CN111085205B - Carbon porous metal-based integral modified TS-1 catalyst, and preparation method and application thereof - Google Patents

Carbon porous metal-based integral modified TS-1 catalyst, and preparation method and application thereof Download PDF

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CN111085205B
CN111085205B CN201811234303.4A CN201811234303A CN111085205B CN 111085205 B CN111085205 B CN 111085205B CN 201811234303 A CN201811234303 A CN 201811234303A CN 111085205 B CN111085205 B CN 111085205B
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porous metal
catalyst
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roasting
carbon porous
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CN111085205A (en
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曹贵平
吕慧
孔小鑫
张政
冯淼
罗朝辉
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East China University of Science and Technology
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    • B01J35/615—100-500 m2/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract

The invention discloses a preparation method of a carbon porous metal-based integral modified TS-1 catalyst, which comprises the following steps: soaking the carbon porous metal in the modified TS-1 glue solution according to the proportion of the carbon porous metal to the modified TS-1 glue solution, taking out the carbon porous metal after soaking until the surface liquid is completely leached, placing the carbon porous metal on the liquid level in a pressure reactor filled with ammonia or amine solution, heating and keeping reaction, cooling to room temperature, taking out the carbon porous metal, drying, heating for roasting, cooling to room temperature, and taking out to obtain the integral modified TS-1 catalyst. When in use, the catalyst is stacked to a certain height, so that good strength is kept, the catalyst cannot be cracked, and mutual extrusion deformation cannot occur; the catalyst also has a good lifetime and catalytic activity and selectivity do not decay over long runs.

Description

Monolithic modified TS-1 catalyst based on carbon porous metal, preparation method and application
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to an integral modified TS-1 catalyst, and a preparation method and application thereof.
Background
The propylene oxide is an important chemical raw material, is applied to synthesis of polyether polyol, propylene glycol ether, dimethyl carbonate, polypropylene carbonate, nonionic surfactant and the like, and is an essential raw material for polyurethane industry. Plays an important role in the chemical industry.
The demand of the propylene oxide increases year by year, and particularly, with the rapid development of economic technologies in China, higher requirements are put forward on the safety, cleanliness and high efficiency of the propylene oxide production technology. For years, the production method of propylene oxide in China is mainly a chlorohydrin method with high pollution, which brings great pressure to the environment, and the chlorohydrin method is strictly prohibited to be used in developed countries such as Europe, america and the like. In recent years, the use of chlorohydrin processes for producing propylene oxide has also begun to be banned in our country. Although the co-oxidation method is advanced in technology, the co-oxidation method also has the defects of high proportion of co-produced products, large organic sewage treatment capacity, high energy consumption, high investment cost, high technology transfer cost in foreign countries and the like. The method for preparing the propylene oxide by the one-step direct oxidation of the propylene is a clean and economic process technical route, and China also advocates the method for producing the propylene oxide. The catalyst used in the one-step direct oxidation method mainly takes a TS-1 catalyst, and long-term research of scientists shows that the preparation technology of the TS-1 catalyst and related scientific theories make important progress, and the activity and the selectivity reach better levels, but the TS-1 is extremely tiny particles with nanometer pores, and the bottleneck problem that the tiny particles are extremely difficult to separate from liquid exists in the industrial process. Although abundant literature reports TS-1 molding synergistic methods such as spray drying granulation, extrusion molding granulation, carrier surface coating, hollow microsphere and the like, the method has the problems of obvious reduction of activity and selectivity, and slows down the industrial process. Although the catalyst formed and synergized is also provided with a matched reactor and an operation mode thereof to make up the defects of the catalyst, such as a semi-continuous stirred tank reactor, a fixed bed reactor and the like, the problems can not be fundamentally solved.
Disclosure of Invention
The invention aims to provide an integral modified TS-1 catalyst, which solves the problem of a catalyst for preparing propylene oxide by direct oxidation of propylene in the prior one-step method, greatly improves the selectivity of a main product propylene oxide after the catalyst is used, solves the problem of separation of the catalyst from a reaction solution, greatly improves the production efficiency and reduces the production cost.
The second purpose of the invention is to provide a preparation method of the integral modified TS-1 catalyst.
The third purpose of the invention is to provide the application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method, and the problem of separation of the catalyst and a reaction liquid is solved by adopting the continuous operation of a fixed bed reactor.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a monolithic modified TS-1 catalyst, which is a cylindrical structure with the height of 2 mm-500 mm, wherein 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 0.5 mu m-0.75 mm; the diameter of the micro-mesoporous channel of the TS-1 layer on the surface of the pore channel is 0.5-10nm, the BET specific surface area is 150-300 m 2 Per g, pore volume of 0.1-12 cm 3 /g。
The second aspect of the invention provides a preparation method of the integral modified TS-1 catalyst, which comprises the following steps:
soaking the carbon porous metal in the modified TS-1 glue solution according to the proportion that the modified TS-1 glue solution completely immerses the carbon porous metal, taking out the carbon porous metal after soaking, draining off surface liquid, placing the carbon porous metal 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 metal, drying, heating for roasting, cooling to room temperature, and taking out to obtain the integral modified TS-1 catalyst.
The temperature of the carbon porous metal soaked in the modified TS-1 glue solution is 20-80 ℃, and the time is 3-60 min.
The amine solution is at least one of water solution of methylamine, ethylamine, ethylenediamine, n-propylamine, isopropylamine, dimethylamine, trimethylamine, diethylamine and triethylamine, and the concentration of the ammonia or the amine solution is 0.25-25%.
The ammonia solution is ammonia water.
The heating is carried out to keep the reaction temperature at 125-195 ℃ for 10-80 h.
After drying, heating for roasting, wherein the drying temperature is 100-120 ℃, the drying time is 1-10 h, preferably 105 ℃, and the drying time is 5h; the roasting temperature is 450-650 ℃, and the roasting time is 2-8 h.
