CN113198543A - Preparation of nano-structured catalytic film by using metal coordination compound as precursor - Google Patents
Preparation of nano-structured catalytic film by using metal coordination compound as precursor Download PDFInfo
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- CN113198543A CN113198543A CN202110507725.XA CN202110507725A CN113198543A CN 113198543 A CN113198543 A CN 113198543A CN 202110507725 A CN202110507725 A CN 202110507725A CN 113198543 A CN113198543 A CN 113198543A
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Images
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/23—
-
- B01J35/59—
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
Abstract
The invention discloses a method for preparing a nano-structured catalytic film by using a metal coordination compound as a precursor. The precursor fluid of the metal coordination compound enters the membrane pore canal in a diffusion or flowing mode, then the fluid with the functions of reduction, oxidation, vulcanization and ion exchange enters the membrane pore canal, and the metal coordination compound is prepared into nano metal simple substance, metal oxide, metal sulfide and bimetal with corresponding functions. Finally obtaining the catalytic membrane with the nano structure along the direction of the membrane pores. The catalytic membrane may be used as a monolithic catalyst for batch reaction operations or as a separate catalytic bed in a fixed bed-like flow-through membrane mode of operation. Compared with a common fixed bed reactor, the uniformity, the dispersibility and the confinement of the membrane pore channel can strengthen the contact between the reaction fluid and the nano catalytic material and improve the reaction rate.
Description
Technical Field
The invention relates to the field of catalytic membranes with nanostructures, in particular to a method for preparing an immobilized nano catalytic material in a membrane pore channel by using a metal as a precursor by using a coordination compound.
Background
The nano material has the advantages of high activity, large specific surface area and the like when being used for catalytic reaction. The powdered nano material is involved in separation and recovery in the using process, and the powder is generally required to be bonded or extruded into particles with certain shapes in practical industrial application. The shaped particles show a significant amplification effect when used in a fixed bed reactor. The membrane with the micro-nano pore canal is a good carrier of the nano material, and if the nano material can be fixedly loaded in the whole membrane pore canal along the depth direction of the membrane pore canal, a composite material of the nano catalyst and the membrane can be formed. The catalytic composite membrane with the nano structure along the depth direction of the membrane hole can realize the cooperative reinforcement of catalytic reaction on the nano structure scale, the membrane pore size and the catalytic bed scale in the process similar to the general fixed bed flow-through reaction.
The key to realize the catalytic composite membrane with the nano structure is that the nano catalytic material is effectively supported in each membrane pore passage and uniformly distributed along the depth direction of the membrane pore. The method for compounding the prepared nano material and the membrane (such as blending, suction filtration and the like) is a common method at present. Because the nano materials are easy to agglomerate, the method is difficult to ensure that the nano materials are uniformly immobilized in each membrane pore channel along the thickness direction of the membrane. Furthermore, sequentially immersing the porous base membrane into different precursor reaction solutions may be desirable to prepare and immobilize the nanomaterial within the membrane pore channels. In this case, since the liquid has surface tension, the resistance of the reaction solution to the pores of the membrane is large. In order to further improve the efficiency of in-situ immobilization of the nano material in the membrane pore canalThe applicant previously invented a flow-reaction synergistic method to immobilize nanomaterials in situ in membrane pores. The homogeneous catalyst material precursor fluid can overcome the surface tension of liquid in the process of flowing through the membrane, flows in each membrane pore channel, and finally is chemically deposited in the membrane pore to form nano particles1-4。
In the preparation of nano materials, under appropriate conditions, a metal coordination compound formed by metal ions and organic ligands through coordination bonds can be broken and lead to continuous release of the metal ions in the metal coordination compound, thereby providing the precondition for preparing nano metal catalytic materials. The metal ions are slowly released, the metal ions for synthesizing and preparing the nano material can be controlled in a relatively constant range, and thermodynamics and kinetics in the growth process of the nano material are adjusted, so that the nano material with uniform particle size and narrow particle size distribution is formed. The literature reports that the metal-organic framework material formed by coordination bonds is used as a precursor, the slow and uniform growth of nano particles is realized on a graphene substrate, and the conditions of agglomeration and uneven distribution caused by the gradual reduction of the concentration of metal ions in a liquid phase system are effectively avoided5. If the metal coordination compound is fixed in the membrane pore canal and used as a precursor for preparing the metal nano catalytic material, the structure uniformity of the nano material can be realized by utilizing the metal ion slow release effect, the content of the nano catalytic material in the membrane pore canal can be improved by utilizing the larger surface area of the membrane pore canal, and finally, the good catalytic performance is realized.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a nano-structure catalytic membrane prepared by taking a metal coordination compound as a precursor, wherein the catalytic membrane has good stability and strengthens a catalytic process.
