CN113145116B - Integral TS-1 catalyst carrier and preparation and application thereof - Google Patents

Integral TS-1 catalyst carrier and preparation and application thereof Download PDF

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CN113145116B
CN113145116B CN202110078069.6A CN202110078069A CN113145116B CN 113145116 B CN113145116 B CN 113145116B CN 202110078069 A CN202110078069 A CN 202110078069A CN 113145116 B CN113145116 B CN 113145116B
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propylene
hydrogen peroxide
selectivity
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CN113145116A (en
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曹贵平
吕慧
高鹏
纪爽
张政
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • 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

Abstract

The invention relates to a monolithic TS-1 catalyst carrier and preparation and application thereof, wherein a metal framework is taken firstly, cleaned and dried and then placed in a chemical vapor deposition furnace; then, fully mixing the raw materials containing Si and C with inert gas or mixed gas of the inert gas and hydrogen in a gas form, introducing the mixture into a chemical vapor deposition furnace, and heating to grow a Si-doped carbon layer on the metal framework; and after the growth is finished, cooling to room temperature to obtain the target product integral TS-1 catalyst carrier. After the catalyst carrier is used, the TS-1 can be structured, which is beneficial to the operation of a fixed bed reactor, solves the problem of separation of a catalyst and a reaction liquid, and moreover, due to the structuring of the carrier, the TS-1 is covered on the surface of the carrier in a micro crystal grain form, so that the catalytic performance of the TS-1 is exerted to the maximum extent, the internal diffusion is effectively eliminated, the selectivity of side reactions is reduced, the selectivity of a main product, namely propylene oxide is greatly improved, the production efficiency is greatly improved, and the production cost is reduced.

Description

Integral TS-1 catalyst carrier and preparation and application thereof
Technical Field
The invention belongs to the technical field of an integral TS-1 catalyst carrier, a catalyst and preparation thereof, and relates to an integral TS-1 catalyst carrier, and preparation and application thereof.
Background
Propylene oxide is an important chemical raw material, is a synthetic raw material of polyether polyol, propylene glycol ether, dimethyl carbonate, polypropylene carbonate, nonionic surfactant and the like, and is an essential raw material in the polyurethane industry. Plays an important role in the chemical industry.
The demand of propylene oxide increases year by year, and especially with the rapid development of economic technology in China, higher requirements are put forward on the safety, cleanness and high efficiency of propylene oxide production technology. The production method of propylene oxide in China is mainly a chlorohydrin method with high pollution for many years, which brings great pressure to the environment, and the chlorohydrin method is strictly prohibited in developed countries and regions such as Europe, america and the like. In recent years, our country forbids new production-increasing energy for producing propylene oxide by chlorohydrin method. 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 puts the propylene oxide into a new green technology which is mainly developed. 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 and products are extremely difficult to separate exists in the industrial process. Although abundant literature reports TS-1 molding synergy methods, such as a spray drying granulation method, an extrusion molding granulation method, a carrier surface coating method, a hollow microsphere method and the like, the method has the problems of obvious reduction of activity and selectivity, increased side reactions and slow down of the industrialization process. Although the catalyst formed and synergized is also prepared by adopting 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 cannot be fundamentally solved.
Disclosure of Invention
The invention aims to provide an integral TS-1 catalyst carrier and preparation and application thereof, which aim to solve the problem of separation of the existing catalyst and reaction liquid, and due to the integral structure of the carrier, TS-1 covers the surface of the carrier in a micro crystal grain form, so that the catalytic performance of TS-1 is exerted to the maximum extent, internal diffusion is effectively eliminated, the selectivity of side reaction is reduced, the selectivity of a main product propylene oxide is greatly improved, the production efficiency is greatly improved, and the production cost is reduced.
The purpose of the invention can be realized by the following technical scheme:
in one aspect, the invention provides a monolithic TS-1 catalyst carrier, which comprises a metal framework and a Si-doped carbon layer, wherein the metal framework is internally provided with three-dimensional pore channels which are communicated with each other, and the Si-doped carbon layer is grown on the metal framework.
Furthermore, the carrier is in a cylindrical structure with the diameter of 5 mm-900 mm and the height of 1 mm-3000 mm, and the average pore diameter of the three-dimensional pore canal is 0.1 μm-500 μm.
Further, the metal component used for the metal framework comprises one or more alloys of transition metals of Fe, co, ni and Cu. Furthermore, the metal component can also be added with a metal auxiliary component which is selected from one or more of Cr, mo or Ti. The metal skeleton with three-dimensional through-holes inside can also be called foam metal or metal foam, before use, cleaning and impurity removing treatment is needed, and the common treatment method comprises ultrasonic cleaning in ethanol with the concentration of 50-100% for 5-60 min, washing with pure water, and N at 50-110 DEG C 2 And drying in the atmosphere, wherein the drying is specifically prepared by a 3D printing method, and can also be directly purchased in the market or customized by a merchant.
