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

Monolithic modified TS-1 catalyst based on carbon porous ceramic, and preparation method and application thereof Download PDF

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CN111085264B
CN111085264B CN201811234304.9A CN201811234304A CN111085264B CN 111085264 B CN111085264 B CN 111085264B CN 201811234304 A CN201811234304 A CN 201811234304A CN 111085264 B CN111085264 B CN 111085264B
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porous ceramic
catalyst
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reactor
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CN111085264A (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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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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

Monolithic modified TS-1 catalyst based on carbon porous ceramic, and preparation method and application thereof
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 epoxypropane is an important chemical raw material, is applied to synthesis of polyether polyol, propylene glycol ether, dimethyl carbonate, polypropylene carbonate, a nonionic surfactant and the like, and is a necessary raw material in the 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, our country has also started to ban the use of chlorohydrin processes for producing propylene oxide. 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 by the one-step direct oxidation method mainly takes a TS-1 catalyst, and through years of research, the TS-1 catalyst has made an important progress, the activity and the selectivity reach better levels, however, TS-1 is an extremely fine particle having a nanopore, and there is a bottleneck problem that it is extremely difficult to separate a fine particle from a liquid in an 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 after forming and synergism is also prepared by adopting a suitable reactor to make up for the defects of the catalyst, such as a semi-continuous tank reactor, a fixed bed reactor and the like, the problem cannot be fundamentally solved.
Disclosure of Invention
The first purpose of the invention is to provide an integral modified TS-1 catalyst, which solves the problem of the catalyst for preparing propylene oxide by direct oxidation of propylene in the prior one-step method, the catalyst has the advantages of greatly improving the selectivity of the main product propylene oxide, greatly improving the production efficiency and reducing 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 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, the structure of the catalyst is a cylindrical structure with the diameter of 3-100 mm and the height of 2-50 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 0.1-0.75 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。
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 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 to drain the surface liquid, and placing the mixture on the liquid level in a pressure reactor filled with ammonia or an amine solution, heating the mixture to keep reaction, cooling the mixture to room temperature, taking out the carbon porous ceramic, drying the carbon porous ceramic, heating the carbon porous ceramic for roasting, cooling the carbon porous ceramic to room temperature, and taking out the carbon porous ceramic to obtain the integral modified TS-1 catalyst.
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; preferably, the following components are used: the temperature is 45-65 ℃, and the time is 15-40 min.
The amine solution is at least one aqueous solution of methylamine, ethylamine, ethylenediamine, n-propylamine, isopropylamine, dimethylamine, trimethylamine, diethylamine and triethylamine, preferably at least one aqueous solution of trimethylamine, triethylamine, dimethylamine and isopropylamine; the concentration of the ammonia or 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 up for roasting, wherein the drying temperature is 100-120 ℃, the time is 1-10 h, preferably, the temperature is 105 ℃, and the time is 5h; the roasting temperature is 450-650 ℃, and the roasting time is 2-8 h.
The preparation method of the carbon porous ceramic comprises the following steps:
cutting the cleaned porous ceramic, soaking in metal salt solution, the ratio of the porous ceramic to the metal salt solution is based on the fact that the solution can immerse the porous ceramic, the porous ceramic is taken out and dried, and the solution is placed 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 cleaned porous ceramic is obtained by washing the porous ceramic with clear water at least three times, drying to remove ash impurities and the like that may be present.
The porous ceramic is a pore canal which contains a three-dimensional network open pore structure communicated with each other, the size of the pore canal is 0.1-0.75 mm, preferably 0.5-0.55 mm; the porous ceramic is a cylindrical structure with the diameter of 3-100 mm and the height of 2-50 mm.
The porous ceramic is prepared from corundum sand, silicon carbide, cordierite and other raw materials as main materials through molding, foaming and sintering, can be purchased from the market or customized by manufacturers, and mainly comprises SiO as a chemical component 2 、Al 2 O 3 、CaO、MgO、Na 2 O、TiO 2 And the ratio of the catalyst to the catalyst is determined according to the production ratio of a porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the invention.