According to the nano-structure catalytic membrane, the nano-catalytic material takes a metal coordination compound as a precursor fluid, and the slow release of metal ions is realized by utilizing the non-stability of coordination bonds. In the process of slowly releasing the metal ions, the metal ions for synthesizing the nano metal catalytic material can be maintained in a relatively constant concentration range, and under the action of a reducing agent, an oxide, a sulfide and a second metal salt, a nano metal simple substance, a nano metal oxide, a nano metal sulfide and a bimetal nano material with a catalytic function are respectively formed. In the process of preparing the nano catalytic material, the nano material can be directly immobilized in the membrane pore channel, or a corresponding catalyst carrier can be immobilized in the membrane pore channel firstly, and then the nano catalytic material is immobilized on the carrier in the membrane pore channel.
The nano-structure catalytic membrane has the structure that nano-materials with catalytic function are uniformly and fixedly loaded in all membrane pore channels along the depth direction of the membrane pore. By utilizing the dispersion effect of the membrane pore canal, the nano material is prevented from agglomerating in the range larger than the size of the membrane pore canal, the surface utilization rate of the nano material is improved, and the contact between the reaction fluid and the nano catalytic material in the reaction process is strengthened. If the catalytic reaction is carried out in the operation mode of passing through the membrane, the catalytic reaction can be limited in the membrane pore canal with micro-nano scale by utilizing the domain limiting effect of the membrane pore canal, thereby greatly reducing the mass transfer distance in the catalytic reaction process and strengthening the mass transfer in the process.
In order to support the nano-catalytic material in the membrane pore channels, the precursor fluid of the coordination compound can be introduced into the membrane pore channels in a diffusion mode by adopting an impregnation method, and can also be introduced into the membrane pore channels in a flow mode by adopting a mode of passing through the membrane. And drying the membrane to realize the immobilization of the metal coordination compound in a membrane pore channel, then adopting a fluid with a reduction function, an oxidation function, a vulcanization function and an ion exchange function to enter the membrane pore in a diffusion or flowing manner, and reacting with the metal coordination compound in the membrane pore channel to finally obtain the nano metal simple substance, the metal oxide, the metal sulfide or the bimetal with the corresponding catalytic function. The solid-supported content of the nano catalytic material in the membrane pore channel is regulated and controlled by changing the cycle times of the coordination compound precursor fluid and the functional fluid entering the membrane pore channel.
The porous base membrane adopted by the invention can adopt but is not limited to polymer material, metal material, ceramic material and the like, such as: polyether sulfone, polytetrafluoroethylene, polypropylene, polyvinylidene fluoride, metal titanium, metal nickel, metal copper, stainless steel, aluminum oxide, zirconium oxide and the like. The porous base membrane can be prepared by phase inversion, sintered at high temperature and processed by electrostatic spinning. The pore channel shape of the porous base film may be, but is not limited to, finger-shaped pores, mesh-shaped pores, stepped pores, and the like. The base film structure may be a homogeneous film or a composite film. The pore size of the base membrane is in the range of 10nm-10 μm, and the pore size distribution can be uniform along the thickness direction of the membrane and can also be gradually changed along the thickness direction of the membrane.
The grain diameter of the nanometer material with catalytic function in the pore canal of the membrane is in the range of 1nm-200nm, and the nanometer material is fixed and loaded in the pore canal of the whole membrane. The nano catalytic material can be materials with different grain diameters distributed along the film thickness direction, and can also be materials with the same grain diameter distributed along the film thickness direction.
The constructed nano catalytic membrane can be used in typical catalytic reaction processes, including but not limited to methanol direct dehydrogenation, ethanol direct dehydrogenation, methanol steam reforming hydrogen production, ethanol steam reforming hydrogen production, methyl orange reductive degradation, rhodamine reductive degradation, methylene blue reductive degradation, and the like. In the catalytic reaction process, the catalytic membrane can be used as a monolithic catalyst for the catalytic process in a batch operation mode, and can also be used as an independent catalytic bed layer for the catalytic reaction in a flow-through operation mode similar to a common fixed bed.
