CN113145116A - Integral TS-1 catalyst carrier and preparation and application thereof - Google Patents

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

Info

Publication number
CN113145116A
CN113145116A CN202110078069.6A CN202110078069A CN113145116A CN 113145116 A CN113145116 A CN 113145116A CN 202110078069 A CN202110078069 A CN 202110078069A CN 113145116 A CN113145116 A CN 113145116A
Authority
CN
China
Prior art keywords
reactor
propylene
hydrogen peroxide
selectivity
cvd
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110078069.6A
Other languages
Chinese (zh)
Other versions
CN113145116B (en
Inventor
曹贵平
吕慧
高鹏
纪爽
张政
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN202110078069.6A priority Critical patent/CN113145116B/en
Publication of CN113145116A publication Critical patent/CN113145116A/en
Application granted granted Critical
Publication of CN113145116B publication Critical patent/CN113145116B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

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 and solves the separation problem of the catalyst and 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, a metal auxiliary component selected from one or more of Cr, Mo or Ti can be added into the metal component. The metal skeleton with three-dimensional through-holes inside can also be called foam metal or metal foam, and before use, the metal skeleton needs to be cleaned and decontaminated, and the general treatment method is to perform ultra-treatment in ethanol with the concentration of 50-100 percentCleaning with sound for 5-60 min, washing with pure water at 50-110 deg.C N2And drying in the atmosphere, specifically, the drying agent can be 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 general formula of the Sialkane is SiR4、RxSiR’(4-x)Or (RO)xSiR’(4-x)R, R' is independently H or C1-C5 alkyl, x is 0, 1, 2, 3 or 4, more specifically, Si-alkane may be silane, tetramethylsilane, tetraethylsilane, trimethylethylsilane, dimethyldiethylsilane, methyltriethylsilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, etc., but is not limited to the examples listed. The alkane is C1-C8 straight chain alkane or cycloalkane, and concretely can be methane, ethane, propane, cyclohexane and the like, but is not limited to the listed alkane;
the olefin is C1-C8 linear 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, F' is respectively independent C1-C6 alkyl and/or aryl, such as dimethyl ether, methyl ethyl ether, diethyl ether, anisole, phenetole, diphenyl ether, etc.;
the chemical general formula of the ketone is A (CO) A ', A, A' which are respectively and independently C1-C6 alkyl, such as acetone, methylethylketone, cyclohexanone, benzophenone, etc.;
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 isIG:nH2:nSi:nC100 (0 to 500) (0.01 to 50) (0.5 to 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 N2。
Further, in the step (2), the space velocity in the chemical deposition gas phase furnace is 0.1h-1～1000h-1The preferable range is 0.5h-1～800h-1The optimal range is 1h-1～500h-1The 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), growth is carried outStopping H in the cooling process after the completion2Feeding 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 is used as a carrier for C layer growth, and the metal also plays a role in catalyzing the 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. H2Is to eliminate possible oxidizing species present in the Si source and the C source; n is a radical of2The diluting function is realized, and the growth speed and the structure of the C layer are regulated and controlled. 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 of the starting materials and the treatment techniques are conventional and commercially available 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 furnaceIntroducing Ar and H into the CVD furnace2Pumping tetraethyl silane and dimethyl ether into a CVD furnace by a metering pump, wherein the molar ratio of the tetraethyl silane to the dimethyl ether is 100:100:10:90, and the space velocity of a CVD reactor is 1h-1The temperature in the furnace is 950 ℃, after the growth is carried out for 60min, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 20 mm. Pumping a solvent methanol from the upper part of the reactor at a certain flow rate, heating to reach the 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 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 largely the same except that the tetraethyl silane is omitted, i.e., the doping with Si element is not performed.
The reactor was operated continuously, the conversion of hydrogen peroxide was 85%, the selectivity of propylene oxide from hydrogen peroxide was 74%, the selectivity of propylene oxide from propylene was 82%, and the selectivity of propylene glycol ether was 13%.
Comparative example 2
Compared with example 1, most of the results are the same, except that the introduction of H is omitted2This section. 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 furnace2、H2Methyl triethyl silicane and n-propanol with a molar ratio of 100:250:50:50 and a space velocity of the CVD reactor of 500h-1The temperature in the furnace is 30 DEGAfter growing for 10min at 0 ℃, closing the CVD heating power supply and H2And 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 500 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Tetramethoxysilane and methyl ethyl ether in a molar ratio of 100:350:5:5, at a space velocity of the CVD reactor of 500h-1The temperature in the furnace is 1100 ℃, after the growth is carried out for 20min, the CVD heating power supply is closed, and H is closed2And 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 500 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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, and allowing to pass throughSonic 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 furnace2Methyl triethyl silicane and isobutene in the molar ratio of 100 to 50 to 30 to 20, the space velocity of the CVD reactor of 1H-1, the temperature in the furnace of 600 ℃, after 150min of growth, the CVD heating power supply is turned off, and H is turned off2And 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 5 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The reactor is operated continuously, 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, and introducing Ar and H into the CVD furnace2Dimethyl diethyl silane and tertiary butanol in a molar ratio of 100:200:5:60, at a space velocity of the CVD reactor of 0.1h-1The temperature in the furnace is 1200 ℃, after 120min of growth, the CVD heating power supply is closed, and H is closed2And 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 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The reactor is continuously operated, the conversion rate of hydrogen peroxide is 97%, the selectivity of the hydrogen peroxide to propylene oxide is 96%, and propylene is generated to be ringThe selectivity to propylene oxide was 96% and to 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 furnace2Trimethylethylsilane and propyne in a molar ratio of 100:300:30:1 at a space velocity of the CVD reactor of 800h-1The temperature in the furnace is 300 ℃, after the growth is carried out for 20min, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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, framework 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 furnace2Silane and methane in a molar ratio of 100:100:20:0.5, at a space velocity of the CVD reactor of 1000h-1The