The metal ion in the metal salt solution is Fe 2+ 、Fe 3+ 、Co 2+ 、Ni 2+ 、Cu 2+ At least one of (1) and (b) wherein the anion paired with the metal ion is formate (HCOO) - ) Acetate (CH) 3 COO - ) Propionate (CH) 3 CH 2 COO - ) Citrate, lactate, 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 preferably at least one of ferrous acetate, nickel nitrate, cobalt citrate, copper nitrate, and copper phosphate.
The clean porous ceramic is cut and soaked in a metal salt solution at the temperature of 15-80 ℃ for 5 min-12 h.
Said is in N 2 The drying temperature in the air flow is 100-120 ℃, and the drying time is 2-5 h.
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 maintaining time under the mixed gas flow is as follows: will N 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) is 0.1 to (200) min, and the time of introduction is 1 to (200) min.
The C, H, O-containing small molecular substance is methane, ethane, acetylene, ethylene, propylene, propyne, methanol, ethanol, acetone, benzene, toluene and ethylbenzene, preferably ethane, propane, acetylene, ethylene, propylene, propyne, ethanol and benzene.
The preparation method of the modified TS-1 glue solution comprises 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 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, tetraisopropyl silicate and tetra-n-propyl silicate.
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.
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 oxidation method of propylene.
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 (98.5-99.8%) of hydrogen peroxide, and generating the selectivity (93.5-98.5%) of the propylene oxide.
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 overall efficiency enhancement of the catalyst, the change of the operation mode and the optimization of the operation conditions, 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 with higher boiling point, water and propylene glycol 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, the water with the purity meeting the requirement can be used as industrial water, heat in the water can be recycled and then the water is discharged after reaching the standard, and the problem in the existing propylene oxide production technology is solved.
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, adsorption-activation-reaction is carried out on the surfaces of the pore channels, products can be desorbed and diffused outside the catalyst in time and flow out of the fixed bed layer along with the main material flow, and in addition, the catalyst is stacked to a certain height, so that good strength is kept, the cracking is avoided, and the 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.
Example 1
Cutting porous ceramic with pore channel size of 0.1 μm into cylindrical structure with diameter of 3mm and height of 5mm, washing porous ceramic with clear water for at least three times, drying to remove ash impurities, etc., wherein the porous ceramic contains pore channels with three-dimensional network-like open pore structure, which are communicated with each other, and is prepared from corundum sand, silicon carbide, cordierite, etc. as main materials by molding, foaming and sintering, and can be purchased from market or customized by manufacturer, and the chemical component is mainly SiO 2 、Al 2 O 3 、CaO、MgO、Na 2 O、TiO 2 And the ratio of the catalyst to the catalyst is determined according to the production ratio of a porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the invention. Soaking in 0.15% ferrous acetate water solution at 15 deg.C for 5min. Taking out, drying, putting in a tubular high-temperature furnace, and reacting in N 2 Drying at 105 deg.C for 2h, heating to 180 deg.C, and calcining for 1h; the temperature is raised to 375 ℃ and N is added 2 Switch to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (2) is 0.1, and the introduction time is 30min; switching the gas to N 2 Adjusting the temperature to 350 ℃ for 45min to reduce the metal into fine particles and attach the fine particles to the surface of the porous ceramic; will N 2 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; and generating and attaching a layer of carbon substance on the surface of the porous ceramic pore channel, analyzing the carbon substance to obtain a mixture of carbon nanofibers with a graphene structure, carbon nanotubes and graphene sheets, and cooling to obtain the carbon porous ceramic.