Further, the structure of the Si-doped carbon layer is one or a mixture of amorphous C, carbon nano-tube, carbon nano-fiber and graphene.
In another aspect, the present invention also provides a method for preparing the monolithic TS-1 catalyst carrier, comprising the following steps:
(1) Cleaning and drying a metal framework, and then placing the metal framework in a chemical vapor deposition furnace;
(2) Then fully mixing the raw materials containing Si and C with inert gas or mixed gas of the inert gas and hydrogen in a gas form, introducing the mixture into a chemical vapor deposition furnace, and heating to grow a Si-doped carbon layer on the metal framework;
(3) After the growth is finished, cooling to room temperature to obtain the target product.
Further, the raw material containing Si and C is selected from Si alkane or a mixture of Si alkane and one or more of alkane, alkene, alkyne, alcohol, ether, ketone and ester;
wherein the chemical formula of the Si alkane is SiR 4 、R x SiR’ (4-x) Or (RO) x SiR’ (4-x) R and R' are each independently H or C1-C5 alkyl, x =0, 1, 2, 3 or 4, more specifically, si alkyl may be silane, tetramethylsilane, tetraethylsilane, trimethylethylsilane, dimethyldiethylsilane, methyltriethylsilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, etc., but is not limited to the listed examples. The alkane is C1-C8 straight-chain alkane or cycloalkane, and specifically can be methane, ethane, propane, cyclohexane and the like, but is not limited to the list;
the olefin is C1-C8 linear olefin or cyclic olefin, such as ethylene, propylene, 1-butene, 2-butene, isobutene, 1, 3-butadiene, cyclohexene, cyclopentadiene, norbornene, etc., but not limited to the list;
the alkyne can be acetylene, propine, butyne, phenylacetylene and the like;
the alcohol can be methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, etc.;
the chemical general formula of the ether is FOF ', F and F' are respectively and independently C1-C6 alkyl and/or aryl, such as dimethyl ether, methyl ethyl ether, diethyl ether, anisole, phenetole, diphenyl ether and the like;
the chemical general formula of the ketone is A (CO) A ', A and A' are respectively and independently C1-C6 alkyl, such as acetone, methylethylketone, cyclohexanone, benzophenone and the like;
the chemical formula of the ester is M (COO) M ', and M' are C1-C6 alkyl and/or aryl, such as methyl formate, ethyl acetate, methyl acetate, ethyl formate, methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, etc.
Further, in the step (2), when the raw materials containing Si and C are in a gaseous state, the raw materials are directly mixed with a mixed gas of hydrogen and inert gas;
when the raw materials containing Si and C are liquid, firstly adding the raw materials into a vaporizer, heating and then gasifying the raw materials, and then mixing the raw materials with the mixed gas of hydrogen and inert gas;
in the chemical deposition process, the molar ratio of the introduced amounts of the raw material containing Si and C, hydrogen and Inert Gas (IG) satisfies the following conditions: n is a radical of an alkyl radical IG :n H2 :n Si :n C =100, (0-500), (0.01-50), (0.5-100). When the amount of hydrogen added is 0, it means that hydrogen is not added at this time.
Further, the inert gas may be Ar or N 2 。
Further, in the step (2), the space velocity in the chemical deposition gas phase furnace is 0.1h -1 ～1000h -1 The preferable range is 0.5h -1 ～800h -1 The optimum range is 1h -1 ～500h -1 The heating temperature is 300-1200 deg.C, the preferred temperature range is 400-1100 deg.C, and the most preferred temperature range is 600-950 deg.C.
Further, in the step (3), in the cooling process after the growth is finished, stopping H 2 Feeding raw materials containing Si and C, keeping introducing inert gas, and then naturally cooling.
In still another aspect, the present invention also provides a use of the above-mentioned monolithic TS-1 catalyst carrier for preparing a monolithic TS-1 catalyst, wherein the TS-1 is covered on the surface of the monolithic TS-1 catalyst carrier in the form of fine crystal grains. Therefore, the TS-1 catalytic performance can be exerted to the maximum extent, internal diffusion is effectively eliminated, the selectivity of side reaction is reduced, the selectivity of a main product propylene oxide is greatly improved, the production efficiency is greatly improved, and the production cost is reduced.
In the preparation process of the catalyst carrier, the metal framework is provided with a three-dimensional channel, and the three-dimensional channel is used as a carrier for C layer growth and simultaneously plays a role in catalyzing C layer growth. And decomposing and growing the Si source and the C source under the catalytic action of the metal framework to obtain a C layer. H 2 Is to eliminate possible oxidizing species present in the Si source and the C source; n is a radical of 2 Get thinRelease function, regulate and control the growth speed and structure of the C layer. The temperature is the thermodynamics and the kinetics basis of the growth of the C layer, the Si source and the C source cannot react to generate the C layer at too low temperature and the speed is too low; if the temperature is too high, the growth speed is high, and the process and the C layer structure cannot be effectively controlled.