Compared with a common fixed bed reactor, the nano catalytic material with small particle size and uniform size distribution is directly immobilized in the membrane pore canal without particle forming, and the reaction fluid can be contacted with the nano catalytic material in a flowing manner, so that the effective contact area in the catalytic reaction process is increased. If a fixed bed-like flow-through membrane is adopted for reaction, the catalytic reaction process is limited in a membrane pore channel with a micro-nano scale, the transfer distance from a flowing main body to the surface of a catalyst is greatly shortened, and the heat and mass transfer process in the membrane pore channel is enhanced.
Drawings
FIG. 1 is a schematic of a nanostructured catalytic membrane
FIG. 2 flow of coordination compound precursor fluid to form nanocatalyst material within membrane pore channels
FIG. 3 catalytic reaction mode of nanostructured catalytic membranes
FIG. 4 is a graph showing the relationship between the conversion of nitrophenol solution and its membrane speed.
Detailed Description
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to the following examples, and various modifications and implementations are included within the technical scope of the present invention without departing from the content and scope of the present invention.
Example 1:
in the embodiment, a porous polyethersulfone film with the aperture of 0.45 mu m and the diameter of 100mm is selected as a carrier, and a copper nano-catalyst is selected as an active center. In order to test the catalytic performance of the catalytic membrane, the hydrogenation catalysis of p-nitrophenol is selected as a reaction model. The specific implementation steps are as follows:
(1) the porous membrane was fixed in a positive pressure filter and 50mL of copper nitrate solution was percolated through the porous polyethersulfone membrane within 20-30min by nitrogen pressurization. Then, putting the porous polyether sulfone film into a 60 ℃ oven for drying for 30 min;
(2) fixing a porous polyether sulfone film rich in copper nitrate crystals in a positive pressure filter, and infiltrating 50mL of 2-methylimidazole solution through the porous polyether sulfone film within 20-30min by pressurizing with nitrogen;
(3) ultrasonic cleaning with deionized water to remove unstable nanoparticles on the surface of the membrane, and drying in a 60 ℃ oven;
(4) fixing the porous polyethersulfone film rich in copper ions and 2-methylimidazole coordination compounds in a positive pressure filter, and infiltrating 250mL of 50mM sodium borohydride aqueous solution through the porous polyethersulfone film within 20-30min under the pressure of nitrogen to obtain the copper nano catalytic membrane.
(5) Continuous catalysis of copper nano catalytic films prepared by taking metal coordination compounds as precursors: the reaction solution is p-nitrophenol solution, the molar concentration is 0.00025mol/L, and the concentration of sodium borohydride is 0.025 mol/L. The prepared copper nano catalytic membrane is arranged on a detachable filterIn the device, is arranged at the outlet of the injector. The speed of the reaction solution permeating the membrane is adjusted by adjusting the injection speed of the injection pump. The injection speed ranges from 0.16 to 9.55mL cm-2·min-1。
(6) Real-time detection: and collecting the solution at the downstream of the filter at different flow rates, measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer, and calculating the conversion rate of the p-nitrophenol.
Example 2:
in the embodiment, a porous polyethersulfone film with the aperture of 0.45 mu m and the diameter of 100mm is selected as a carrier, and a silver nano catalyst is selected as an active center. In order to test the catalytic performance of the catalytic membrane, the hydrogenation catalysis of p-nitrophenol is selected as a reaction model. The specific implementation steps are as follows:
(1) the porous membrane was fixed in a positive pressure filter and 50mL of silver nitrate solution was percolated through the porous polyethersulfone membrane within 20-30min by nitrogen pressurization. Then, putting the porous polyether sulfone film into a 60 ℃ oven for drying for 30 min;
(2) fixing a porous polyether sulfone film rich in silver nitrate crystals in a positive pressure filter, and infiltrating 50mL of 2-methylimidazole solution through the porous polyether sulfone film within 20-30min by pressurizing with nitrogen;
(3) ultrasonic cleaning with deionized water to remove unstable nanoparticles on the surface of the membrane, and drying in a 60 ℃ oven;
(4) fixing the porous polyethersulfone film rich in silver ions and 2-methylimidazole coordination compounds in a positive pressure filter, and infiltrating 250mL of 50mM sodium borohydride aqueous solution through the porous polyethersulfone film within 20-30min under the pressure of nitrogen to obtain the silver nano catalytic membrane.