The preparation method of the carbon porous metal comprises the following steps:
roasting the cleaned porous metal in a nitrogen atmosphere at the temperature of 100-120 ℃ for 4-6 h; the roasting is switched to air or oxygen roasting, the roasting temperature is 210-750 ℃, and the roasting time is 0.5-7 h; the nitrogen roasting is switched, the roasting temperature is 275-750 ℃, and the roasting time is 1-200 min; is switched to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of the water inlet pipe is 0.1-50, and the inlet time is 30 min-5 h; switching to nitrogen for roasting at 350-900 deg.c for 1-200 min; switching into small molecular substance containing C, H and O and N 2 The mixed gas of C, H, O-containing small molecular substances and N 2 The flow ratio of (1) to (10) and the introduction time of (1) to (200) min; and switching to nitrogen for cooling to obtain the carbon porous metal.
The cleaned porous metal is washed by ethanol and pure water for at least three times in sequence and dried to remove impurities such as pollutants and the like which may exist.
The porous metal is mainly composed of at least one or more of Fe, co, ni and Cu alloy, and is obtained by molding, foaming and sintering, and can be purchased from the market or directly customized by manufacturers. The pore canal of the porous metal is a three-dimensional network open pore structure which is mutually communicated, and the average pore diameter of the three-dimensional pore canal is 0.1 mu m-0.75 mm; the diameter of the micro-mesoporous channel of the TS-1 layer on the surface of the pore channel is 0.5-10nm, the BET specific surface area is 150-300 m 2 Per g, pore volume of 0.1-12 cm 3 /g。
The C, H and O-containing micromolecule substance is methane, ethane, acetylene, ethylene, propylene, propine, methanol, ethanol, acetone, benzene, toluene and ethylbenzene, preferably ethane, propane, acetylene, ethylene, propylene, propine, ethanol and benzene.
The preparation method of the modified TS-1 glue solution comprises the following steps:
adding tetraalkyl silicate and functionalized trialkoxy silane into aqueous solution containing template agent, stirringStirring, adding an aqueous solution of a pH regulator, continuing stirring, adding an alcoholic solution of tetraalkyl titanate, and stirring at room temperature to form gel, thereby obtaining a modified TS-1 colloidal 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), (0.01-0.65), (0.01-0.175), (0.5-2.0) and (2.0-25).
The tetraalkyl silicate is tetramethyl silicate, tetraethyl silicate, tetra-isopropyl silicate and tetra-n-propyl silicate.
The functionalized trialkoxysilane is aniline methyl trimethoxy silane, aniline methyl triethoxy silane, gamma-mercaptopropyl trimethoxy silane, gamma-mercaptopropyl triethoxy silane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma- (2, 3-epoxypropoxy) propyl triethoxy silane and beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane.
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 titanate is tetramethyl titanate, tetraethyl 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.
The third aspect of the invention provides an application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method.
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 (5-15) to (2-20) to (1.5-9), and the space velocity LHSV (the amount of raw materials passing through a unit catalyst in unit time) of the reactor is 200-1000 h -1 Controlling the temperature of the reactorThe temperature of the fixed bed layer is controlled to be 35-90 ℃, the materials react in the catalyst bed layer, the mixture generated by the reaction is discharged from the reactor, the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide, the sampling analysis is carried out at the outlet of the reactor in the reaction process, the conversion rate of hydrogen peroxide (97.5-99.9%) is calculated, and the selectivity of the generated propylene oxide (89-93.8%) is calculated.
The solvent is at least one of acetonitrile, acetone, dioxane, methanol and ethanol.
The concentration of the hydrogen peroxide is 30-70%.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the invention provides an integral modified TS-1 catalyst, which is filled in a designed fixed bed reactor through repeated experiments and comparative optimization, reactants of propylene, hydrogen peroxide and a solvent are respectively and continuously added into the fixed bed reactor at a certain flow rate, a catalyst bed layer is controlled at a certain temperature, and propylene is directly oxidized by hydrogen peroxide to generate propylene oxide under the action of a catalyst in the fixed bed. Due to the increase of the catalyst structure, the change of the operation mode and the optimization of the operation condition, the liquid material flowing out of the fixed bed reactor is separated from the catalyst and only contains the product propylene oxide, unreacted propylene, hydrogen peroxide and solvent and a small amount of propylene glycol generated by the hydration of the propylene oxide. The effluent mixture is firstly passed through a separation column to separate propylene and propylene oxide with low boiling point from water with high boiling point, solvent and propylene glycol as a byproduct. Separating propylene from epoxypropane to obtain epoxypropane with purity meeting the requirement, and returning the propylene obtained by separation to a feed inlet of the reactor for recycling. The solvent, water and propylene glycol with higher boiling points are rectified and separated, the solvent with the purity meeting the requirement returns to the inlet of the reactor for recycling, the propylene glycol with the purity meeting the requirement is sold as a byproduct, and the water with the purity meeting the requirement can be used as industrial water and can be discharged after heat in the water is recovered to reach the standard. Solves the difficult problems in the existing propylene oxide production technology.
The integral modified TS-1 catalyst provided by the invention has a certain dimension, can be used for being filled into a fixed bed to form a bed layer with a certain height, and during catalytic reaction, materials such as propylene, hydrogen peroxide, a solvent and the like can smoothly flow through the catalyst bed layer without generating large pressure drop. When the materials flow through the catalyst bed layer, the reaction materials such as propylene, hydrogen peroxide and the like can conveniently enter the pore channels of the catalyst, the adsorption-activation-reaction is carried out on the surfaces of the pore channels, and the products can be desorbed in time and diffused to the outside of the catalyst and flow out of the fixed bed layer along with the main material flow. In addition, the catalyst is stacked to a certain height, so that good strength is kept, the catalyst cannot be cracked, and mutual extrusion deformation is avoided; the catalyst also has a good lifetime and catalytic activity and selectivity do not decay over long runs.