Detailed Description
The present invention will be described in detail with reference to specific examples. In the present embodiment, the technical solution of the present invention is used as a precondition for implementation, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the starting materials and treatment techniques are conventional commercially available materials or conventional treatment techniques in the art.
Example 1
Placing metal Co-Ni foam with diameter of 10mm and height of 20mm (aperture 300 μm, skeleton thickness 500 μm) in anhydrous ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Tetraethyl silane and dimethyl ether were pumped into the CVD furnace by a metering pump at a molar ratio of 100 -1 The temperature in the furnace is 950 ℃, after the growth is carried out for 60min, the CVD heating power supply is turned off, and H is turned off 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. Thus obtaining the foam Co-Ni skeleton growth Si doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 10mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor is operated continuously, the conversion rate of hydrogen peroxide is 99.5%, the selectivity of propylene oxide generated by hydrogen peroxide is 96.5%, the selectivity of propylene oxide generated by propylene sound field is 97.5%, and the selectivity of propylene glycol ether generated is 2.5%.
Comparative example 1
Compared with example 1, the composition is mostly the same except that tetraethyl silane is omitted, i.e., the doping of Si element is not performed.
The reactor is operated continuously, the conversion rate of the hydrogen peroxide is 85 percent, the selectivity of the hydrogen peroxide to the propylene oxide is 74 percent, the selectivity of the propylene to the propylene oxide is 82 percent, and the selectivity to the propylene glycol ether is 13 percent.
Comparative example 2
Compared with example 1, is largely identical, except that the introduction of H is omitted 2 This portion. At this time, the C vector hardly grew, and the next experiment was not carried out.
Example 2
Placing metal Co foam with diameter of 200mm and height of 500mm (aperture of 10 μm, framework thickness of 5 μm) in 100% ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transferring into a CVD furnace, and introducing N into the CVD furnace 2 、H 2 Methyl triethyl silane and n-propanol in a molar ratio of 100, 50, the space velocity of the CVD reactor is 500h -1 The temperature in the furnace is 300 ℃, after the growth is carried out for 10min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Co skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from propylene was 98%, and the selectivity of propylene glycol ether was 4%.
Example 3
Placing metal Ni foam with diameter of 100mm and height of 500mm (aperture of 5 μm, skeleton thickness of 0.5 μm) in 80% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 105 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Tetramethoxysilane and methyl ethyl ether in a molar ratio of 100 -1 The temperature in the furnace is 1100 ℃, after the growth is carried out for 20min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Ni skeleton growth Si-doped C carrier.
The resulting catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 95%, the selectivity of propylene oxide from hydrogen peroxide was 94%, the selectivity of propylene oxide from propylene was 98%, and the selectivity of propylene glycol ether was 2%.
Example 4
Placing metal Fe foam with diameter of 100mm and height of 5mm (aperture of 0.1 μm, skeleton thickness of 500 μm) in 50% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 105 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Methyl triethyl silicane and isobutene, wherein the molar ratio of the methyl triethyl silicane to the isobutene is 100 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Fe skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor is continuously operated, the conversion rate of hydrogen peroxide is 96%, the selectivity of propylene oxide generated by hydrogen peroxide is 94%, the selectivity of propylene oxide generated by propylene is 98%, and the selectivity of propylene glycol ether generated by propylene glycol ether is 2%.
Example 5
Placing metal Fe-Cu foam with diameter of 5mm and height of 10mm (aperture 500 μm, framework thickness 5 μm) in 100% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, introducing Ar and H into the CVD furnace 2 Dimethyldiethylsilane and tert-butanol at a molar ratio of 100 -1 The temperature in the furnace is 1200 ℃, after 120min of growth, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Fe-Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 10mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 97%, the selectivity of propylene oxide from hydrogen peroxide was 96%, the selectivity of propylene oxide from propylene was 96%, and the selectivity of propylene glycol ether was 4%.
Example 6
Placing metal Fe-Ni foam with diameter of 200mm and height of 10mm (aperture of 0.1 μm, skeleton thickness of 0.5 μm) in 50% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 105 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Trimethylethylsilane and propyne at a molar ratio of 100 -1 The temperature in the furnace is 300 ℃, after the growth is carried out for 20min, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. Thus obtaining the foam Fe-Ni framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 10mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. Emptying of the reactorThe speed is 1h -1 The reactor is operated continuously, the conversion rate of the hydrogen peroxide is 97%, the selectivity of the hydrogen peroxide to the propylene oxide is 96%, the selectivity of the propylene to the propylene oxide is 97%, and the selectivity of the propylene glycol ether is 3%.