Example 2
Cutting porous ceramic with pore channel size of 0.75mm into cylindrical structure with diameter of 5mm and height of 5mm, and cleaning with clear waterWashing porous ceramic for at least three times, drying to remove ash impurities possibly existing, wherein the porous ceramic contains interpenetrated pore channels with three-dimensional network-shaped open pore structures, is obtained by molding, foaming and sintering raw materials such as corundum sand, silicon carbide, cordierite and the like as main materials, can be purchased from the market or customized by manufacturers, and mainly contains SiO as a chemical component 2 、Al 2 O 3 、CaO、MgO、Na 2 O、TiO 2 And the ratio of the catalyst to the catalyst is determined according to the production ratio of a porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the invention. Soaking in 20% nickel nitrate water solution at 75 deg.C for 12 hr. Taking out, drying, placing in a tubular high-temperature furnace, and reacting in N 2 Drying at 105 deg.C for 5h, heating to 350 deg.C, and calcining for 7h; the temperature is raised to 750 ℃ and N is added 2 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 the gas to N 2 Adjusting the temperature to 900 ℃ for 50min to reduce the metal into fine particles and attach the fine particles to the surface of the porous ceramic; will N 2 Switching to acetylene and N 2 Mixed gas of (2), acetylene and N 2 The flow ratio of (2) is 10, and the introducing time is 200min; and generating and attaching a layer of carbon substance on the surface of the porous ceramic pore channel, analyzing the carbon substance to obtain a mixture of carbon nanofibers with a graphene structure, carbon nanotubes and graphene sheets, and cooling to obtain the carbon porous ceramic.
Example 3
Cutting porous ceramic with pore channel size of 0.55mm into cylindrical structure with diameter of 5mm and height of 5mm, washing porous ceramic with clear water for at least three times, drying to remove ash impurities, etc., wherein the porous ceramic contains pore channels with three-dimensional network-like open pore structure communicated with each other, and is prepared from corundum sand, silicon carbide, cordierite, etc. as main materials by molding, foaming and sintering, and can be purchased from market or customized by manufacturer, and the chemical component is mainly SiO 2 、Al 2 O 3 、CaO、MgO、Na 2 O、TiO 2 Etc. in the proportions between themThe production ratio of the porous ceramic supplier is determined, and the activity of the catalyst in the invention is not obviously influenced. Soaking in 5% cobalt citrate water solution at 45 deg.C for 1 hr. Taking out, drying, placing in a tubular high-temperature furnace, and reacting in N 2 Drying at 105 deg.C for 3h, heating to 450 deg.C, and calcining for 3h; the temperature is raised to 550 ℃ and N is added 2 Switch to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (2) is 25, and the introduction time is 2.5h; switching the gas to N 2 Adjusting the temperature to 480 ℃ for 65min to reduce the metal into fine particles and attach the fine particles to the surface of the porous ceramic; n is to be 2 Switching to ethylene and N 2 Mixed gas of (2), ethylene and N 2 The flow ratio of (2) is 0.5, and the introducing time is 40min; and generating and attaching a layer of carbon substance on the surface of the porous ceramic pore channel, analyzing the carbon substance to obtain a mixture of carbon nanofibers with a graphene structure, carbon nanotubes and graphene sheets, and cooling to obtain the carbon porous ceramic.
Example 4
Cutting porous ceramic with pore channel size of 0.15mm into cylindrical structure with diameter of 5mm and height of 5mm, washing porous ceramic with clear water for at least three times, drying to remove ash impurities, etc., wherein the porous ceramic contains pore channels with three-dimensional network-like open pore structure communicated with each other, and is prepared from corundum sand, silicon carbide, cordierite, etc. as main materials by molding, foaming and sintering, and can be purchased from market or customized by manufacturer, and the chemical component is mainly SiO 2 、Al 2 O 3 、CaO、MgO、Na 2 O、TiO 2 And the ratio of the catalyst to the catalyst is determined according to the production ratio of a porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the invention. Soaking in 7.5% copper nitrate water solution at 50 deg.C for 2 hr. Taking out, drying, placing in a tubular high-temperature furnace, and reacting in N 2 Drying at 105 deg.C for 3h, heating to 475 deg.C, and roasting for 2.5h; the temperature is raised to 600 ℃ and N is added 2 Switch to H 2 And N 2 Mixed gas of H 2 And N 2 At a flow ratio of 5, is introducedThe time is 1.5h; switching the gas to N 2 Adjusting the temperature to 520 ℃ for 105min to reduce the metal into fine particles and attach the fine particles to the surface of the porous ceramic; n is to be 2 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 60min; and generating and attaching a layer of carbon substance on the surface of the porous ceramic pore channel, analyzing the carbon substance to obtain a mixture of carbon nanofibers with a graphene structure, carbon nanotubes and graphene sheets, and cooling to obtain the carbon porous ceramic.