Detailed Description
In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The porous metal provided by the embodiment of the invention is obtained by molding, foaming and sintering an alloy with at least one or more of Fe, co, ni and Cu as the main component, wherein the pore channel of the porous metal is a three-dimensional network open pore structure which is mutually communicated, and the average pore diameter of the three-dimensional pore channel is 0.1-0.75 mm; the diameter of the micro-mesoporous channel of the TS-1 layer on the surface of the channel is 0.5-10nm, the BET specific surface area is 150-300 m 2 Per g, pore volume of 0.1-12 cm 3 (iv) g. The porous metal is a general chemical material, can be purchased by a seller, and can also be directly customized by a manufacturer.
Preparation example of carbon porous Metal
Example 1
Washing porous Fe with the average pore diameter of 0.1 μm with ethanol and pure water for at least three times, drying to remove impurities such as possible pollutants, placing porous Fe in a tubular high temperature furnace with pore channels of three-dimensional network open pore structure, and roasting at 105 deg.C for 5 hr in nitrogen atmosphere; switched to air atmosphere bakingSintering at the temperature of 210 ℃ for 0.5h; switching to nitrogen roasting at 275 deg.C for 50min; is switched to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (2) is 0.1, and the introducing time is 30min; switching to nitrogen for roasting at 350 deg.C for 45min; switching to methane and N 2 Mixed gas of methane and N 2 The flow ratio of (1) is 0.1, and the introduction time is 1min; generating and attaching a layer of carbon substance on the surface of the porous Fe pore channel, and analyzing the carbon substance to obtain a mixture of carbon nanofibers, carbon nanotubes and graphene sheets with a graphene structure; and switching to nitrogen to cool to room temperature to obtain the carbon porous Fe.
Example 2
Washing porous Cu with pore channel size of 0.55mm with ethanol and pure water sequentially for at least three times, drying to remove impurities such as possible pollutants, placing porous Cu in a tubular high temperature furnace with pore channel of three-dimensional network open pore structure, and roasting at 105 deg.C for 5 hr in nitrogen atmosphere; roasting in oxygen atmosphere at 750 deg.c for 7 hr; switching to nitrogen roasting at 275 deg.C for 65min; switch to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (2) is 50, and the introduction time is 5h; switching to nitrogen for roasting at 900 deg.C for 75min; switching to ethane and N 2 Mixed gas of ethane and N 2 The flow ratio of (2) is 10, and the introduction time is 200min; generating and attaching a layer of carbon substance on the surface of a porous Cu pore channel, and analyzing the carbon substance to obtain a mixture of carbon nanofibers, carbon nanotubes and graphene sheets with a graphene structure; and switching to nitrogen to cool to room temperature to obtain the carbon porous Cu.
Example 3
Washing porous Co with pore channel size of 0.25mm with ethanol and pure water for at least three times, drying to remove impurities such as possible pollutants, placing porous Co in a tubular high temperature furnace with pore channel of three-dimensional network open pore structure, and calcining in nitrogen atmosphere at 105 deg.C for 5 hr(ii) a Roasting in oxygen atmosphere at 500 deg.c for 5 hr; nitrogen roasting is switched to be performed, wherein the roasting temperature is 550 ℃, and the roasting time is 85min; is switched to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (2) is 20, and the introducing time is 60min; switching to nitrogen for roasting at 425 ℃ for 105min; switching to acetylene and N 2 Mixed gas of acetylene and N 2 The flow ratio of (2) and the introduction time of 50min; a layer of carbon substance is generated and attached to the surface of the porous Co pore channel, and the carbon substance is a mixture of carbon nanofibers, carbon nanotubes and graphene sheets with a graphene structure after analysis; and switching to nitrogen and cooling to room temperature to obtain the carbon porous Co.
Example 4
Washing porous Ni with pore channel size of 0.5 μm with ethanol and pure water sequentially for at least three times, drying to remove impurities such as possible pollutants, placing porous metal with pore channel of three-dimensional network open pore structure in a tubular high temperature furnace, and calcining in nitrogen atmosphere at 105 deg.C for 5 hr; the roasting is switched to air atmosphere roasting, the roasting temperature is 625 ℃, and the roasting time is 3.5 hours; nitrogen roasting is switched, the roasting temperature is 575 ℃, and the roasting time is 75min; switch to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (3) to (5) is 3.5, and the introduction time is 45min; switching to nitrogen for roasting at 535 ℃ for 115min; switching to ethylene and N 2 Mixed gas of (2), ethylene and N 2 The flow ratio of (2) is 5.5, and the introducing time is 45min; generating and attaching a layer of carbon substance on the surface of the porous Ni pore channel, and analyzing the carbon substance to obtain a mixture of carbon nanofibers, carbon nanotubes and graphene sheets with a graphene structure; and switching to nitrogen and cooling to room temperature to obtain the carbon porous Ni.
Example 5
Washing porous Fe-Ni with pore channel size of 0.75mm with ethanol and pure water for at least three times, drying to remove impurities such as pollutant, placing porous metal with pore channel of three-dimensional network open pore structure in tubular high temperature furnace, roasting in nitrogen atmosphere, and calciningThe temperature of the reaction kettle is 105 ℃, and the time is 5 hours; the roasting is switched to air atmosphere roasting, the roasting temperature is 625 ℃, and the roasting time is 5.5 hours; switching to nitrogen roasting at 575 deg.C for 25min; is switched to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (3) is 0.8, and the feeding time is 3.25h; switching to nitrogen for roasting at 495 ℃ for 35min; switching to ethanol and N 2 Mixed gas of (2), ethanol and N 2 The flow ratio of (2) is 0.25, and the introduction time is 105min; generating and attaching a layer of carbon substance on the surface of the porous Ni pore channel, and analyzing the carbon substance to obtain a mixture of nano carbon fibers, nano carbon tubes and graphene sheets with a graphene structure; and switching to nitrogen to cool to room temperature to obtain the carbon porous Fe-Ni.