Example 7
Placing metal Co foam with diameter of 10mm and height of 500mm (aperture 300 μm, skeleton thickness 5 μm) in 80% ethanol, ultrasonic cleaning for 60min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Silane and methane, in a molar ratio of 100 -1 The temperature in the furnace is 1200 ℃, after the growth is carried out for 10min, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. And obtaining the foam Co skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 10mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 93%, the selectivity of propylene oxide from hydrogen peroxide was 96%, the selectivity of propylene oxide from propylene was 94%, and the selectivity of propylene glycol ether was 7%.
Example 8
Placing metal Cu foam with diameter of 10mm and height of 10mm (aperture 300 μm, skeleton thickness 0.5 μm) in 100% ethanol, ultrasonic cleaning for 60min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Trimethyl methoxysilane and acetone in a molar ratio of 100 to 30, wherein the space velocity of the CVD reactor is 1000h -1 The temperature in the furnace is 600 ℃, after 50min of growth, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Cu framework growth Si-doped C carrier.
Loading the obtained catalyst into the inner diameterIn a 10mm fixed bed reactor, the height of the bed layer is 10mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor is continuously operated, the conversion rate of hydrogen peroxide is 98%, the selectivity of the hydrogen peroxide to the propylene oxide is 97%, the selectivity of the propylene to the propylene oxide is 96%, and the selectivity to the propylene glycol ether is 4%.
Example 9
Placing Co-Cu foam with diameter of 10mm and height of 5mm (aperture 500 μm, skeleton thickness 500 μm) in 100% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Tetramethylsilane and butyl methacrylate in a molar ratio of 100, 25, the space velocity of the CVD reactor being 0.5h -1 The temperature in the furnace is 300 ℃, after 120min of growth, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Co-Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 10mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor is operated continuously, the conversion rate of the hydrogen peroxide is 95%, the selectivity of the hydrogen peroxide to the propylene oxide is 96%, the selectivity of the propylene to the propylene oxide is 95%, and the selectivity of the propylene glycol ether is 5%.
Example 10
Placing metal Fe-Co foam with diameter of 10mm and height of 20mm (aperture of 0.1 μm, skeleton thickness of 0.05 μm) in 75% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 105 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Tetramethylsilane and cyclohexanone in a molar ratio of 100, 60, the space velocity of the cvd reactor being 0.5h -1 The temperature in the furnace is 600 ℃, after 50min of growth, the CVD heating power supply is turned off, H is turned off 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Fe-Co skeleton-grown Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 10mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 93%, the selectivity of propylene oxide from hydrogen peroxide was 94%, the selectivity of propylene oxide from propylene was 95%, and the selectivity of propylene glycol ether was 5%.
Example 11
Placing metal Fe foam with diameter of 5mm and height of 500mm (aperture 500 μm, skeleton thickness 500 μm) in 100% ethanol, ultrasonic cleaning for 60min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Dimethyldimethoxysilane and 1-butene in a molar ratio of 100 to 40, the space velocity of the cvd reactor being 500h -1 The temperature in the furnace is 950 ℃, after the growth is carried out for 200min, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. And obtaining the foam Fe skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 95%, the selectivity of propylene oxide from propylene was 95.5%, and the selectivity of propylene glycol ether was 4.5%.
Example 12
Gold with a diameter of 100mm and a height of 10mm (aperture of 10 μm, thickness of skeleton of 5 μm)Placing Cu foam in 80% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Dimethyldimethoxysilane and ethyl acetate in a molar ratio of 100 to 0.5, the space velocity of the cvd reactor being 1h -1 The temperature in the furnace is 1100 ℃, after the growth is carried out for 10min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 10mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 95%, the selectivity of propylene oxide from propylene was 96.5%, and the selectivity of propylene glycol ether was 3.5%.
Example 13
Placing metal Fe-Co foam with diameter of 10mm and height of 20mm (aperture of 0.1 μm, skeleton thickness of 500 μm) in 75% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Trimethyl methoxysilane and cyclohexane in a molar ratio of 100 to 50, wherein the space velocity of the CVD reactor is 800h -1 The temperature in the furnace is 1200 ℃, after the growth is carried out for 30min, the CVD heating power supply is turned off, and H is turned off 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Fe-Co skeleton-grown Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 10mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor is continuously operated, the conversion rate of the hydrogen peroxide is 94 percent,the selectivity of propylene oxide from hydrogen peroxide was 95%, the selectivity of propylene oxide from propylene was 96.5%, and the selectivity of propylene glycol ether was 3.5%.