Example 5
Cutting porous ceramic with pore channel size of 0.35mm into cylindrical structure with diameter of 5mm and height of 5mm, washing porous ceramic with clear water for at least three times, drying to remove ash impurities, etc., wherein the porous ceramic contains pore channels with three-dimensional network-like open pore structure communicated with each other, and is prepared from corundum sand, silicon carbide, cordierite, etc. as main materials by molding, foaming and sintering, and can be purchased from market or customized by manufacturer, and the chemical component is mainly SiO 2 、Al 2 O 3 、CaO、MgO、Na 2 O、TiO 2 And the ratio of the catalyst to the catalyst is determined according to the production ratio of a porous ceramic supplier, and has no obvious influence on the activity of the catalyst in the invention. Soaking in 17.5% copper phosphate acetic acid solution at 80 deg.C for 6 hr. Taking out, drying, placing in a tubular high-temperature furnace, and reacting in N 2 Drying at 105 deg.C for 3h, heating to 515 deg.C, and calcining for 3.5h; the temperature is raised to 625 ℃ and N is added 2 Is switched to H 2 And N 2 Mixed gas of H 2 And N 2 The flow ratio of (2) is 10, and the introduction time is 3h; switching the gas to N 2 Adjusting the temperature to 625 ℃ and the time to 85min to reduce the metal into fine particles and attach the fine particles to the surface of the porous ceramic; n is to be 2 Switching to benzene and N 2 Mixed gas of benzene and N 2 The flow ratio of (2) is 0.15, and the introducing time is 60min; a layer of carbon substance is generated and attached on the surface of the porous ceramic pore channel, and the carbon substance is a mixture of nano carbon fiber, nano carbon tube and graphene sheet with a graphene structure through analysis, so that the carbon content of the porous ceramic pore channel is reducedAnd (4) warming to obtain the carbon porous ceramic.
Example 6
Mixing a template agent and water to prepare a solution, adding a pH regulator, stirring, then adding tetraalkyl silicate and functionalized trialkoxy silane, continuously stirring, finally adding an alcoholic solution of tetraalkyl titanate, continuously stirring, stirring for 2 hours at room temperature to form gel, and obtaining a modified TS-1 glue solution; tetramethyl silicate, vinyltriethoxysilane, tetrapropylammonium hydroxide, methylamine, tetramethyl titanate, ethanol and H 2 The molar ratio of O is 0.5.
Example 7
Mixing a template agent and water to prepare a solution, adding a pH regulator, stirring, then adding tetraalkyl silicate and functionalized trialkoxy silane, continuously stirring, finally adding an alcoholic solution of tetraalkyl titanate, continuously stirring, stirring for 10 hours at room temperature to form gel, and obtaining a modified TS-1 glue solution; tetraethyl silicate, vinyltriethoxysilane, tetrapropylammonium bromide, trimethylamine, tetraethyl titanate, n-propanol, and H 2 The molar ratio of O is 1.5.
Example 8
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 for 7 hours to form gel, thereby obtaining a modified TS-1 glue solution; tetra-isopropyl silicate gamma-aminopropyl trimethoxy silane, tetrapropyl ammonium bromide, ethanediamine, tetra-n-propyl titanate, isopropanol, H 2 The molar ratio of O is 1.1.
Example 9
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 for 5 hours to form gel, thereby obtaining a modified TS-1 glue solution; tetra-n-propyl silicate, gamma-aminopropyl triethoxy silane, tetrapropyl ammonium hydroxide, ammonia water, tetraisopropyl titanate, n-butanol and H 2 The molar ratio of O is 0.8.
Example 10
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 for 6 hours to form gel, thereby obtaining a modified TS-1 glue solution; tetraethyl silicate gamma- (beta-aminoethyl) aminopropyltrimethoxysilane tetrapropylammonium hydroxide isopropylamine tetra-n-butyl titanate isobutyl alcohol H 2 The molar ratio of O is 0.65, 0.015.
Example 11
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 for 5 hours to form gel, thereby obtaining a modified TS-1 glue solution; tetraethyl silicate gamma- (beta-aminoethyl) aminopropyltriethoxysilane tetrapropylammonium bromide methylamine tetraisopropyl titanate n-propanol H 2 The molar ratio of O is 0.75.