Example 6
Washing porous Cu-Ni with pore channel size of 0.25mm with ethanol and pure water sequentially for at least three times, drying to remove impurities such as possible pollutants, placing porous metal with pore channel of three-dimensional network open pore structure in a tubular high temperature furnace, and roasting at 105 deg.C for 5 hr in nitrogen atmosphere; the roasting is switched to an oxygen atmosphere, the roasting temperature is 700 ℃, and the roasting time is 2.75 hours; nitrogen roasting is switched, the roasting temperature is 625 ℃, and the roasting time is 100min; switch to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (2) is 25, and the feeding time is 3h; switching to nitrogen for roasting at 550 ℃ for 80min; switching to benzene and N 2 Mixed gas of benzene and N 2 The flow ratio of (2) is 0.5, and the introduction time is 130min; generating and attaching a layer of carbon substance on the surface of the porous Cu-Ni pore channel, and analyzing the carbon substance to obtain a mixture of carbon nanofibers, carbon nanotubes and graphene sheets with a graphene structure; and switching to nitrogen to cool to room temperature to obtain the carbon porous Cu-Ni.
Example 7
Washing porous Co-Cu with pore channel size of 0.15mm with ethanol and pure water for at least three times, drying to remove impurities such as pollutant, etc., wherein the pore channel of the porous metal is three-dimensional network open pore structure, and placing in tubular high temperatureRoasting in a furnace in a nitrogen atmosphere at 105 ℃ for 5 hours; roasting in air or oxygen atmosphere at 615 ℃ for 2.75h; nitrogen roasting is switched, the roasting temperature is 585 ℃, and the roasting time is 45min; switch to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (1) to (5) and the introduction time of 45min; switching to nitrogen for roasting at 850 ℃ for 65min; switching to acetone and N 2 Mixed gas of (2), acetone and N 2 The flow ratio of (2) is 3, and the introducing time is 75min; a layer of carbon substance is generated and attached to the surface of the porous Co-Cu pore channel, and the carbon substance is a mixture of carbon nanofibers, carbon nanotubes and graphene sheets with a graphene structure through analysis; and switching to nitrogen and cooling to room temperature to obtain the carbon porous Co-Cu.
Preparation example of modified TS-1 glue solution
Example 8
Adding tetraalkyl silicate and functionalized trialkoxysilane into an aqueous solution containing a template agent, stirring, adding an aqueous solution of a pH regulator, continuing stirring, adding an alcoholic solution of tetraalkyl titanate, and stirring for 2 hours at room temperature to form gel, thereby obtaining a modified TS-1 colloidal solution; the tetramethyl silicate comprises aniline methyl triethoxysilane, tetrapropyl ammonium hydroxide, trimethylamine, tetramethyl titanate, methanol and H 2 The molar ratio of O is 0.5.
Example 9
Adding tetraalkyl silicate and functionalized trialkoxysilane into an aqueous solution containing a template agent, stirring, adding an aqueous solution of a pH regulator, continuing stirring, adding an alcoholic solution of tetraalkyl titanate, and stirring for 10 hours at room temperature to form gel, thereby obtaining a modified TS-1 colloidal solution; the tetraethyl silicate comprises aniline methyl triethoxysilane, tetrapropyl ammonium bromide, ammonia water, tetraethyl titanate, ethanol and H 2 The molar ratio of O is 1.5.
Example 10
Adding tetraalkyl silicate and functionalized trialkoxysilane into water solution containing template agent, stirring, adding water solution of pH regulator, stirring, adding titanic acidStirring the alcoholic solution of the tetraalkyl ester for 8 hours at room temperature to form gel to obtain modified TS-1 gel liquid; the silicic acid tetra-n-propyl ester comprises gamma-mercaptopropyl trimethoxy silane, tetrapropyl ammonium bromide, ethylamine, tetraisopropyl titanate, isopropanol and H 2 The molar ratio of O is 1.2.
Example 11
Adding tetraalkyl silicate and functionalized trialkoxysilane into an aqueous solution containing a template agent, stirring, adding an aqueous solution of a pH regulator, continuing stirring, adding an alcoholic solution of tetraalkyl titanate, and stirring at room temperature for 6 hours to form gel, thereby obtaining a modified TS-1 colloidal solution; the tetraisopropyl silicate comprises gamma-mercaptopropyltriethoxysilane, tetrapropylammonium hydroxide, ethylenediamine, tetra-n-butyl titanate, n-butyl alcohol and H 2 The molar ratio of O is 0.75.
Example 12
Adding tetraalkyl silicate and functionalized trialkoxysilane into an aqueous solution containing a template agent, stirring, adding an aqueous solution of a pH regulator, continuing stirring, adding an alcoholic solution of tetraalkyl titanate, and stirring for 9 hours at room temperature to form gel, thereby obtaining a modified TS-1 colloidal solution; the tetraethyl silicate comprises gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, tetrapropyl ammonium bromide, isopropylamine, tetraethyl titanate, isobutanol and H 2 The molar ratio of O is 0.85, 0.12.
Example 13
Adding tetraalkyl silicate and functionalized trialkoxysilane into an aqueous solution containing a template agent, stirring, adding an aqueous solution of a pH regulator, continuing stirring, adding an alcoholic solution of tetraalkyl titanate, and stirring for 5 hours at room temperature to form gel, thereby obtaining a modified TS-1 colloidal solution; the tetraethyl silicate comprises gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, tetrapropylammonium hydroxide, ethylenediamine, tetraisopropyl titanate, isopropanol and H 2 The molar ratio of O is 1.35.
Example 14
Adding tetraalkyl silicate and functionalized trialkoxysilane into water solution containing template agent, stirring, adding water solution of pH regulator, stirring, adding alcoholic solution of tetraalkyl titanateStirring at room temperature for 8.5h to form gel, and obtaining modified TS-1 glue solution; the tetraisopropyl silicate comprises beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, tetrapropyl ammonium bromide, n-propylamine, tetra-n-propyl titanate, n-butyl alcohol and H 2 The molar ratio of O is 1.15.