Example 14
Placing metal Co foam with diameter of 100mm and height of 5mm (aperture 500 μm, skeleton thickness 5 μm) in 100% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Dimethyldiethylsilane and acetylene at a molar ratio of 100 -1 The temperature in the furnace is 1100 ℃, after the growth is carried out for 10min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Co skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 95%, the selectivity of propylene oxide from propylene was 97.5%, and the selectivity of propylene glycol ether was 2.5%.
Example 15
Placing metal Fe-Ni foam with diameter of 200mm and height of 20mm (aperture of 10 μm, skeleton thickness of 500 μm) in 75% ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, introducing Ar and H into the CVD furnace 2 Dimethyl diethyl silane and methyl formate in a molar ratio of 100 to 450, 20, wherein the space velocity of the CVD reactor is 800h -1 The temperature in the furnace is 1100 ℃, after the growth is carried out for 100min, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. And obtaining the foam Fe-Ni skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 96%, the selectivity of propylene oxide from propylene was 96%, and the selectivity of propylene glycol ether was 4%.
Example 16
Putting metal Ni foam with diameter of 5mm and height of 20mm (aperture of 10 μm, skeleton thickness of 0.05 μm) in 80% ethanol, ultrasonic cleaning for 60min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, introducing Ar and H into the CVD furnace 2 Tetramethoxysilane and methanol in a molar ratio of 100 to 150, at a space velocity of the CVD reactor of 0.1h -1 The temperature in the furnace is 950 ℃, after the growth is carried out for 20min, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. Thus obtaining the foam Ni skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 96%, the selectivity of propylene oxide from propylene was 96.6%, and the selectivity of propylene glycol ether was 3.4%.
Example 17
Placing metal Fe-Cu foam with diameter of 100mm and height of 20mm (aperture 500 μm, framework thickness 0.05 μm) in 80% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Silane and ethane in a molar ratio of 100, 0.1 -1 The temperature in the furnace is 300 ℃, after 50min of growth, the CVD heating power supply is closedClosing H 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. And obtaining the foam Fe-Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 96%, the selectivity of propylene oxide from propylene was 96.9%, and the selectivity of propylene glycol ether was 3.1%.
Example 18
Placing metal Fe-Co foam with diameter of 200mm and height of 20mm (aperture 300 μm, framework thickness 5 μm) in 50% ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 105 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Tetramethylsilane and benzophenone in a molar ratio of 100 -1 The temperature in the furnace is 400 ℃, after 80min of growth, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. And obtaining the foam Fe-Co framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 96%, the selectivity of propylene oxide from propylene was 96.7%, and the selectivity of propylene glycol ether was 3.3%.
Example 19
Putting Ni-Cu foam with diameter of 100mm and height of 500mm (aperture 300 μm, skeleton thickness 0.05 μm) in 50% ethanol, ultrasonic cleaning for 60min, taking outAfter washing with pure water, it was dried at 105 ℃. Transferring into a CVD furnace, introducing Ar and H into the CVD furnace 2 Trimethylethylsilane and 2-butene in a molar ratio of 100, 1, the space velocity of the cvd reactor being 1h -1 The temperature in the furnace is 1100 ℃, after the growth is carried out for 100min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Ni-Cu framework growth Si-doped C carrier.
The resulting catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 97%, the selectivity of propylene oxide from propylene was 97%, and the selectivity of propylene glycol ether was 3%.
Example 20
Placing Co foam with diameter of 100mm and height of 500mm (aperture 300 μm, skeleton thickness 0.5 μm) in 100% ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 105 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Dimethyldimethoxysilane and 1, 3-butadiene in a molar ratio of 100 to 10, the space velocity of the CVD reactor being 800h -1 The temperature in the furnace is 300 ℃, after 120min of growth, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Co skeleton growth Si-doped C carrier.
The resulting catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor is operated continuously, the conversion rate of the hydrogen peroxide is 94 percent, the selectivity of the hydrogen peroxide to the propylene oxide is 97 percent, and the propylene is generatedThe selectivity to propylene oxide was 97% and the selectivity to propylene glycol ether was 3%.
Example 21
Placing metal Ni foam with diameter of 200mm and height of 5mm (aperture 500 μm, skeleton thickness 0.05 μm) in 80% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 105 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Methyltrimethoxysilane and cyclopentadiene in a molar ratio of 100:45, at a space velocity of the cvd reactor of 500h -1 The temperature in the furnace is 400 ℃, after 80min of growth, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Ni skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 97%, the selectivity of propylene oxide from propylene was 97%, and the selectivity of propylene glycol ether was 3%.