(5) Continuous catalysis of silver nanocatalysis films prepared by taking metal coordination compounds as precursors: the reaction solution is p-nitrophenol solution, the molar concentration is 0.00025mol/L, and the concentration of sodium borohydride is 0.025 mol/L. The prepared same nano catalytic membrane is arranged in a detachable filter and is placed at the outlet of an injector. The speed of the reaction solution passing through the membrane is adjusted by adjusting the injection speed of the injection pump. The injection speed ranges from 0.16 to 9.55mL cm-2·min-1。
(6) Real-time detection: and collecting the solution at the downstream of the filter at different flow rates, measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer, and calculating the conversion rate of the p-nitrophenol.
Example 3:
in the embodiment, a porous polyethersulfone film with the aperture of 0.45 mu m and the diameter of 100mm is selected as a carrier, and a copper-silver bimetallic core-shell nano catalyst is selected as an active center. In order to test the catalytic performance of the catalytic membrane, the hydrogenation catalysis of p-nitrophenol is selected as a reaction model. The specific implementation steps are as follows:
(1) the porous membrane was fixed in a positive pressure filter and 50mL of copper nitrate solution was percolated through the porous polyethersulfone membrane within 20-30min by nitrogen pressurization. Then, putting the porous polyether sulfone film into a 60 ℃ oven for drying for 30 min;
(2) fixing a porous polyether sulfone film rich in copper nitrate crystals in a positive pressure filter, and infiltrating 50mL of 2-methylimidazole solution through the porous polyether sulfone film within 20-30min by pressurizing with nitrogen;
(3) ultrasonic cleaning with deionized water to remove unstable nanoparticles on the surface of the membrane, and drying in a 60 ℃ oven;
(4) fixing a porous polyethersulfone film rich in copper ions and 2-methylimidazole coordination compounds in a positive pressure filter, and infiltrating 250mL of 50mM sodium borohydride aqueous solution through the porous polyethersulfone film within 20-30min by pressurizing with nitrogen to obtain a copper nano catalytic film;
(5) fixing a porous polyether sulfone membrane rich in a copper nano catalyst in a positive pressure filter, and infiltrating 250mL of 1mM silver nitrate solution through the porous polyether sulfone membrane within 20-30min by pressurizing with nitrogen to obtain a copper-silver bimetallic core-shell nano catalytic membrane;
(6) continuous catalysis of copper nano catalytic films prepared by taking metal coordination compounds as precursors: the reaction solution is p-nitrophenol solution, the molar concentration is 0.00025mol/L, and the concentration of sodium borohydride is 0.025 mol/L. The prepared same nano catalytic membrane is arranged in a detachable filter and is placed at the outlet of an injector. By adjusting the injection speed of the injection pumpThe speed of the solution through the membrane is used. The injection speed ranges from 0.16 to 9.55mL cm-2·min-1。
(6) Real-time detection: and collecting the solution at the downstream of the filter at different flow rates, measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer, and calculating the conversion rate of the p-nitrophenol.
Example 4:
in the embodiment, a porous polyethersulfone film with the aperture of 0.45 mu m and the diameter of 100mm is selected as a carrier, and a copper-silver bimetallic core-shell nano catalyst is selected as an active center. In order to test the catalytic performance of the catalytic membrane, the hydrogenation catalysis of p-nitrophenol is selected as a reaction model. The specific implementation steps are as follows:
(1) the porous membrane was fixed in a positive pressure filter and 50mL of copper nitrate solution was percolated through the porous polyethersulfone membrane within 20-30min by nitrogen pressurization. Then, putting the porous polyether sulfone film into a 60 ℃ oven for drying for 30 min;
(2) fixing a porous polyether sulfone film rich in copper nitrate crystals in a positive pressure filter, and infiltrating 50mL of 2-methylimidazole solution through the porous polyether sulfone film within 20-30min by pressurizing with nitrogen;
(3) ultrasonic cleaning with deionized water to remove unstable nanoparticles on the surface of the membrane, and drying in a 60 ℃ oven;
(4) fixing a porous polyethersulfone film rich in copper ions and 2-methylimidazole coordination compounds in a positive pressure filter, and infiltrating 250mL of 50mM sodium borohydride aqueous solution through the porous polyethersulfone film within 20-30min by pressurizing with nitrogen to obtain a copper nano catalytic film;
(5) fixing a porous polyether sulfone membrane rich in a copper nano catalyst in a positive pressure filter, and infiltrating 250mL of 2mM silver nitrate solution through the porous polyether sulfone membrane within 20-30min by pressurizing with nitrogen to obtain a copper-silver bimetallic core-shell nano catalytic membrane;
(6) continuous catalysis of copper nano catalytic films prepared by taking metal coordination compounds as precursors: the reaction solution is p-nitrophenol solution, the molar concentration is 0.00025mol/L, and the concentration of sodium borohydride is 0.025 mol/L. The same nano catalytic membrane prepared by the method is arranged on a catalystThe filter is disassembled and is placed at the outlet of the syringe. The speed of the reaction solution passing through the membrane is adjusted by adjusting the injection speed of the injection pump. The injection speed ranges from 0.16 to 9.55mL cm-2·min-1。
(7) Real-time detection: and collecting the solution at the downstream of the filter at different flow rates, measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer, and calculating the conversion rate of the p-nitrophenol.