temperature in the furnace is 1200 ℃, after the growth is carried out for 10min, the CVD heating power supply is closed, and H is closed2And 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 10mm and a bed height of 500 mm. Pumping the solvent methanol from the upper part of the reactor at a certain flow rate, heating to 55 ℃,pumping in hydrogen peroxide and adding propylene, wherein the molar ratio of methanol to hydrogen peroxide to propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Trimethyl methoxysilane and acetone in the molar ratio of 100:350:0.01:30 and the space velocity of the CVD reactor is 1000h-1The temperature in the furnace is 600 ℃, after 50min of growth, the CVD heating power supply is closed, and H is closed2And 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 10mm and a bed height of 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The reactor is operated continuously, the conversion rate of the 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 of 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 furnace2Tetramethylsilane and butyl methacrylate in a molar ratio of 100:0:25:5, at a space velocity of the CVD reactor of 0.5h-1The temperature in the furnace is 300 ℃, after 120min of growth, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. Namely, it isAnd 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 5 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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, 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 furnace2Tetramethylsilane and cyclohexanone in a molar ratio of 100:250:35:60, at a space velocity of the CVD reactor of 0.5h-1The temperature in the furnace is 600 ℃, after 50min of growth, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 10mm and a bed height of 20 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Dimethyldimethoxysilane and 1-butene in a molar ratio of 100:400:25:40 and a space velocity of the CVD reactor of 500h-1The temperature in the furnace is 950 ℃, after the growth is carried out for 200min, the CVD heating power supply is closed, and H is closed2And 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 5mm and a bed height of 500 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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
Placing metal Cu foam with diameter of 100mm and height of 10mm (aperture of 10 μm, framework thickness of 5 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 furnace2Dimethyl dimethoxy silane and ethyl acetate in the molar ratio of 100:300:10:0.5 and the space velocity of the CVD reactor of 1h-1The temperature in the furnace is 1100 ℃, after the growth is carried out for 10min, the CVD heating power supply is closed, and H is closed2And 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 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Trimethyl methoxy silane and cyclohexane in the molar ratio of 100:100:45:50, and the space velocity of the CVD reactor is 800h-1The temperature in the furnace is 1200 ℃, after the growth is carried out for 30min, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 10mm and a bed height of 20 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 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 furnace2Dimethyl diethyl silane and acetylene in a molar ratio of 100:200:35:60, and a space velocity of the CVD reactor of 1h-1The temperature in the furnace is 1100 ℃, after the growth is carried out for 10min, the CVD heating power supply is closed, and H is closed2And 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 5 mm. Pumping methanol solvent from the upper part of the reactor at a certain flow rate, heating to 55 deg.C, pumping hydrogen peroxide, and adding propylene, methanol, hydrogen peroxide and propyleneThe molar ratio of the alkene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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, and introducing Ar and H into the CVD furnace2Dimethyl diethyl silane and methyl formate in the molar ratio of 100:450:20:20, and the space velocity of the CVD reactor is 800h-1The temperature in the furnace is 1100 ℃, after the growth is carried out for 100min, the CVD heating power supply is closed, and H is closed2And 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 200mm and a bed height of 20 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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
Placing 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, and introducing Ar and H into the CVD furnace2Tetramethoxysilane and methanol in a molar ratio of 100:150:0.1:40 at a space velocity of the CVD reactor of 0.1h-1The temperature in the furnace is 950 ℃, after the growth is carried out for 20min, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 20 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Silane and ethane in a molar ratio of 100:500:0.1:5, at a space velocity of the CVD reactor of 800h-1The temperature in the furnace is 300 ℃, after 50min of growth, the CVD heating power supply is closed, and H is closed2And 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 100mm and a bed height of 20 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Tetramethylsilane and benzophenone in their molsThe ratio of 100:100:15:0.5, the space velocity of the CVD reactor is 0.1h-1The temperature in the furnace is 400 ℃, after 80min of growth, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 20 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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
Placing metal 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 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 furnace2Trimethylethylsilane and 2-butene in a molar ratio of 100:150:15:1 at a space velocity of the CVD reactor of 1h-1The temperature in the furnace is 1100 ℃, after the growth is carried out for 100min, the CVD heating power supply is closed, and H is closed2And 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 500 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Dimethyldimethoxysilane and 1, 3-butadiene in a molar ratio of 100:200:25:10 at a CVD reactor space velocity of 800h-1The temperature in the furnace is 300 ℃, after 120min of growth, the CVD heating power supply is closed, and H is closed2And 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 500 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 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 furnace2Methyltrimethoxysilane and cyclopentadiene at a molar ratio of 100:50:45:70 at a CVD reactor space velocity of 500h-1The temperature in the furnace is 400 ℃, after 80min of growth, the CVD heating power supply is closed, and H is closed2And 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 5 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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
Placing 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, and introducing Ar and H into the CVD furnace2Trimethylethylsilane and isobutanol in a molar ratio of 100:400:0.01:30, at a space velocity of the CVD reactor of 0.5h-1When the temperature in the furnace is 1200 ℃, after the growth is carried out for 60min, the CVD heating power supply is closed, and H is closed2And 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 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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, and introducing Ar and H into the CVD furnace2Tetraethyl silane and norbornene in a molar ratio of 100:500:0.01:100, at a space velocity of the CVD reactor of 0.1h-1The temperature in the furnace is 950 ℃, after the growth is carried out for 60min, the CVD heating power supply is closed, and H is closed2And 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.