Example 22
Putting metal Ni-Cu foam with diameter of 5mm and height of 10mm (aperture of 0.1 μm, skeleton thickness of 0.5 μm) in 50% ethanol, ultrasonic cleaning for 60min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transferring into a CVD furnace, introducing Ar and H into the CVD furnace 2 Trimethylethylsilane and isobutanol at a molar ratio of 100: 0.01 -1 The temperature in the furnace is 1200 ℃, after the growth is carried out for 60min, the CVD heating power supply is turned off, and H is turned off 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Ni-Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 10mm. Pumping solvent methanol from the upper part of the reactor at a certain flow rate, and heatingAnd after the reaction temperature is reached to 55 ℃, hydrogen peroxide is pumped in and propylene is added, wherein the molar ratio of methanol to hydrogen peroxide to propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 94%, the selectivity of propylene oxide from hydrogen peroxide was 97%, the selectivity of propylene oxide from propylene was 97%, and the selectivity of propylene glycol ether was 3%.
Example 23
Placing metal Fe foam with diameter of 200mm and height of 5mm (aperture of 10 μm, framework thickness of 0.5 μm) in 75% ethanol, ultrasonic cleaning for 60min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transferring into a CVD furnace, introducing Ar and H into the CVD furnace 2 Tetraethylsilane and norbornene in a molar ratio of 100: 0.01 -1 The temperature in the furnace is 950 ℃, after the growth is carried out for 60min, the CVD heating power supply is turned off, and H is turned off 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Fe skeleton-grown Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 95%, the selectivity of propylene oxide from hydrogen peroxide was 98%, the selectivity of propylene oxide from propylene was 97.5%, and the selectivity of propylene glycol ether was 2.5%.
Example 24
Placing metal Fe foam with diameter of 10mm and height of 500mm (aperture of 10 μm, framework thickness of 0.5 μm) in 75% ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Trimethylmethoxysilane and cyclohexene in a molar ratio of 100 -1 The temperature in the furnace is 950 ℃, after 30min of growth, the CVD heating power supply is turned off, H is turned off 2 Si source, C source in Ar gasThe flow naturally cools to room temperature. And obtaining the foam Fe skeleton-grown Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 10mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 95%, the selectivity of propylene oxide from hydrogen peroxide was 98%, the selectivity of propylene oxide from propylene was 97.7%, and the selectivity of propylene glycol ether was 2.3%.
Example 25
Putting metal Ni foam with diameter of 5mm and height of 10mm (aperture of 0.1 μm, skeleton thickness of 500 μm) in 80% ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Trimethylethylsilane and anisole, in a molar ratio of 100 -1 The temperature in the furnace is 300 ℃, after the growth is carried out for 30min, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. And obtaining the foam Ni skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 10mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 95%, the selectivity of propylene oxide from hydrogen peroxide was 98%, the selectivity of propylene oxide from propylene was 97.5%, and the selectivity of propylene glycol ether was 2.5%.
Example 26
Placing metal Co-Cu foam with diameter of 200mm and height of 20mm (aperture of 10 μm, framework thickness of 0.05 μm) in 75% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transfer to CVDIn the furnace, ar and H are introduced into the CVD furnace 2 Tetramethylsilane and methyl ethyl ketone, wherein the molar ratio of the components is 100 -1 The temperature in the furnace is 400 ℃, after the growth is carried out for 150min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Co-Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor is operated continuously, the conversion rate of the hydrogen peroxide is 95%, the selectivity of the hydrogen peroxide to the propylene oxide is 98%, the selectivity of the propylene to the propylene oxide is 97%, and the selectivity of the propylene glycol ether is 3%.
Example 27
Placing metal Cu foam with diameter of 5mm and height of 5mm (aperture of 0.1 μm, skeleton thickness of 5 μm) in 75% ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Tetramethoxysilane and isopropanol in a molar ratio of 100 to 45, the space velocity of the CVD reactor being 500h -1 The temperature in the furnace is 1200 ℃, after the growth is carried out for 150min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is (5). The space velocity of the reactor is 1h -1 The reactor is operated continuously, the conversion rate of the hydrogen peroxide is 95%, the selectivity of the hydrogen peroxide to the propylene oxide is 98%, the selectivity of the propylene to the propylene oxide is 97%, and the selectivity of the propylene glycol ether is 3%.
Example 28
Placing metal Fe-Ni foam with diameter of 10mm and height of 5mm (aperture of 10 μm, framework thickness of 5 μm) in 80% ethanol, ultrasonic cleaning for 60min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Silane and butyne at a molar ratio of 100 to 20, and a space velocity of the cvd reactor of 0.5h -1 The temperature in the furnace is 400 ℃, after the growth is carried out for 60min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Fe-Ni skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 10mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 95%, the selectivity of propylene oxide from hydrogen peroxide was 98%, the selectivity of propylene oxide from propylene was 94.7%, and the selectivity of propylene glycol ether was 5.3%.