Example 12
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 for 4 hours at room temperature to form gel, thereby obtaining a modified TS-1 glue solution; tetramethyl silicate gamma-aminoureidopropyltrimethoxysilane tetrapropylammonium hydroxide isopropylamine tetraisopropyl titanate ethanol H 2 The molar ratio of O is 0.95.
Example 13
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 for 10 hours at room temperature to form gel, thereby obtaining a modified TS-1 glue solution; tetraethyl silicate, gamma-aminoureidopropyltriethoxysilane, tetrapropylammonium hydroxide, ammonia water, tetra-n-propyl titanate, n-propanol, H 2 The molar ratio of O is 0.75.
Preparation example of a Modularly modified TS-1 catalyst
The monolithic modified TS-1 catalyst is prepared by soaking the carbon porous ceramic in the modified TS-1 glue solution for recrystallization, and the combination of the carbon porous ceramic and the modified TS-1 glue solution is only partially listed in the following examples, but the combination and the conditions of the following examples are not limited.
The structure of the integral modified TS-1 catalyst obtained below is a cylindrical structure with the diameter of 3-100 mm and the height of 2-50 mm, the catalyst contains three-dimensional pore canals which are communicated with each other, and the average pore diameter of the three-dimensional pore canals 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。
Example 14
Soaking the carbon porous ceramic obtained in the example 1 in the modified TS-1 glue solution obtained in the example 6 at 35 ℃ for 3min, taking out the carbon porous ceramic, draining off the surface liquid, placing the carbon porous ceramic on an upper grid frame in a pressure kettle filled with 0.25% ammonia water solution, heating the pressure kettle to 125 ℃, keeping the temperature for 10h, cooling the pressure kettle to room temperature, taking out the carbon porous ceramic, placing the carbon porous ceramic in a high-temperature furnace, drying the carbon porous ceramic at 105 ℃ for 5h, heating the carbon porous ceramic to 450 ℃, roasting the carbon porous ceramic for 2h, cooling the carbon porous ceramic to room temperature, and taking out the carbon porous ceramic to obtain the integral modified TS-1 catalyst.
Example 15
Soaking the carbon porous ceramic obtained in example 5 in the modified TS-1 glue solution obtained in example 13 at 85 ℃ for 60min, taking out the carbon porous ceramic, draining off the surface liquid, placing the carbon porous ceramic on an upper grid frame in a pressure kettle filled with 25% triethylamine solution, heating the pressure kettle to 195 ℃, keeping the temperature for 80h, cooling the pressure kettle to room temperature, taking out the carbon porous ceramic, placing the carbon porous ceramic in a high-temperature furnace, drying the carbon porous ceramic for 5h at 105 ℃, heating the carbon porous ceramic to 650 ℃, roasting the carbon porous ceramic for 8h, cooling the carbon porous ceramic to room temperature, and taking out the carbon porous ceramic to obtain the integral modified TS-1 catalyst.
Example 16
Soaking the carbon porous ceramic obtained in the example 3 in the modified TS-1 glue solution obtained in the example 7 at 65 ℃ for 20min, taking out the carbon porous ceramic, draining off surface liquid, placing the carbon porous ceramic on an upper grid frame in a pressure kettle filled with 7.5% trimethylamine solution, heating the pressure kettle to 165 ℃, keeping the temperature for 50h, cooling the pressure kettle to room temperature, taking out the carbon porous ceramic, placing the carbon porous ceramic in a high-temperature furnace, drying the carbon porous ceramic at 105 ℃ for 5h, heating the temperature to 560 ℃ and roasting the carbon porous ceramic for 4.5h, and taking out the carbon porous ceramic after cooling to room temperature to obtain the integral modified TS-1 catalyst.