Loading the obtained catalystFilling the mixture in a fixed bed reactor with the inner diameter of 200mm, wherein the height of a bed layer is 5 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Trimethyl methoxysilane and cyclohexene in a molar ratio of 100:250:30:40, at a CVD reactor space velocity of 1000h-1The temperature in the furnace is 950 ℃, after the growth is carried out for 30min, the CVD heating power supply is closed, and H is closed2And 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 10mm and a bed height of 500 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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
Placing 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 furnace2Trimethylethylsilane and anisole in a molar ratio of 100:150:10:10, space velocity of the CVD reactorIs 1000h-1The temperature in the furnace is 300 ℃, after the growth is carried out for 30min, the CVD heating power supply is closed, and H is closed2And 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 5mm and a bed height of 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace2Tetramethylsilane and methyl ethyl ketone in a molar ratio of 100:300:50:30, at a space velocity of the CVD reactor of 1 hour-1The temperature in the furnace is 400 ℃, after the growth is carried out for 150min, the CVD heating power supply is closed, and H is closed2And 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 20 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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
Mixing the mixture with a diameter of 5mm and a height of 5mm (aperture of 0.1 μm, skeleton thickness)5 μm) metal Cu foam 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 furnace2Tetramethoxysilane and isopropanol in a molar ratio of 100:500:45:70 and a space velocity of the CVD reactor of 500h-1The temperature in the furnace is 1200 ℃, after the growth is carried out for 150min, the CVD heating power supply is closed, and H is closed2And 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 5 mm. Pumping methanol as a 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Silane and butyne in a molar ratio of 100:50:20:90, at a space velocity of the CVD reactor of 0.5h-1The temperature in the furnace is 400 ℃, after the growth is carried out for 60min, the CVD heating power supply is closed, and H is closed2And 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 5 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The reactor is operated continuously, the conversion rate of hydrogen peroxide is 95 percent, and the selection of the propylene oxide generated by the hydrogen peroxide isThe selectivity was 98%, the selectivity for propylene to propylene oxide was 94.7%, and the selectivity for 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, framework 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 furnace2Methyl triethyl silicane and n-butanol, the molar ratio of which is 100:450:0.1:100, and the space velocity of the CVD reactor is 1000h-1The temperature in the furnace is 400 ℃, after the growth is carried out for 20min, the CVD heating power supply is closed, and H is closed2And 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 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Dimethyl diethyl silane and phenylacetylene in a molar ratio of 100:350:40:10, and a space velocity of the CVD reactor of 0.5h-1The temperature in the furnace is 600 ℃, after the growth is carried out for 30min, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 200mm and a bed height of 500 mm. The solvent methanol is added toPumping in the flow from the upper part of the reactor, raising the temperature to 55 ℃, pumping in hydrogen peroxide and adding propylene, wherein the molar ratio of methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 furnace2Methyltrimethoxysilane and propylene in a molar ratio of 100:0:50:50 at a CVD reactor space velocity of 0.5h-1The temperature in the furnace is 1200 ℃, after 80min of growth, the CVD heating power supply is closed, and H is closed2And 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 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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, and introducing Ar and H into the CVD furnace2Tetraethylsilane and propane in a molar ratio of 100:0:40:80 at a space velocity of the CVD reactor of 0.1h-1The temperature in the furnace is 950 ℃, after 50min of growth, the CVD heating power supply is closed, and the CVD heating power supply is closedH2And the Si source and the C source are naturally cooled 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 5 mm. Pumping methanol as a 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 95.3%, and the selectivity of propylene glycol ether was 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 furnace2Silane and diphenyl ether in a molar ratio of 100:0:35:70 and a space velocity of the CVD reactor of 1000h-1The temperature in the furnace is 400 ℃, after the growth is carried out for 200min, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 100mm and a bed height of 5 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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 cooling at 110 deg.CAnd (5) drying. Transferring into a CVD furnace, and introducing Ar and H into the CVD furnace2Methyltriethylsilane and ethylene in a molar ratio of 100:450:15:20 at a CVD reactor space velocity of 0.1h-1The temperature in the furnace is 1100 ℃, after the growth is carried out for 200min, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled to room temperature in Ar gas flow. Thus obtaining the foam Fe-Co 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 20 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The 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
Placing Co-Ni foam with diameter of 10mm and 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 furnace2Methyltrimethoxysilane and ethanol in a molar ratio of 100:400:40:80 at a CVD reactor space velocity of 500h-1The temperature in the furnace is 600 ℃, after 80min of growth, the CVD heating power supply is closed, and H is closed2And the Si source and the C source are naturally cooled 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 500 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The reactor is continuously operated, the conversion rate of the hydrogen peroxide is 95 percent, the selectivity of the propylene oxide generated by the propylene is 95.5 percent,the selectivity to 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, and introducing Ar and H into the CVD furnace2Tetraethyl silane and phenetole in a molar ratio of 100:50:5:1 and a space velocity of the CVD reactor of 800h-1The temperature in the furnace is 600 ℃, after the growth is carried out for 100min, the CVD heating power supply is closed, and H is closed2And 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 10 mm. Pumping a solvent methanol 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 the methanol to the hydrogen peroxide to the propylene is 5:2.5: 1. The space velocity of the reactor is 1h-1The reactor was operated continuously, the conversion of hydrogen peroxide was 95%, the selectivity of propylene oxide from propylene was 96.8%, and the selectivity of propylene glycol ether was 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 (10)