Example 15
Adding tetraalkyl silicate and functionalized trialkoxy silane into a template-containing aqueous solution, stirring, adding a pH regulator aqueous solution, continuing stirring, adding a tetraalkyl titanate alcoholic solution, stirring at room temperature for 7.5 hours to form gel, and obtaining a modified TS-1 glue solution; the silicic acid tetraisopropyl ester comprises beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane, tetrapropyl ammonium bromide, isopropylamine, tetramethyl titanate, methanol and H 2 The molar ratio of O is 0.55.
Examples of preparation of integrally modified TS-1 catalysts
Any of the carbon porous metals obtained in examples 1 to 7 was immersed in any of the modified TS-1 dope solutions obtained in examples 8 to 15, and a modified TS-1 catalyst of a monolith form was obtained in the following manner, but the scope of the catalyst is not limited to the range described in the examples.
The following integral modified TS-1 catalyst is a cylindrical structure with the height of 2 mm-500 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 0.5 mu m-0.75 mm; the diameter of the micro-mesoporous channel of the TS-1 layer on the surface of the channel is 0.5-10nm, the BET specific surface area is 150-300 m 2 Per g, pore volume of 0.1-12 cm 3 /g。
Example 16
Soaking the carbon porous metal obtained in the example 1 in the modified TS-1 glue solution obtained in the example 8 at the ratio of 20 ℃ and 3min, taking out the carbon porous metal, draining off the surface liquid, placing the carbon porous metal on an upper grid frame in a pressure kettle filled with 0.25% ammonia water solution, heating the pressure kettle to 125 ℃ and keeping the temperature for 10h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing the carbon porous metal in a high-temperature furnace, drying at 105 ℃ for 5h, heating to 450 ℃ and roasting for 2h, cooling to room temperature and taking out the carbon porous metal to obtain the integral modified TS-1 catalyst.
Example 17
Soaking the carbon porous metal obtained in example 7 in the modified TS-1 glue solution obtained in example 15 at 80 ℃ for 60min, taking out the carbon porous metal, draining off surface liquid, placing on an upper grid frame in a pressure kettle filled with 25% methylamine solution, heating the pressure kettle to 195 ℃, keeping the temperature for 80h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing in a high-temperature furnace, drying at 105 ℃ for 5h, heating to 650 ℃ for roasting for 8h, cooling to room temperature, and taking out to obtain the overall-structure-type modified TS-1 catalyst.
Example 18
Soaking the carbon porous metal obtained in the example 3 in the modified TS-1 glue solution obtained in the example 10 at a ratio of 55 ℃ to 45min based on the fact that the modified TS-1 glue solution completely immerses the carbon porous metal, taking out the carbon porous metal, draining off surface liquid, placing the carbon porous metal on an upper grid frame in a pressure kettle filled with 15% ethylamine solution, heating the pressure kettle to 155 ℃ for 48h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing the carbon porous metal in a high-temperature furnace, drying the carbon porous metal at 105 ℃ for 5h, heating to 550 ℃ for roasting for 6h, cooling to room temperature, and taking out the carbon porous metal to obtain the integral modified TS-1 catalyst.
Example 19
Soaking the carbon porous metal obtained in the example 2 in the modified TS-1 glue solution obtained in the example 9 at the soaking temperature of 35 ℃ for 30min, taking out the carbon porous metal, draining off surface liquid, placing the carbon porous metal on an upper grid frame in a pressure kettle filled with 11.5% ethylenediamine solution, heating the pressure kettle to 165 ℃, keeping the temperature for 60h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing the carbon porous metal in a high-temperature furnace, drying the carbon porous metal at 105 ℃ for 5h, heating the carbon porous metal to 515 ℃ for roasting 7h, cooling the carbon porous metal to room temperature, and taking out the carbon porous metal to obtain the integral modified TS-1 catalyst.
Example 20
The carbon porous metal obtained in example 5 was immersed in the modified TS-1 colloidal solution obtained in example 12 at a ratio of 55 ℃ for 38min based on the fact that the modified TS-1 colloidal solution was completely immersed in the carbon porous metal, the immersion temperature was 55 ℃, the carbon porous metal was taken out, the surface liquid was drained off, the carbon porous metal was placed on an upper grid in a autoclave containing 2.5% n-propylamine solution, the autoclave was heated to 135 ℃ and kept for 24h, the autoclave was cooled to room temperature, the carbon porous metal was taken out and placed in a high temperature furnace, dried at 105 ℃ for 5h, then heated to 625 ℃ and calcined for 4.5h, and the carbon porous metal was taken out after cooling to room temperature, thereby obtaining an overall modified TS-1 catalyst.
Example 21
Soaking the carbon porous metal obtained in the example 6 in the modified TS-1 glue solution obtained in the example 11 at a ratio of 42.5 ℃ for 15min based on the fact that the modified TS-1 glue solution completely immerses the carbon porous metal, taking out the carbon porous metal, draining off surface liquid, placing the carbon porous metal on an upper grid frame in a pressure kettle filled with 17.5% n-propylamine solution, heating the pressure kettle to 158 ℃, keeping the temperature for 65h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing the carbon porous metal in a high-temperature furnace, drying at 105 ℃ for 5h, heating to 575 ℃ and roasting for 3.8h, cooling to room temperature and taking out to obtain the overall-form modified TS-1 catalyst.
Example 22
Soaking the carbon porous metal obtained in the example 4 in the modified TS-1 glue solution obtained in the example 13 at the soaking temperature of 45.5 ℃ for 36min, taking out the carbon porous metal, draining off the surface liquid, placing on an upper grid frame in a pressure kettle filled with 18.5% isopropylamine solution, heating the pressure kettle to 175 ℃, keeping the temperature for 70h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing in a high-temperature furnace, drying at 105 ℃ for 5h, heating to 515 ℃ for roasting for 6.2h, cooling to room temperature, and taking out to obtain the overall-formula modified TS-1 catalyst.