Example 17
Soaking the carbon porous ceramic obtained in the example 2 in the modified TS-1 glue solution obtained in the example 11 at 40 ℃ for 35min, taking out the carbon porous ceramic, draining off surface liquid, placing the carbon porous ceramic on an upper grid frame in a pressure kettle filled with 11% isopropylamine solution, heating the pressure kettle to 175 ℃, keeping the temperature for 65h, cooling the pressure kettle to room temperature, taking out the carbon porous ceramic, placing the carbon porous ceramic in a high-temperature furnace, drying the carbon porous ceramic at 105 ℃ for 5h, heating the carbon porous ceramic to 490 ℃, roasting the carbon porous ceramic for 6.5h, cooling the carbon porous ceramic to room temperature, and taking out the carbon porous ceramic to obtain the integral modified TS-1 catalyst.
Example 18
Soaking the carbon porous ceramic obtained in the example 4 in the modified TS-1 glue solution obtained in the example 9 at 32.5 ℃ for 50min, taking out the carbon porous ceramic, draining off the surface liquid, placing the carbon porous ceramic on an upper grid frame in a pressure kettle filled with 20% dimethylamine solution, heating the pressure kettle to 170 ℃, keeping the temperature for 70h, cooling the pressure kettle to room temperature, taking out the carbon porous ceramic, placing the carbon porous ceramic in a high-temperature furnace, drying the carbon porous ceramic at 105 ℃ for 5h, heating the carbon porous ceramic to 650 ℃, roasting the carbon porous ceramic for 7.5h, cooling the carbon porous ceramic to room temperature, and taking out the carbon porous ceramic to obtain the integral modified TS-1 catalyst.
Example 19
Soaking the carbon porous ceramic obtained in the example 2 in the modified TS-1 glue solution obtained in the example 8 at 70 ℃ for 45min, taking out the carbon porous ceramic, draining off surface liquid, placing the carbon porous ceramic on an upper grid frame in a pressure kettle filled with 17.5% dimethylamine solution, heating the pressure kettle to 155 ℃, keeping the temperature for 48h, cooling the pressure kettle to room temperature, taking out the carbon porous ceramic, placing the carbon porous ceramic in a high-temperature furnace, drying the carbon porous ceramic at 105 ℃ for 5h, heating the carbon porous ceramic to 625 ℃, roasting the carbon porous ceramic for 7h, cooling the carbon porous ceramic to room temperature, and taking out the carbon porous ceramic to obtain the integral modified TS-1 catalyst.
Example 20
Soaking the carbon porous ceramic obtained in the example 5 in the modified TS-1 glue solution obtained in the example 12 at the soaking temperature of 52.5 ℃ for 48min, taking out the carbon porous ceramic, draining off the surface liquid, placing the carbon porous ceramic on an upper grid frame in a pressure kettle filled with 12.5% isopropylamine solution, heating the pressure kettle to 155 ℃, keeping the temperature for 40h, cooling the pressure kettle to room temperature, taking out the carbon porous ceramic, placing the carbon porous ceramic in a high-temperature furnace, drying the carbon porous ceramic at 105 ℃ for 5h, heating the carbon porous ceramic to 635 ℃, roasting the carbon porous ceramic for 6.8h, cooling the carbon porous ceramic to room temperature, and taking out the carbon porous ceramic to obtain the integral modified TS-1 catalyst.
Propylene one-step direct epoxidation example
Propylene oxide was prepared by direct oxidation of propylene with hydrogen peroxide in a fixed bed reactor using the overall modified TS-1 catalysts prepared in examples 14 to 20. In the following examples, only some of the catalysts and combinations of the reaction conditions thereof are listed, but the catalysts and the reaction conditions thereof are not limited to those listed in the following examples.
In the examples below, the diameter of the monolithic catalyst is 50mm and the height of the catalyst bed is 1500mm.
Example 21
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 14 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 flow ratio of propylene, dioxane and hydrogen peroxide was 1.5, the reactor space velocity was 200h -1 The concentration of hydrogen peroxide is 30 percent, the temperature of the reactor bed layer is controlled to be 30 ℃, 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 (99.8%) of hydrogen peroxide, and obtaining the propylene oxide with the selectivity of 95 percentAt times, about 5% 1,2-propanediol is present. Unreacted propylene returns to the reactor for recycling, the solvent obtained by separation returns to the reactor for recycling, and the water obtained by separation can be used as industrial water and can also be discharged as water reaching the standard. The isolated by-product 1,2-propanediol is sold as a by-product. Depending on the type of solvent, if an alcohol solvent is used, the propylene oxide and the alcohol undergo a small amount of side reaction to produce a propylene glycol ether as a byproduct, and the propylene glycol ether is separated and sold as a byproduct.