1. The 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 through holes, and the Si-doped carbon layer grows on the metal framework.
2. A monolithic TS-1 catalyst support according to claim 1, wherein the support is a cylindrical structure with a diameter of 5mm to 900mm and a height of 1mm to 3000mm, and the average pore diameter of the three-dimensional pores is 0.1 μm to 500 μm.
3. A monolithic TS-1 catalyst support according to claim 1 wherein the metal component of the metal framework comprises an alloy of one or more of the transition metals Fe, Co, Ni, Cu.
4. A monolithic TS-1 catalyst support according to claim 3 wherein the metal component further comprises a promoter metal component selected from one or more of Cr, Mo or Ti.
5. The carrier of claim 1, wherein the structure of the Si-doped carbon layer is one or more of amorphous C, carbon nanotube, carbon nanofiber and graphene.
6. A process for the preparation of a catalyst support of the monolithic formula TS-1 according to any one of claims 1 to 5, 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.
7. The method for preparing a catalyst carrier of the integral formula TS-1 according to claim 6, 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 SiR4、RxSiR’(4-x)Or (RO)xSiR’(4-x)R, R' is independently H or C1-C5 alkyl, x is 0, 1, 2, 3 or 4;
the alkane is straight chain alkane or cycloalkane of C1-C8;
the olefin is C1-C8 linear chain olefin or cycloolefine;
the chemical general formula of the ether is FOF ', F, F' is C1-C6 alkyl and/or aryl respectively and independently;
the chemical general formula of the ketone is A (CO), A ', A, A' is 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.
8. The process for preparing a catalyst support of the monolith formula TS-1 according to claim 6, 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 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 introduction amount of raw materials containing Si and C, hydrogen and inert gas meets the following requirements: n isInert gas:nH2:nSi:nC＝100:(0～500):(0.01～50):(0.5～100)。
9. The method for preparing a catalyst carrier of the integral formula TS-1 according to claim 6, wherein in the step (2), the space velocity in the chemical deposition vapor phase furnace is 0.1h-1～1000h-1The heating temperature is 300-1200 ℃.
10. Use of a monolithic TS-1 catalyst support according to any one of claims 1 to 5 for the preparation of a monolithic TS-1 catalyst, wherein the resulting monolithic TS-1 catalyst has TS-1 in the form of fine crystallites covering the surface of the monolithic TS-1 catalyst support.
CN202110078069.6A 2021-01-20 2021-01-20 Integral TS-1 catalyst carrier and preparation and application thereof Active CN113145116B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110078069.6A CN113145116B (en) 2021-01-20 2021-01-20 Integral TS-1 catalyst carrier and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110078069.6A CN113145116B (en) 2021-01-20 2021-01-20 Integral TS-1 catalyst carrier and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN113145116A true CN113145116A (en) 2021-07-23
CN113145116B CN113145116B (en) 2022-12-20