Example 23
Soaking the carbon porous metal obtained in the example 6 in the modified TS-1 glue solution obtained in the example 14 at the soaking temperature of 70 ℃ for 55min, taking out the carbon porous metal, draining off the surface liquid, placing the carbon porous metal on an upper grid frame in a pressure kettle filled with 17.5% isopropylamine solution, heating the pressure kettle to 170 ℃, keeping the temperature for 48h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing the carbon porous metal in a high-temperature furnace, drying the carbon porous metal at 105 ℃ for 5h, heating the carbon porous metal to 525 ℃ and roasting the carbon porous metal for 7.5h, cooling the carbon porous metal to the room temperature and taking out the carbon porous metal to obtain the overall-structure-type modified TS-1 catalyst.
Example 24
Soaking the carbon porous metal obtained in the example 2 in the modified TS-1 glue solution obtained in the example 15 at the soaking temperature of 32.5 ℃ for 51min, taking out the carbon porous metal, draining off the surface liquid, placing the carbon porous metal on an upper grid frame in a pressure kettle filled with trimethylamine solution with the concentration of 18%, heating the pressure kettle to 160 ℃, keeping the temperature for 52h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing the carbon porous metal in a high-temperature furnace, drying the carbon porous metal at 105 ℃ for 5h, heating the pressure kettle to 595 ℃ again, roasting the carbon porous metal for 4h, cooling the temperature to room temperature, and taking out the carbon porous metal to obtain the integral modified TS-1 catalyst.
Example 25
Soaking the carbon porous metal obtained in the example 6 in the modified TS-1 glue solution obtained in the example 12 at the soaking temperature of 62.5 ℃ for 52.5min in proportion of the modified TS-1 glue solution completely immersing the carbon porous metal, taking out the carbon porous metal, draining off surface liquid, placing on an upper grid frame in a pressure kettle filled with 16.5% triethylamine solution, heating the pressure kettle to 160 ℃, keeping the temperature for 36h, cooling the pressure kettle to room temperature, taking out the carbon porous metal, placing in a high-temperature furnace, drying at 105 ℃ for 5h, heating to 475 ℃ and roasting for 5.6h, cooling to room temperature and taking out to obtain the overall-form modified TS-1 catalyst.
Propylene one-step direct epoxidation example
The catalysts of the overall modified TS-1 prepared in examples 16 to 25 were used in the one-step propylene oxidation process for producing propylene oxide, and propylene oxide was obtained in the following examples, but they are not limited to the scope of the examples.
In the examples below, the diameter of the monolithic catalyst is 50mm and the height of the catalyst bed is 1500mm.
Example 26
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in example 16 was loaded in a fixed bed reactor, the size of the fixed bed reactor was designed and determined according to the general principle of chemical engineering, in combination with the size of the catalyst, the flow rate of the reaction materials and the process conditions, propylene was metered into the reactor at a pressure of 0.4MPa, acetonitrile and hydrogen peroxide were fed into the reactor respectively, the volume flow ratio of propylene, acetonitrile, hydrogen peroxide was 10 -1 The concentration of hydrogen peroxide is 30 percent, the temperature of the reactor bed layer is controlled to be 35 ℃, the materials react in the catalyst bed layer, and the mixture generated by the reaction is discharged from the reactor. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analyzing from the outlet of the reactor in the reaction process, calculating the conversion rate (99.5%) of hydrogen peroxide, wherein the selectivity of the generated propylene oxide is 90%, the propylene is slightly excessive, the selectivity of the propylene is 95%, the reaction outlet material enters a storage tank, further separating according to a separation principle and a separation method in chemical engineering to obtain a product propylene oxide, recovering and recycling the acetonitrile and unreacted propylene obtained by separation, and the water obtained by separation meets the discharge standard and can be used as industrial water or directly discharged. The energy efficiency of the whole process is optimized through energy integration.
Example 27
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in example 25 was loaded into a fixed bed reactor, propylene was metered into the reactor at 0.4MPa, propylene, ethanol, hydrogen peroxideThe volume flow ratio of (1) is 5 -1 The concentration of hydrogen peroxide is 70 percent, the temperature of the reactor bed layer is controlled to be 75 ℃, the materials react in the catalyst bed layer, and the mixture generated by the reaction is discharged from the reactor. And the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analyzing from the outlet of the reactor in the reaction process, calculating the conversion rate (99.6%) of hydrogen peroxide, wherein the selectivity of the generated propylene oxide is 91%, the propylene is slightly excessive, the selectivity of the propylene is 96%, the reaction outlet material enters a storage tank for further separation to obtain products of propylene oxide, ethanol and propylene, the ethanol and the propylene are recycled, and the water obtained by separation meets the discharge standard and can be used as industrial water or directly discharged.
Example 28
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in example 18 was loaded in a fixed bed reactor, propylene was metered into the reactor at a pressure of 0.4MPa, dioxane and hydrogen peroxide were fed into the reactor, the volume flow ratio of propylene, dioxane and hydrogen peroxide was 15 -1 The concentration of hydrogen peroxide is 50 percent, the temperature of a reactor bed layer is controlled to be 55 ℃, materials react in a catalyst bed layer, and a mixture generated by the reaction is discharged from the reactor. And the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. In the reaction process, sampling and analyzing are carried out at the outlet of the reactor, the conversion rate (99.7%) of hydrogen peroxide is calculated, and the selectivity of the generated propylene oxide is 89%. The propylene selectivity was 94.5% with a slight excess of propylene. And (3) feeding the reaction outlet material into a storage tank, further separating to obtain a product of propylene oxide, a solvent and unreacted propylene, recycling the solvent and the unreacted propylene, and separating to obtain water which meets the discharge standard and can be used as industrial water or directly discharged. The energy efficiency of the whole process is optimized through energy integration.