Example 22
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 metering at a pressure of 0.4MPa, acetone and hydrogen peroxide are respectively introduced into the reactor, the flow ratio of the propylene to the acetone to the hydrogen peroxide is 1 -1 The concentration of hydrogen peroxide is 70 percent, the temperature of the reactor bed layer is controlled to be 90 ℃, 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. During the reaction, the sample was taken from the outlet of the reactor and analyzed, and the conversion rate of hydrogen peroxide (99.8%) was calculated, and the selectivity to propylene oxide was 93.5% with about 6.5% of 1,2-propanediol. The unreacted propylene returns to the reactor for recycling, the solvent obtained by separation returns to the reactor for recycling, and the water obtained by separation is used as industrial water and can also be discharged as water reaching the standard. The isolated by-product 1,2-propanediol is sold as a by-product. Depending on the type of solvent, if an alcohol solvent is used, the propylene oxide and the alcohol undergo a small amount of side reaction to produce a propylene glycol ether as a byproduct, and the propylene glycol ether is separated and sold as a byproduct.
Example 23
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 monolith modified TS-1 catalyst prepared in example 15The agent is filled in a fixed bed reactor, propylene is added into the reactor under the pressure of 0.4MPa through metering, acetonitrile and hydrogen peroxide are respectively introduced into the reactor, the flow ratio of the propylene to the acetonitrile to the hydrogen peroxide is 1.4, and the airspeed of the reactor is 500h -1 The concentration of hydrogen peroxide is 50 percent, the temperature of a reactor bed layer is controlled to be 50 ℃, 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. During the reaction, the outlet of the reactor was sampled and analyzed, and the conversion of hydrogen peroxide (99.5%) was calculated, and the selectivity to propylene oxide was 96.5%, while about 3.5% of 1,2-propanediol was present. The unreacted propylene returns to the reactor for recycling, the solvent obtained by separation returns to the reactor for recycling, and the water obtained by separation is used as industrial water and can also be discharged as water reaching the standard. The separated by-product 1,2-propanediol is sold as a by-product. Depending on the type of solvent, if an alcohol solvent is used, the propylene oxide and the alcohol undergo a small amount of side reaction to produce propylene glycol ether as a byproduct, and the propylene glycol ether is separated and sold as a byproduct.
Example 24
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 is filled in a fixed bed reactor, propylene is added into the reactor by metering at a pressure of 0.4MPa, methanol and hydrogen peroxide are respectively introduced into the reactor, the flow ratio of propylene to methanol to hydrogen peroxide is 1.0, the space velocity of the reactor is 350h -1 The concentration of hydrogen peroxide is 45 percent, the temperature of the reactor bed layer is controlled to be 40 ℃, 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. During the reaction, the sample was taken from the outlet of the reactor and analyzed, and the conversion rate of hydrogen peroxide (98.5%) was calculated, and the selectivity to propylene oxide was 93.5%, while about 4.5% of 1,2-propanediol and 2% of propylene glycol methyl ether were present. The unreacted propylene is returned to the reactor for recycling, and the solvent obtained by separation is returned to the reactor for recyclingThe water obtained by separation can be used as industrial water and can also be discharged as standard water. The separated by-product 1,2-propanediol is sold as a by-product. Depending on the type of solvent, if an alcohol solvent is used, the propylene oxide and the alcohol undergo a small amount of side reaction to produce a propylene glycol ether as a byproduct, and the propylene glycol ether is separated and sold as a byproduct.