Example 29
Placing metal Fe-Cu foam with diameter of 5mm and height of 10mm (aperture of 0.1 μm, skeleton thickness of 5 μm) in 80% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Methyltriethylsilane and n-butanol at a molar ratio of 100, 0.1 -1 The temperature in the furnace is 400 ℃, after the growth is carried out for 20min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Fe-Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 10mm. Pumping methanol solvent from the upper part of the reactor at a certain flow rate, heating to 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of methanol to hydrogen peroxide to propylene is5:2.5:1. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 96%, the selectivity of propylene oxide from hydrogen peroxide was 98%, the selectivity of propylene oxide from propylene was 96.8%, and the selectivity of propylene glycol ether was 3.2%.
Example 30
Placing metal Co-Ni foam with diameter of 200mm and height of 500mm (aperture of 0.1 μm, skeleton thickness of 0.5 μm) in 50% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Dimethyl diethyl silane and phenylacetylene, wherein the molar ratio of the dimethyl diethyl silane to the phenylacetylene is 100 -1 The temperature in the furnace is 600 ℃, after the growth is carried out for 30min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Co-Ni skeleton-grown Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of a reactor at a certain flow rate, heating to reach a reaction temperature of 55 ℃, pumping hydrogen peroxide and adding propylene, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 96%, the selectivity of propylene oxide from hydrogen peroxide was 98%, the selectivity of propylene oxide from propylene was 94.8%, and the selectivity of propylene glycol ether was 5.2%.
Example 31
Placing metal Ni-Cu foam with diameter of 100mm and height of 10mm (aperture of 10 μm, framework thickness of 0.05 μm) in 75% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 105 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Methyltrimethoxysilane and propylene, in a molar ratio of 100, 50, the space velocity of the cvd reactor being 0.5h -1 The temperature in the furnace is 1200 ℃, after 80min of growth, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Ni-Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 10mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 96%, the selectivity of propylene oxide from hydrogen peroxide was 98%, the selectivity of propylene oxide from propylene was 96.8%, and the selectivity of propylene glycol ether was 3.2%.
Example 32
Placing metal Cu foam with diameter of 5mm and height of 5mm (aperture 300 μm, skeleton thickness 0.05 μm) in 100% ethanol, ultrasonic cleaning for 40min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, introducing Ar and H into the CVD furnace 2 Tetraethylsilane and propane, in a molar ratio of 100 -1 The temperature in the furnace is 950 ℃, after 50min of growth, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. Thus obtaining the foam Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, heating, pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5.5. The space velocity of the reactor is 1h -1 The reactor is operated continuously, the conversion rate of hydrogen peroxide is 96%, the selectivity of the hydrogen peroxide to the propylene oxide is 98%, the selectivity of the propylene to the propylene oxide is 95.3%, and the selectivity to the propylene glycol ether is 4.7%.
Example 33
Placing metal Fe-Ni foam with diameter of 100mm and height of 5mm (aperture 500 μm, skeleton thickness 0.5 μm) in 50% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Silane and diphenyl ether in a molar ratio of 100:70,space velocity of the CVD reactor was 1000h -1 The temperature in the furnace is 400 ℃, after the growth is carried out for 200min, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. And obtaining the foam Fe-Ni skeleton growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 100mm and a bed height of 5mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 96%, the selectivity of propylene oxide from hydrogen peroxide was 98%, the selectivity of propylene oxide from propylene was 96.7%, and the selectivity of propylene glycol ether was 3.3%.
Example 34
Placing metal Fe-Co foam with diameter of 5mm and height of 20mm (aperture 500 μm, skeleton thickness 0.5 μm) in 50% ethanol, ultrasonic cleaning for 5min, taking out, cleaning with pure water, and oven drying at 110 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Methyltriethylsilane and ethylene in a molar ratio of 100 to 450, at a space velocity of the CVD reactor of 0.1h -1 The temperature in the furnace is 1100 ℃, after the growth is carried out for 200min, the CVD heating power supply is closed, and H is closed 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Fe-Co skeleton-grown Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 5mm and a bed height of 20mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 95%, the selectivity of propylene oxide from propylene was 96.5%, and the selectivity of propylene glycol ether was 3.5%.
Example 35
The diameter of the mixture is 10mm,Placing metal Co-Ni foam with height of 500mm (aperture 300 μm, skeleton thickness 500 μm) in 50% ethanol, ultrasonic cleaning for 60min, taking out, cleaning with pure water, and oven drying at 75 deg.C. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace 2 Methyltrimethoxysilane and ethanol in a molar ratio of 100, 80, the space velocity of the cvd reactor being 500h -1 The temperature in the furnace is 600 ℃, after 80min of growth, the CVD heating power supply is turned off, H is turned off 2 And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. And obtaining the foam Co-Ni skeleton-grown Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 10mm and a bed height of 500mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 The reactor was operated continuously, the conversion of hydrogen peroxide was 95%, the selectivity of propylene oxide from propylene was 95.5%, and the selectivity of propylene glycol ether was 4.5%.
Example 36
Placing Co-Cu foam with diameter of 200mm and height of 10mm (aperture 300 μm, skeleton thickness 500 μm) in 75% ethanol, ultrasonic cleaning for 30min, taking out, cleaning with pure water, and oven drying at 50 deg.C. Transferring into a CVD furnace, introducing Ar and H into the CVD furnace 2 Tetraethylsilane and phenetole in a molar ratio of 100, 1, the space velocity of the cvd reactor was 800h -1 The temperature in the furnace is 600 ℃, after the growth is carried out for 100min, the CVD heating power supply is closed, and H is closed 2 And naturally cooling the Si source, the C source to room temperature in Ar gas flow. And obtaining the foam Co-Cu framework growth Si-doped C carrier.
The obtained catalyst was packed in a fixed bed reactor having an inner diameter of 200mm and a bed height of 10mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, raising the temperature, and pumping hydrogen peroxide and adding propylene after the reaction temperature reaches 55 ℃, wherein the molar ratio of the methanol to the hydrogen peroxide to the propylene is 5. The space velocity of the reactor is 1h -1 Continuous operation of the reactorThe conversion rate of the hydrogen peroxide is 95%, the selectivity of the hydrogen peroxide to the propylene oxide is 95%, the selectivity of the propylene to the propylene oxide is 96.8%, and the selectivity of the propylene glycol ether to the propylene glycol ether is 3.2%.
The embodiments described above are described to facilitate an understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.

Claims (7)

1. A monolithic TS-1 catalyst carrier is characterized by comprising a metal framework and a Si-doped carbon layer, wherein the metal framework is internally provided with three-dimensional pore channels which are communicated with each other, and the Si-doped carbon layer grows on the metal framework;
the carrier is a cylindrical structure with the diameter of 5 mm-900 mm and the height of 1 mm-3000 mm, and the average aperture of the three-dimensional pore canal is 0.1 μm-500 μm;
the metal components used by the metal framework comprise one or more alloys of transition metals of Fe, co, ni and Cu;
the structure of the Si-doped carbon layer is one or a mixture of amorphous C, carbon nano tubes, carbon nano fibers and graphene.
2. A monolithic TS-1 catalyst support according to claim 1 wherein the metal component further comprises a promoter metal component selected from one or more of Cr, mo or Ti.
3. A process for the preparation of a catalyst support of the monolithic formula TS-1 according to claim 1 or 2, comprising the following steps:
(1) Cleaning and drying a metal framework, and then placing the metal framework in a chemical vapor deposition furnace;
(2) Then, fully mixing the raw materials containing Si and C with inert gas or mixed gas of the inert gas and hydrogen in a gas form, introducing the mixture into a chemical vapor deposition furnace, and heating to grow a Si-doped carbon layer on the metal framework;
(3) After the growth is finished, cooling to room temperature to obtain the target product.
4. The method for preparing a catalyst carrier of the integral formula TS-1 according to claim 3, wherein the Si-containing and C-containing raw materials are selected from Si alkane or a mixture thereof with one or more of alkane, alkene, alkyne, alcohol, ether, ketone and ester;
wherein the chemical general formula of the Sialkane is SiR 4 、R x SiR’ (4-x) Or (RO) x SiR’ (4-x) R and R' are respectively H or C1-C5 alkyl, and x =0, 1, 2, 3 or 4;
the alkane is straight-chain alkane or cycloalkane of C1-C8;
the olefin is C1-C8 linear olefin or cycloolefin;
the chemical general formula of the ether is FOF ', and F' are respectively and independently C1-C6 alkyl and/or aryl;
the chemical general formula of the ketone is A (CO) A ', A and A' are respectively and independently C1-C6 alkyl;
the chemical general formula of the ester is M (COO) M ', and M' are C1-C6 alkyl and/or aryl.
5. The process for preparing a catalyst support of the monolith formula TS-1 according to claim 3, wherein in the step (2), when the Si-containing and C-containing raw materials are in a gaseous state, they are directly mixed with a mixed gas of hydrogen and an inert gas;
when the raw materials containing Si and C are in liquid state, the raw materials are added into a vaporizer, gasified after being heated, and mixed with the hydrogen and the inert gas;
in the chemical deposition process, the input amount of raw materials containing Si and C, hydrogen and inert gas meets the following requirements: n is Inert gas :n H2 :n Si :n C ＝100:(0～500):(0.01～50):(0.5～100)。
6. The process of claim 3, wherein in step (2), the space velocity in the CVD furnace is 0.1 hr -1 ～1000h -1 The heating temperature is 300-1200 ℃.
7. Use of a catalyst support of the monolithic TS-1 according to claim 1 or 2 for the preparation of a catalyst of the monolithic TS-1, wherein the resulting catalyst of the monolithic TS-1 has TS-1 in the form of fine crystallites covering the surface of the catalyst support of the monolithic TS-1.
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