Example 29
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in the example 20 is filled in a fixed bed reactor, propylene is added into the reactor by measuring at the pressure of 0.4MPa, acetone and hydrogen peroxide are respectively introduced into the reactor, the volume flow ratio of the propylene to the acetone to the hydrogen peroxide is 5 -1 The concentration of hydrogen peroxide is 45 percent, the temperature of the reactor bed layer is controlled to be 45 ℃, the materials react in the catalyst bed layer, and the mixture generated by the reaction is discharged from the reactor. And the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analyzing from the outlet of the reactor in the reaction process, and calculating the conversion rate (99.9%) of hydrogen peroxide, wherein the selectivity of the generated propylene oxide is 90.5%. The propylene selectivity was 94.5% with a slight excess of propylene. And (3) feeding the material at the reaction outlet into a storage tank, further separating to obtain products of propylene oxide, acetone and propylene, recycling acetone and propylene, and separating to obtain water for use as reclaimed water.
Example 30
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in the example 17 is filled in a fixed bed reactor, propylene is added into the reactor by measuring at the pressure of 0.4MPa, methanol and hydrogen peroxide are respectively introduced into the reactor, the volume flow ratio of the propylene to the methanol to the hydrogen peroxide is 9 -1 The concentration of hydrogen peroxide is 50 percent, the temperature of a reactor bed layer is controlled to be 45 ℃, materials react in a catalyst bed layer, and a mixture generated by the reaction is discharged from the reactor. And the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. In the reaction process, sampling and analyzing are carried out at the outlet of the reactor, the conversion rate (98.7%) of hydrogen peroxide is calculated, and the selectivity of the generated propylene oxide is 91.5%. The propylene was in slight excess, and the selectivity to propylene was 93.8%. The materials at the reaction outlet enter a storage tank, the propylene oxide, the methanol and the propylene are further separated, the methanol and the propylene are recycled, and the water obtained by separation meets the discharge standard and can be used as a working fluidThe industrial water is used.
Example 31
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in example 22 is loaded in a fixed bed reactor, propylene is added into the reactor by metering at a pressure of 0.4MPa, acetonitrile and hydrogen peroxide are respectively introduced into the reactor, the volume flow ratio of the propylene to the acetonitrile to the hydrogen peroxide is 5 -1 The concentration of hydrogen peroxide is 55 percent, the temperature of the bed layer of the reactor is controlled to be 65 ℃, the materials react in the catalyst bed layer, and the mixture generated by the reaction is discharged from the reactor. And the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analyzing from the outlet of the reactor in the reaction process, and calculating the conversion rate (98.9%) of hydrogen peroxide, wherein the selectivity of the generated propylene oxide is 93.8%. The propylene was in slight excess, with a propylene selectivity of 96.4%. And (3) feeding the reaction outlet material into a storage tank, further separating to obtain a product epoxypropane, recycling acetonitrile and propylene obtained by separation, wherein water obtained by separation meets the discharge standard, can be used as industrial water, and can also be directly discharged.
Example 32
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in example 23 was loaded in a fixed bed reactor, propylene was metered into the reactor at a pressure of 0.4MPa, methanol and hydrogen peroxide were fed into the reactor, respectively, the volume flow ratio of propylene, methanol, hydrogen peroxide was 5 -1 The concentration of hydrogen peroxide is 55 percent, the temperature of the bed layer of the reactor is controlled to be 65 ℃, the materials react in the catalyst bed layer, and the mixture generated by the reaction is discharged from the reactor. And the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analyzing from the outlet of the reactor in the reaction process, and calculating the conversion rate (98.9%) of hydrogen peroxide, wherein the selectivity of the generated propylene oxide is 92.3%. Slight excess of propylene, CThe selectivity to alkene was 93.8%. And further separating the reaction materials to obtain a product of propylene oxide, separating to obtain methanol and propylene, recycling, and separating to obtain water meeting the discharge standard. The energy efficiency of the whole process is optimized through energy integration.
Example 33
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in example 21 was loaded in a fixed bed reactor, propylene was metered into the reactor at a pressure of 0.4MPa, dioxane and hydrogen peroxide were fed into the reactor respectively, the volumetric flow ratio of propylene, dioxane and hydrogen peroxide was 6 -1 The concentration of hydrogen peroxide is 55 percent, the temperature of the bed layer of the reactor is controlled to be 45 ℃, the materials react in the catalyst bed layer, and the mixture generated by the reaction is discharged from the reactor. And the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analyzing from the outlet of the reactor in the reaction process, and calculating the conversion rate (99.5%) of hydrogen peroxide, wherein the selectivity of the generated propylene oxide is 91.5%. The propylene was in slight excess, and the selectivity to propylene was 96.2%. And separating reaction materials to obtain a product of propylene oxide, recycling the obtained dioxane and unreacted propylene, wherein the water obtained by separation meets the discharge standard, can be used as industrial water and can also be directly discharged.
Example 34
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in example 19 was loaded in a fixed bed reactor, propylene was metered into the reactor at a pressure of 0.4MPa, acetonitrile, ethanol and hydrogen peroxide were fed into the reactor respectively, the volume flow ratio of propylene, mixed solvent and hydrogen peroxide was 10 -1 Controlling the temperature of the reactor bed layer to be 80 ℃ and the concentration of hydrogen peroxide to be 40 percent, and reacting the materials in the catalyst bed layer to generateIs discharged from the reactor. The discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analyzing from the outlet of the reactor in the reaction process, and calculating the conversion rate (97.5%) of hydrogen peroxide, wherein the selectivity of the generated propylene oxide is 91.5%. The propylene selectivity was 93.8% with a slight excess of propylene. And further separating the reaction materials to obtain a product of propylene oxide, recycling the solvent obtained by separation and unreacted propylene, wherein the water obtained by separation meets the discharge standard, can be used as industrial water and can also be directly discharged.