Example 25
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 15 was loaded in a fixed bed reactor, propylene was metered into the reactor at a pressure of 0.4MPa, ethanol and hydrogen peroxide were fed into the reactor, respectively, at a flow ratio of propylene, ethanol, hydrogen peroxide of 1.0, at a reactor airspeed of 600h -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. During the reaction, the sample was taken from the outlet of the reactor and analyzed, and the conversion rate of hydrogen peroxide (99.2%) was calculated, and the selectivity to propylene oxide was 94.5%, while about 3.5% of 1,2-propanediol and 2% of propylene glycol ether were present. Unreacted propylene returns to the reactor for recycling, the solvent obtained by separation returns to the reactor for recycling, and the water obtained by separation can be used as industrial water and can also be discharged as water reaching the standard. The isolated by-product 1,2-propanediol is sold as a by-product. Depending on the type of solvent, if an alcohol solvent is used, the propylene oxide and the alcohol undergo a small amount of side reaction to produce a propylene glycol ether as a byproduct, and the propylene glycol ether is separated and sold as a byproduct.
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 catalyst modified by the monolith form TS-1 prepared in example 16 was loaded in a fixed bed reactor, propylene was metered into the reactor at a pressure of 0.4MPa, and dioxane was addedAnd respectively introducing acetonitrile and hydrogen peroxide into the reactor, wherein the flow ratio of propylene to dioxane to acetonitrile to hydrogen peroxide is 1.35 -1 The concentration of hydrogen peroxide is 45 percent, the temperature of the reactor bed layer is controlled to be 62 ℃, 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. During the reaction, the sample was taken from the outlet of the reactor and analyzed, and the conversion rate of hydrogen peroxide (99.3%) was calculated, and the selectivity to propylene oxide was 97.5% while about 2.5% of 1,2-propanediol was present. The unreacted propylene returns to the reactor for recycling, the solvent obtained by separation returns to the reactor for recycling, and the water obtained by separation is used as industrial water and can also be discharged as water reaching the standard. The separated by-product 1,2-propanediol is sold as a by-product. Depending on the type of solvent, if an alcohol solvent is used, the propylene oxide and the alcohol undergo a small amount of side reaction to produce a propylene glycol ether as a byproduct, and the propylene glycol ether is separated and sold as a byproduct.
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 17 is loaded in a fixed bed reactor, propylene is added into the reactor by metering at a pressure of 0.4MPa, acetone, acetonitrile and hydrogen peroxide are respectively introduced into the reactor, the flow ratio of the propylene to the acetone to the acetonitrile to the hydrogen peroxide is 1.45, the space velocity of the reactor is 560h -1 The concentration of hydrogen peroxide is 50 percent, the temperature of the reactor bed layer is controlled to be 47.5 ℃, 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. During the reaction, the sample was taken from the outlet of the reactor and analyzed, and the conversion rate of hydrogen peroxide (99.7%) was calculated, and the selectivity of propylene oxide production was 98.5%, while about 1.5% of 1,2-propanediol was present. The unreacted propylene is returned to the reactor for recycling, the solvent obtained by separation is returned to the reactor for recycling, and the water obtained by separation is used as industrial water and can also be used as industrial waterDischarging the water reaching the standard. The isolated by-product 1,2-propanediol is sold as a by-product. Depending on the type of solvent, if an alcohol solvent is used, the propylene oxide and the alcohol undergo a small amount of side reaction to produce a propylene glycol ether as a byproduct, and the propylene glycol ether is separated and sold as a byproduct.
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, methanol, acetonitrile, and hydrogen peroxide were fed into the reactor, respectively, the flow ratio of propylene, methanol, acetonitrile, and hydrogen peroxide was 1.8 -1 The concentration of hydrogen peroxide is 35 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. During the reaction, the sample was taken from the outlet of the reactor and analyzed, and the conversion rate of hydrogen peroxide (99.5%) was calculated, and the selectivity to propylene oxide was 97.5%, while about 1.5% of 1,2-propylene glycol and 1% of propylene glycol ether were present. Unreacted propylene returns to the reactor for recycling, the solvent obtained by separation returns to the reactor for recycling, and the water obtained by separation can be used as industrial water and can also be discharged as water reaching the standard. The isolated by-product 1,2-propanediol is sold as a by-product. Depending on the type of solvent, if an alcohol solvent is used, the propylene oxide and the alcohol undergo a small amount of side reaction to produce a propylene glycol ether as a byproduct, and the propylene glycol ether is separated and sold as a byproduct.
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 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%.
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