propylene oxide, sampling and analyzing the mixture from the outlet of the reactor in the reaction process, calculating the conversion rate of hydrogen peroxide, and generating the selectivity of the propylene oxide.

7. Use according to claim 6, characterized in that: wherein the solvent is at least one of acetonitrile, acetone, dioxane, methanol and ethanol;

the concentration of the hydrogen peroxide is 30-70%.