Family

ID=76878645

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110078069.6A Active CN113145116B (en) 2021-01-20 2021-01-20 Integral TS-1 catalyst carrier and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN113145116B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113813982A (en) * 2021-10-11 2021-12-21 华东理工大学 Integral N-modified TS-1 catalyst carrier and preparation method thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6534661B1 (en) * 2000-12-28 2003-03-18 Hydrocarbon Technologies, Inc. Integrated process and dual-function catalyst for olefin epoxidation
CN101199941A (en) * 2007-08-03 2008-06-18 华东理工大学 Process for preparing titanium-silicon molecular sieve/nano-carbon fiber fiber composite catalyst
CN101360729A (en) * 2005-12-27 2009-02-04 巴斯夫欧洲公司 Process for epoxidizing propene
US7501532B1 (en) * 2007-11-20 2009-03-10 Lyondell Chemical Technology, L.P. Process for producing hydrogen peroxide
WO2009155674A1 (en) * 2008-06-24 2009-12-30 Quattor Petroqu?Ímica S.A. Preparation of heterogeneous catalysts used in selective hydrogenation of glycerin to propene, and a process for the selective hydrogenation of glycerin to propene
US20120052692A1 (en) * 2009-07-08 2012-03-01 Imec Fabrication of porogen residues free low-k materials with improved mechanical and chemical resistance
CN102962087A (en) * 2011-08-31 2013-03-13 中国科学院金属研究所 Carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof
CN105251273A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Filter screen for preventing and treating haze
CN109516452A (en) * 2019-01-24 2019-03-26 华东理工大学 Three-dimensional grapheme and its preparation method and application
CN111085264A (en) * 2018-10-23 2020-05-01 华东理工大学 Monolithic modified TS-1 catalyst based on carbon porous ceramic, and preparation method and application thereof
CN111085205A (en) * 2018-10-23 2020-05-01 华东理工大学 Carbon porous metal-based integral modified TS-1 catalyst, and preparation method and application thereof
CN111495424A (en) * 2020-04-30 2020-08-07 河南智川节能环保科技有限公司 Graphene composite material for removing formaldehyde and preparation method thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6534661B1 (en) * 2000-12-28 2003-03-18 Hydrocarbon Technologies, Inc. Integrated process and dual-function catalyst for olefin epoxidation
CN101360729A (en) * 2005-12-27 2009-02-04 巴斯夫欧洲公司 Process for epoxidizing propene
CN101199941A (en) * 2007-08-03 2008-06-18 华东理工大学 Process for preparing titanium-silicon molecular sieve/nano-carbon fiber fiber composite catalyst
US7501532B1 (en) * 2007-11-20 2009-03-10 Lyondell Chemical Technology, L.P. Process for producing hydrogen peroxide
WO2009155674A1 (en) * 2008-06-24 2009-12-30 Quattor Petroqu?Ímica S.A. Preparation of heterogeneous catalysts used in selective hydrogenation of glycerin to propene, and a process for the selective hydrogenation of glycerin to propene
US20120052692A1 (en) * 2009-07-08 2012-03-01 Imec Fabrication of porogen residues free low-k materials with improved mechanical and chemical resistance
CN102962087A (en) * 2011-08-31 2013-03-13 中国科学院金属研究所 Carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof
CN105251273A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Filter screen for preventing and treating haze
CN111085264A (en) * 2018-10-23 2020-05-01 华东理工大学 Monolithic modified TS-1 catalyst based on carbon porous ceramic, and preparation method and application thereof
CN111085205A (en) * 2018-10-23 2020-05-01 华东理工大学 Carbon porous metal-based integral modified TS-1 catalyst, and preparation method and application thereof
CN109516452A (en) * 2019-01-24 2019-03-26 华东理工大学 Three-dimensional grapheme and its preparation method and application
CN111495424A (en) * 2020-04-30 2020-08-07 河南智川节能环保科技有限公司 Graphene composite material for removing formaldehyde and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱建强等，: ""乙烯掺杂对硅薄膜沉积速率和形貌的影响"", 《硅酸盐通报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113813982A (en) * 2021-10-11 2021-12-21 华东理工大学 Integral N-modified TS-1 catalyst carrier and preparation method thereof