1.Qiu,B.；Fan,S.；Chen,Y.；Chen,J.；Wang,Y.；Wang,Y.；Liu,J.；Xiao,Z., Micromembrane absorber with deep-permeation nanostructure assembled by flowing synthesis. AlChE J.2021.
2.Qiu,B.；Fan,S.；Wang,Y.；Chen,J.；Xiao,Z.；Wang,Y.；Chen,Y.；Liu,J.；Qin, Y.；Jian,S.,Catalytic membrane micro-reactor with nano ZIF-8immobilized in membrane pores for enhanced Knoevenagel reaction of Benzaldehyde and Ethyl cyanoacetate.Chemical Engineering Journal 2020,400,125910.
3.Chen,Y.；Mai,Z.；Fan,S.；Wang,Y.；Qiu,B.；Wang,Y.；Chen,J.；Xiao,Z., Synergistic enhanced catalysis of micro-reactor with nano MnO2/ZIF-8immobilized in membrane pores by flowing synthesis.Journal of Membrane Science 2021,628.
4.Qin,Y.；Jian,S.；Bai,K.；Wang,Y.；Mai,Z.；Fan,S.；Qiu,B.；Chen,Y.；Wang,Y.； Xiao,Z.,Catalytic Membrane Reactor of Nano(Ag+ZIF-8)@Poly(tetrafluoroethylene)Built by Deep-Permeation Synthesis Fabrication.Industrial&Engineering Chemistry Research 2020,59 (21),9890-9899.
5.Li,H.；Wu,P.；Xiao,Y.；Shao,M.；Shen,Y.；Fan,Y.；Chen,H.；Xie,R.；Zhang, W.；Li,S.；Wu,J.；Fu,Y.；Zheng,B.；Zhang,W.；Huo,F.,Metal-Organic Frameworks as Metal Ion Precursors for the Synthesis of Nanocomposites for Lithium-Ion Batteries.Angew Chem Int Ed Engl 2020,59(12),4763-4769. 。
Claims (10)
1. A catalytic film with nano structure is prepared from the metallic coordination compound as precursor and features that the nano material with catalytic function is prepared from the metallic coordination compound as precursor.
2. According to claim 1, the nano-material having the catalytic function is uniformly supported in the pore channels of the membrane along the depth direction of the pore channels.
3. According to claim 2, the nano-material with catalytic function can be directly immobilized on the surface of the membrane pore channel, or the nano-catalytic material can be immobilized on the carrier in the membrane pore channel after the carrier of the nano-catalytic material is immobilized in the membrane pore channel.
4. According to claim 2, the nanomaterial with catalytic function is synthesized in situ in the membrane pore by a precursor fluid and immobilized in the membrane pore, including but not limited to diffusion of the precursor fluid into the membrane pore or flow of the precursor fluid through the membrane into the membrane pore.
5. The nano-material according to claim 1, wherein the nano-material includes, but is not limited to, elemental metal, metal sulfide, metal oxide, bimetal, etc.
6. According to claim 5, the nanomaterial has a size in the range of 1nm to 200 nm.
7. The porous base membrane according to claim 1, wherein the porous base membrane includes but is not limited to polymer membrane, metal membrane, ceramic membrane, etc., and the pore structure of the base membrane includes but is not limited to finger-shaped pores, mesh-shaped pores, etc.
8. According to claim 7, the pore size of the base film is in the range of 10nm to 10 μm.
9. According to claim 1, the nanostructured membrane is used in catalytic applications including, but not limited to, hydrogen production by alcohol reforming, organic dye degradation, and the like.
10. According to claim 9, in the catalytic reaction process, the catalytic membrane can be used as a monolithic catalyst for batch operation reactions and can also be used as a catalytic bed reaction fluid in a flow-through manner through the membrane.
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