Example 35
The application of the integral modified TS-1 catalyst in the preparation of propylene oxide by a direct propylene oxidation method comprises the following steps:
the integral modified TS-1 catalyst prepared in example 24 was loaded in a fixed bed reactor, propylene was added to the reactor by metering at a pressure of 0.4MPa, acetonitrile, acetone, and hydrogen peroxide were fed to the reactor respectively, the volume flow ratio of propylene, mixed solvent, and hydrogen peroxide was 10.5, the ratio of acetonitrile to acetone in the mixed solvent was 5 -1 The concentration of hydrogen peroxide is 70 percent, the temperature of the reactor bed layer is controlled to be 55 ℃, the materials react in the catalyst bed layer, and the mixture generated by the reaction is discharged from the reactor. And the discharged mixture is subjected to subsequent separation to obtain pure propylene oxide. Sampling and analyzing from the outlet of the reactor in the reaction process, calculating the conversion rate (99.6%) of hydrogen peroxide, and the selectivity of the generated propylene oxide is 89.7%. The propylene was in slight excess, and the selectivity to propylene was 93.8%. And further separating the reaction materials to obtain a product of propylene oxide, recycling the solvent obtained by separation and unreacted propylene, wherein the water obtained by separation meets the discharge standard, can be used as industrial water, and can also be directly discharged.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. A monolithic modified TS-1 catalyst is prepared by a preparation method comprising the following steps:
soaking the carbon porous metal in the modified TS-1 glue solution according to the proportion that the modified TS-1 glue solution completely immerses the carbon porous metal, taking out the carbon porous metal after soaking, draining off surface liquid, placing the carbon porous metal 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 metal, drying, heating for roasting, cooling to room temperature, and taking out to obtain the integral modified TS-1 catalyst;
the carbon porous metal is prepared by a preparation method comprising the following steps:
roasting the cleaned porous metal in a nitrogen atmosphere at the temperature of 100-120 ℃ for 4-6 h; the roasting is switched to air or oxygen roasting, the roasting temperature is 210-750 ℃, and the roasting time is 0.5-7 h; switching to nitrogen roasting at 275-750 deg.c; switch to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of the water inlet pipe is 0.1-50, and the inlet time is 30 min-5 h; switching to nitrogen for roasting at the roasting temperature of 350-900 ℃; switching into small molecular substance containing C, H and O and N 2 The mixed gas of C, H, O-containing small molecular substances and N 2 The flow ratio of (1) to (10) and the introduction time of (1) to (200) min; switching to nitrogen for cooling to obtain the carbon porous metal;
the modified TS-1 glue solution is prepared by a preparation method comprising the following steps:
adding tetraalkyl silicate and functionalized trialkoxysilane into a template-containing aqueous solution, stirring, adding a pH regulator aqueous solution, continuing stirring, adding a tetraalkyl titanate alcohol solution, and stirring at room temperature to form a gel, thereby obtaining a modified TS-1 gel 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), (0.01-0.65), (0.01-0.175), (0.5-2.0) and (2.0-25);
the integral modified TS-1 catalyst is of a cylindrical structure with the height of 2 mm-500 mm, three-dimensional pore channels which are communicated with each other are contained in the catalyst, and the average pore diameter of the three-dimensional pore channels is 0.5 mu m-0.75 mm; the diameter of the micro-mesoporous channel of the TS-1 layer on the surface of the channel is 0.5-10nm, the BET specific surface area is 150-300 m 2 Per g, pore volume of 0.1-12 cm 3 /g；
Wherein, the main component of the porous metal is at least one or more of Fe, co, ni and Cu;
the functionalized trialkoxysilane is aniline methyl trimethoxy silane, aniline methyl triethoxy silane, gamma-mercaptopropyl trimethoxy silane, gamma-mercaptopropyl triethoxy silane, gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane, gamma- (2, 3-epoxy propoxy) propyl triethoxy silane and beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane.
2. The integrally modified TS-1 catalyst of claim 1 wherein: wherein the temperature of soaking the carbon porous metal in the modified TS-1 glue solution is 20-80 ℃, 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 for keeping the reaction temperature at 125-195 ℃ and the reaction time at 10-80 h;
and after drying, heating for roasting, wherein the drying temperature is 100-120 ℃, and the drying time is 1-10 h.
3. The monolith modified TS-1 catalyst of claim 1 wherein the treated clean porous metal is washed with ethanol, pure water at least three times in sequence, dried;
the pore channels of the porous metal are three-dimensional network-shaped open pore junctions which are mutually communicatedThe average aperture of the three-dimensional pore canal is 0.1 mu m-0.75 mm; the diameter of the micro-mesoporous channel of the TS-1 layer on the surface of the pore channel is 0.5-10nm, the BET specific surface area is 150-300 m 2 Per g, pore volume of 0.1-12 cm 3 /g；
The C, H and O-containing micromolecule substance is methane, ethane, acetylene, ethylene, propylene, propine, methanol, ethanol, acetone, benzene, toluene and ethylbenzene.
4. The structurally-modified TS-1 catalyst of claim 1 wherein the tetraalkyl silicate is tetramethyl silicate, tetraethyl silicate, tetraisopropyl silicate, tetra-n-propyl silicate;
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 titanate is tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, 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 catalyst of the formula-modified TS-1 according to any one of claims 1 to 4 for the preparation of propylene oxide by direct oxidation of propylene.
6. The use of claim 5, wherein: 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 (5-15) to (2-20) to (1.5-9), and the space velocity LHSV of the reactor is 200-1000 h -1 Controlling the temperature of the reactor at 35-90 ℃, controlling the temperature of the fixed bed layer at 35-90 ℃, reacting the materials in the catalyst bed layer, and obtaining a mixtureAnd (3) discharging from the reactor, carrying out subsequent separation on the discharged mixture to obtain pure propylene oxide, sampling and analyzing from an outlet of the reactor in the reaction process, and calculating the conversion rate of hydrogen peroxide to generate the selectivity of the propylene oxide.
7. The use of claim 6, wherein: wherein the solvent is at least one of acetonitrile, acetone, dioxane, methanol and ethanol; the concentration of the hydrogen peroxide is 30-70%.
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