Also Published As

Publication number Publication date
CN113145116B (en) 2022-12-20

Similar Documents

Publication Publication Date Title
CN113457649B (en) Integral boron-doped TS-1 catalyst carrier and preparation and application thereof
CN107335386B (en) Configuration and preparation of catalytic reactor and method for directly synthesizing ethylene by catalyzing methane under anaerobic condition
KR20070086187A (en) Method for preparing single walled carbon nanotubes
CN113145116B (en) Integral TS-1 catalyst carrier and preparation and application thereof
CN108262034B (en) Catalyst, preparation method thereof and application thereof in ammonia synthesis under normal pressure and low temperature
CN109622000A (en) A kind of base metal selective hydrocatalyst of acetylene and its preparation method and application
CN105195238A (en) Method for preparing metal-oxide compound nano catalyst by molecular layer deposition
CN102139227B (en) Catalyst for preparing epoxy propane by propylene liquid-phase epoxidation reaction and preparation method thereof
CN111085205B (en) Carbon porous metal-based integral modified TS-1 catalyst, and preparation method and application thereof
CN107879898A (en) A kind of method that vicinal diamines class compound is synthesized using difunctional characteristic catalyst
KR20130017536A (en) Catalysts with inverse concentration gradient of catalytic element and method for preparing the same
JP4977982B2 (en) Method for producing linear carbon material and method for producing functional device
CN111167462A (en) Direct methanol cracking preparation of H2Catalyst, process for its preparation and its use
CN114870853B (en) Core-shell catalyst for preparing cyclohexanol by catalyzing guaiacol to be subjected to selective hydrodeoxygenation
CN111330588A (en) High-activity propylene gas-phase epoxidation catalyst and preparation method thereof
CN1699151A (en) Process for preparing nano carbon tube
CN1872826A (en) Method for producing lower alcohol continuously
CN102060656A (en) Method for preparing cyclohexanone
CN109513445A (en) Ternary metal oxide film catalyst and preparation method thereof
CN113813982A (en) Integral N-modified TS-1 catalyst carrier and preparation method thereof
CN113426472B (en) Cobalt-based catalyst and CO 2 Method for preparing CO by catalytic hydrogenation
CN114797966B (en) Integral carrier in-situ immobilized TS-1 catalyst and preparation and application thereof
CN107879893A (en) A kind of method that catalytic oxidation prepares vicinal diamines class compound
KR900002456B1 (en) Preparation method of silver catalyst for producing ethylene oxide
KR101659163B1 (en) Preparing method of alkanol

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant