CN113198474A - Paper-like gradient porous microfiber composite Co3O4Catalyst and preparation method and application of MOFs template thereof - Google Patents
Paper-like gradient porous microfiber composite Co3O4Catalyst and preparation method and application of MOFs template thereof Download PDFInfo
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- 239000003658 microfiber Substances 0.000 title claims abstract description 117
- 229920001410 Microfiber Polymers 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 239000000835 fiber Substances 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 40
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- 238000001354 calcination Methods 0.000 claims abstract description 26
- 239000012528 membrane Substances 0.000 claims abstract description 23
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000034655 secondary growth Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 24
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
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- 239000013110 organic ligand Substances 0.000 claims description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
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- 238000007084 catalytic combustion reaction Methods 0.000 claims description 7
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
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- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 238000003915 air pollution Methods 0.000 description 2
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- DAYYOITXWWUZCV-UHFFFAOYSA-L cobalt(2+);sulfate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O DAYYOITXWWUZCV-UHFFFAOYSA-L 0.000 description 2
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- 239000013114 Co-MOF-74 Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002514 Co–Co Inorganic materials 0.000 description 1
- 241001397809 Hakea leucoptera Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
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Abstract
The invention discloses a paper-like gradient porous microfiber composite Co3O4A catalyst and a preparation method and application of MOFs template thereof. The method comprises the following steps: preparing a paper-shaped sintered microfiber carrier; pretreating a paper-shaped sintered microfiber carrier by using 3-aminopropyltriethoxysilane to obtain a pretreated paper-shaped sintered microfiber carrier; adopting a seed crystal secondary growth method to grow an MOFs film on the surface of the pretreated paper-shaped sintered microfiber carrier; calcining the microfiber composite MOFs membrane material in air atmosphere to grow on the surface of the paper-like sintered microfiber carrierThe MOFs film is converted into porous Co3O4. The invention takes microfiber composite MOFs membrane material as a template to form porous Co on the surface of a paper-like sintered fiber carrier3O4The catalyst has high and adjustable porosity and high mechanical strength, and can be filled in a fixed bed to strengthen mass and heat transfer and reduce bed pressure drop; the paper-like gradient microfiber composite porous metal oxide material has a certain application prospect in the field of catalysis.
Description
Technical Field
The invention belongs to the technical field of preparation of a microfiber composite material and an environment functional material, and relates to a paper-like gradient porous microfiber composite Co3O4A catalyst and a preparation method and application of MOFs template thereof.
Background
Volatile Organic Compounds (VOCs) are main substances causing air pollution, and rapid development of industrialization and urbanization leads to rapid increase of VOCs discharged into the air, so that a series of increasingly worsened environmental pollution problems follow, ecological balance is destroyed to a great extent, sustainable development of the society is restricted, and human health is threatened. The discharge of a large amount of waste gas containing VOCs components brings considerable negative effects to the life of people, so that the development of technologies for effectively treating the discharge of VOCs is not slow. The catalytic combustion technology is the most widely and effectively applied technical means for controlling the discharge of VOCs at present, and the most key in the technology is to develop a catalyst with larger surface area, more active sites, higher stability and easy regeneration. Compared with the traditional powder particle catalyst, the metal oxide catalyst prepared by taking the metal organic framework compound as the sacrificial template has larger specific surface area and abundant pore channel structures, and further shows higher catalytic activity.
Metal organic framework compounds (MOFs) have been popular research materials, and have an ultra-large specific surface area, a regularly adjustable pore structure, abundant active sites and the like, so that the metal organic framework compounds are widely applied to the fields of gas adsorption separation, catalysis, sensing and the like. In recent years, many researchers use MOFs as sacrificial templates to prepare porous carbon materials/metal oxides through pyrolysis, and the catalyst prepared by the method is applied to the field of catalytic combustion of VOCs. Okinlevel (publication No. CN 111744521A) et al to prepare Co-MOF-74 particles by centrifugation after hydrothermal reaction with a precipitant added to waterDrying, calcining and tabletting to obtain Co with a certain mesh number3O4The mechanical strength of the catalyst is not enough, and the catalyst has large bed pressure drop and lower mass transfer efficiency compared with a microfiber composite material when being filled in a fixed bed for catalytic combustion of VOCs gas.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a paper-like gradient porous microfiber composite Co3O4A catalyst and a preparation method and application of MOFs template thereof.
Aiming at the problems of low active component loading capacity, uneven distribution, agglomeration and the like of a supported catalyst and the defects of difficult cutting of a carrier, low mass and heat transfer efficiency and the like, the invention provides a paper-like microfiber composite porous Co3O4The gradient porous microfiber composite material obtained by the preparation method of the material has good catalytic combustion performance on VOCs so as to realize effective control on VOCs gas emission and enable the emitted waste gas to meet the environmental protection standard.
In order to realize the purpose, the invention adopts paper-shaped sintered micro-fiber as a carrier, a MOFs film is grown on the surface of the micro-fiber on the carrier modified by pretreatment by adopting a crystal seed secondary growth method, and then the paper-shaped gradient porous micro-fiber composite Co micro-fiber composite MOFs film material is prepared by pyrolyzing the micro-fiber composite MOFs film material at high temperature in air atmosphere3O4A catalyst.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a paper-like gradient porous microfiber composite Co3O4The preparation method of the MOFs template of the catalyst comprises the following steps: preparing a paper-like sintered fiber carrier, pretreating the paper-like sintered fiber carrier (pretreating the paper-like sintered fiber carrier by adopting 3-aminopropyltriethoxysilane to obtain the pretreated paper-like sintered fiber carrier), growing and depositing an MOFs (metal-organic frameworks) film on a seed crystal layer on the surface of the pretreated paper-like sintered fiber carrier and further growing the MOFs film into a film, and compounding the paper-like gradient porous microfiber with Co3O4The catalyst is prepared by high-temperature calcination of a paper-shaped sintered microfiber composite MOFs membrane material serving as a sacrificial template.
The invention provides a paper-like gradient porous microfiber composite Co3O4The preparation method of the MOFs template of the catalyst specifically comprises the following steps:
(1) preparing a paper-like sintered microfiber carrier: adding an adhesive and microfibers into water, uniformly mixing to obtain slurry, making into sheets, drying to obtain a carrier precursor, heating the carrier precursor in an inert atmosphere, and sintering to obtain a paper-like sintered fiber carrier (a paper-like sintered microfiber carrier with a macroporous three-dimensional network structure);
(2) pretreatment of the paper-like sintered microfiber carrier: soaking the paper-like sintered fiber carrier in the step (1) in a solution of 3-Aminopropyltriethoxysilane (APTES), heating to perform a solvothermal reaction, cooling to room temperature, taking out the paper-like sintered fiber carrier, cleaning, and drying to obtain a modified paper-like sintered fiber carrier;
(3) preparing a microfiber composite MOFs film material: soaking the paper-shaped sintered fiber carrier modified in the step (2) in a crystal seed growth solution at normal temperature and normal pressure to enable MOFs crystal seeds to form and grow on the surface of the carrier, taking out the MOFs crystal seeds, and drying to obtain the paper-shaped sintered microfiber carrier with the MOFs crystal seeds deposited; soaking the paper-shaped sintered microfiber carrier with the deposited MOFs crystal seeds in secondary growth liquid, heating to perform solvothermal reaction, further growing the MOFs crystal seeds on the surface of the carrier into an MOFs membrane under the solvothermal condition, taking out, and drying to obtain a microfiber composite MOFs membrane material;
(4) placing the microfiber composite MOFs membrane material obtained in the step (3) in a muffle furnace, heating the membrane material for calcination, and naturally cooling the membrane material to room temperature to obtain the papery gradient porous microfiber composite Co3O4A catalyst.
Further, the adhesive in the step (1) is more than one of cellulose, organic acid resin and thermosetting resin; the micro fiber is more than one of ceramic fiber, glass fiber and metal fiber.
Further, the diameter of the micro fiber in the step (1) is 4-10 μm.
Further, the mass ratio of the adhesive to the microfiber in the step (1) is 1: (1-8). The diameter of the microfibers is in the micron range.
Preferably, the metal fiber is any one of copper, cobalt, nickel, zinc, silver, vanadium, iron, stainless steel and magnesium or alloy fibers formed by the substances.
Preferably, the adhesive is more than one of cellulose and thermosetting resin; the cellulose is needle-leaved wood fiber; the thermosetting resin is more than one of epoxy resin.
Further, the mass ratio of the microfibers to water in the step (1) is 200-: 1 g/ml.
Further, the drying temperature in the step (1) is 110-150 ℃.
Further, the drying time of the step (1) is 0.5-2 h.
Further, the temperature of the sintering treatment in the step (1) is 600-,
further, the time of the sintering treatment in the step (1) is 10-20 min;
further, the inert atmosphere in the step (1) is nitrogen, argon or helium.
Further, in the solution of 3-aminopropyltriethoxysilane in step (2), the concentration of 3-aminopropyltriethoxysilane is 1-5 wt%;
further, the temperature of the solvothermal reaction in the step (2) is 50-150 ℃.
Further, the solvothermal reaction time of the step (2) is 6-24 h.
Preferably, the temperature of the solvothermal reaction in the step (2) is 60-120 ℃.
Preferably, the solvent of the solution of 3-aminopropyltriethoxysilane in step (2) is an organic solvent such as ethanol and methanol.
Further, the seed crystal growth solution in the step (3) is a mixed solution formed by uniformly mixing metal ions, organic ligands and water;
further, the metal ion is Co2+The organic ligand is 2-methylimidazole;
further, the molar ratio of the metal ions to the organic ligands is 1: (40-80);
further, the mass ratio of the metal ions to water is 1: (1000-2000);
further, the modified paper-like sintered fiber carrier in the step (3) is soaked in the seed crystal growth solution for 4-12 h.
Preferably, in the seed crystal growth solution in the step (3), the metal ions can be generated by adding a metal cobalt salt into water, wherein the metal cobalt salt is cobalt nitrate hexahydrate, cobalt chloride hexahydrate or cobalt sulfate hexahydrate.
Preferably, in the seed crystal growth solution in the step (3), water is deionized water.
Preferably, the step (3) of soaking the modified paper-like sintered fiber carrier in a seed crystal growth solution comprises: firstly, soaking the modified paper-shaped sintered fiber carrier in an organic ligand solution, then dropwise adding a metal ion solution into the organic ligand solution, and reacting at normal temperature and normal pressure to form an MOFs (metal-organic frameworks) seed crystal layer on the surface of the paper-shaped sintered fiber carrier.
Further, the secondary growth liquid in the step (3) is a mixed solution formed by uniformly mixing metal ions, organic ligands and an organic solvent;
further, the metal ion is Co2+The organic ligand is 2-methylimidazole;
further, the molar ratio of the metal ions to the organic ligands is 1: (4-20);
further, the mass ratio of the metal ions to the organic solvent is 1: (1000-2000);
further, the organic solvent is an ethanol solvent or a methanol solvent;
further, the temperature of the solvothermal reaction in the step (3) is 50-150 ℃, and the solvothermal reaction time is 12-36 h.
Preferably, the temperature of the solvothermal reaction in the step (3) is 60-120 ℃.
Preferably, in the step (3), the paper-like sintered microfiber carrier on which the MOFs seed crystals are deposited is vertically immersed in a secondary growth solution.
Preferably, in the secondary growth liquid in the step (3), the metal ions may be generated by adding a metal cobalt salt into an organic solvent, wherein the metal cobalt salt is cobalt nitrate hexahydrate, cobalt chloride hexahydrate or cobalt sulfate hexahydrate.
Further preferably, in the secondary growth liquid in the step (3), the metal ions may be generated by adding a metal cobalt salt into an organic solvent, wherein the metal cobalt salt is cobalt chloride hexahydrate.
Further, the temperature of the calcination treatment in the step (4) is 300-550 ℃,
further, the atmosphere of the calcination treatment in the step (4) is an air atmosphere;
further, the time of the calcination treatment in the step (4) is 1-4 h;
further, the temperature rising rate of the step (4) is 1-5 ℃/min.
The invention provides a paper-like gradient porous microfiber composite Co prepared by the MOFs template preparation method3O4A catalyst.
The invention provides a paper-like gradient porous microfiber composite Co3O4Catalyst (paper-like gradient porous microfiber composite Co prepared by taking MOFs membrane as sacrificial template3O4Catalyst) in catalytic combustion of VOCs (applied in the field of air pollution abatement).
The invention takes paper-shaped sintered microfiber as a carrier, adopts a carrier modification and seed crystal secondary growth method to uniformly grow a compact continuous MOFs membrane on the surface of the fiber, then takes the paper-shaped sintered microfiber composite MOFs membrane material as a sacrificial template, and takes porous Co as a sacrificial template3O4The structured supported catalyst is obtained by uniformly loading polyhedrons on the surface of a micron-sized fiber carrier, so that the advantages of MOFs material and a paper-shaped sintered microfiber carrier are effectively combined, the obtained catalyst has the advantages of adjustable porosity, free folding or cutting, high mass and heat transfer efficiency and large specific surface area (5-25 m)2The catalyst has rich pore structure and finally shows good performance of catalyzing, burning and degrading VOCs, and the T of isopropanol90About 270 to 320 ℃.
The invention uses micro-fiber composite MOFs membrane material as a template to sinter fibers in a paper shapeFormation of porous Co on the surface of the support3O4The catalyst has high and adjustable porosity and high mechanical strength, and can be filled in a fixed bed to strengthen mass and heat transfer and reduce bed pressure drop; the paper-like gradient microfiber composite porous metal oxide material has a certain application prospect in the field of catalysis.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method provided by the invention, the MOFs membrane is loaded on the surface of the paper-shaped sintered stainless steel carrier, the paper-shaped sintered microfiber is taken as the carrier, and compared with a powder particle catalyst, the microfiber composite material can be folded or cut into any shape according to the requirement, and meanwhile, the problem of uneven packing density cannot occur when the material is filled in a fixed bed reactor.
(2) The invention provides a paper-like gradient porous microfiber composite Co3O4The catalyst is filled in the fixed bed reactor, and compared with the fixed bed reactor filled with the traditional powder particle catalyst, the catalyst can more effectively degrade the mass transfer and heat transfer resistance, reduce the pressure drop of the bed layer and improve the utilization rate of the bed layer.
(3) The invention provides a paper-like gradient porous microfiber composite Co3O4Compared with the structured catalysts prepared by an impregnation method, a chemical vapor deposition method and the like, the catalyst has larger specific surface area, rich pore channel structures and more active sites, and shows better catalytic combustion performance of VOCs.
Drawings
FIG. 1a is an SEM image of a microfiber composite MOFs film material prepared in step (3) of example 1;
FIG. 1b is an SEM image of the microfiber composite MOFs film material prepared in step (3) of example 4;
FIG. 1c is the thermal stability curves of the microfiber composite MOFs film material prepared in step (3) of example 1 and the microfiber composite MOFs film material prepared in step (3) of example 4;
FIG. 2a shows the paper-like gradient porous microfiber composite Co prepared in example 13O4SEM image of catalyst;
FIG. 2b shows the paper-like gradient porous microfiber composite Co prepared in example 23O4SEM image of catalyst;
FIG. 2c shows the paper-like gradient porous microfiber composite Co prepared in example 33O4SEM image of catalyst;
FIG. 2d shows the paper-like gradient porous microfiber composite Co prepared in example 43O4SEM image of catalyst;
FIG. 3 shows the MOFs membrane material prepared by the step (3) of example 1 and the Co-Co composite material prepared by the gradient porous microfiber materials of examples 1, 2 and 33O4XRD spectrum of catalyst.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Paper-like gradient porous microfiber composite Co3O4The preparation method of the MOFs template of the catalyst comprises the following steps:
(1) preparation of a paper-like sintered stainless steel fiber carrier: adding 2g of adhesive (needle wood fiber is selected) and 8g of microfiber (stainless steel fiber is selected, the fiber diameter is 6.5 microns) into 3000ml of water, uniformly mixing to obtain slurry, using a sheet machine to sheet the slurry, filtering to form a wet filter cake, pressing the filter cake, drying at 105 ℃ for 2h to obtain a carrier precursor, heating the carrier precursor under a nitrogen atmosphere (the flow rate of nitrogen is 2000sccm) to perform sintering treatment, wherein the sintering treatment temperature is 1050 ℃, the sintering treatment time is 60min, and a paper-shaped sintered fiber carrier (the thickness is 2mm and the label is PSSF) is obtained;
(2) modification of a paper-like sintered stainless steel fiber carrier: cutting the paper-shaped sintered fiber carrier obtained in the step (1) into a rectangle of 4cm x 5cm, ultrasonically washing the paper-shaped sintered fiber carrier with deionized water and absolute ethyl alcohol for 3 times, 5min each time, drying to obtain clean PSSF, vertically soaking the clean PSSF in a solution (the concentration is 2 wt% and the solvent is absolute ethyl alcohol) of 3-aminopropyltriethoxysilane, heating to perform a solvothermal reaction (the reaction is performed for 24 hours at 65 ℃), naturally cooling to room temperature, taking out the paper-shaped sintered fiber carrier, washing the paper-shaped sintered fiber carrier for 3 times with the absolute ethyl alcohol, and naturally drying for 24 hours at the room temperature to obtain a modified paper-shaped sintered fiber carrier;
(3) the ZIF-67 film is coated and grown on the surface of the modified stainless steel fiber carrier:
soaking the modified paper-shaped sintered fiber carrier obtained in the step (2) in seed crystal growth liquid (soaking time is 12 hours), wherein the seed crystal growth liquid is prepared by uniformly mixing 0.6568g of 2-methylimidazole, 0.291g of cobalt nitrate hexahydrate and 45mL of deionized water, ZIF-67 seed crystals grow and deposit on the surface of the paper-shaped sintered fiber carrier, taking out, washing three times with absolute ethyl alcohol, removing small particles which are not firmly combined with the stainless steel fiber carrier, and performing vacuum drying at 65 ℃ for 24 hours to obtain the paper-shaped sintered microfiber carrier on which the MOFs seed crystals are deposited;
vertically soaking the paper-shaped sintered microfiber carrier on which the MOFs crystal seeds are deposited in secondary growth solution, wherein the secondary growth solution is a solution obtained by uniformly mixing 1.642g of 2-methylimidazole, 0.281g of cobalt chloride hexahydrate and 80ml of methanol solvent, heating to perform solvothermal reaction (reacting and growing for 24 hours at 100 ℃), naturally cooling, taking out, washing for three times with methanol, and performing vacuum drying for 24 hours at 65 ℃ to obtain a microfiber composite MOFs membrane material;
(4) porous Co3O4Loading on a stainless steel fiber carrier:
placing the microfiber composite MOFs membrane material obtained in the step (3) in a muffle furnace, heating in air atmosphere at a heating rate of 5 ℃/min, at a calcination temperature of 350 ℃, for a calcination time of 2h, and cooling to room temperature to obtain the paper-like gradient porous microfiber composite Co3O4A catalyst.
Example 2
The same procedure as in example 1 was repeated except that the calcination temperature of the paper-like gradient microfiber composite ZIF-67 membrane material (step (4) of example 1) was changedThe calcination treatment) is changed into 450 ℃, and the paper-like gradient porous microfiber composite Co is obtained3O4A catalyst.
Example 3
The procedure of example 1 was repeated except that the calcination temperature of the paper-like gradient microfiber composite ZIF-67 membrane material (calcination treatment described in step (4) of example 1) was changed to 550 ℃ to obtain a paper-like gradient porous microfiber composite Co3O4A catalyst.
Example 4
Except for the following differences, the method is the same as that in example 1 except that the solvothermal reaction time of the secondary growth (the solvothermal reaction time in the step (3) in example 1) is shortened to 12 hours, and the paper-like gradient porous microfiber composite Co is obtained3O4A catalyst.
Example 5
Paper-like gradient porous microfiber composite Co obtained in examples 1, 2, 3 and 43O4Cutting the catalyst into round pieces (diameter of 1cm) respectively to obtain samples to be tested, weighing 0.3g of the samples to be tested, uniformly filling the samples to be tested in a stainless steel tube, fixing, introducing air containing 500ppm isopropanol at an airspeed of 10000h-1Under the operating conditions, the catalytic activity was evaluated at 160-300 ℃. The samples to be detected are respectively the paper-like gradient porous microfiber composite Co obtained in examples 1, 2, 3 and 43O4Catalyst (disk state).
In the catalytic reaction process, detecting the concentration change of the isopropanol by using Agilent 7890A gas chromatography to calculate the degradation conversion rate of the isopropanol, wherein the calculation formula is
T50And T90The reaction temperatures for 50% and 90% conversion of isopropanol, respectively, are summarized in table 1.
TABLE 1
The scanning electron microscope image of the paper-like gradient micro-fiber composite ZIF-67 film material (the micro-fiber composite MOFs film material prepared in step (3) of example 1 is shown in fig. 1a, the scanning electron microscope image of the paper-like gradient micro-fiber composite ZIF-67 film material prepared in example 4 (the micro-fiber composite MOFs film material prepared in step (3) of example 4) is shown in fig. 1b, and the thermal stability thereof is shown in fig. 1 c. It can be seen from FIG. 1c that varying the secondary growth time can vary the loading of the ZIF-67 film.
Example 1 paper-like gradient porous microfiber composite Co prepared by calcination at 350 ℃3O4The scanning electron microscope image of the catalyst is shown in FIG. 2 a; example 2 paper-like gradient porous microfiber composite Co prepared by calcination at 450 deg.C3O4The scanning electron microscope image of the catalyst is shown in FIG. 2 b; example 3 paper-like gradient porous microfiber composite Co prepared by calcination at 550 deg.C3O4The scanning electron microscope image of the catalyst is shown in FIG. 2 c; example 4 paper-like gradient porous microfiber composite Co prepared by calcination at 350 ℃3O4The scanning electron micrograph of the catalyst is shown in FIG. 2 d. As can be seen from FIGS. 2a, 2b and 2c, as the temperature of the calcined ZIF-67 film material increases, Co is added to the composite porous paper-like gradient micro-fiber3O4The difference between the surface micro-morphology of the catalyst and the surface micro-morphology of the ZIF-67 membrane material is larger and larger, and the morphology of the ZIF-67 crystal is gradually lost by the load on the surface of the fiber. From FIG. 2d, it can be seen that the composite Co with the shape gradient porous microfiber is obtained by shortening the secondary growth time3O4The amount of the catalyst loaded with the active component on the surface of the fiber is relatively reduced.
For the paper-like gradient microfiber composite ZIF-67 membrane material prepared in example 1 (i.e., the microfiber composite MOFs membrane material prepared in step (3) of example 1) and the paper-like gradient porous microfiber composite Co prepared in example 1 by calcining at 350 ℃3O4Catalyst, example 2 paper-like gradient porous microfiber composite Co prepared by calcination at 450 ℃3O4Catalyst, example 3 paper-like gradient porous microfiber composite Co prepared by calcination at 550 ℃3O4XRD characterization of the catalyst was performed, and the results are shown in FIG. 3, from which FIG. 3 showsTo see that the paper-shaped gradient porous microfiber is compounded with Co3O4The catalyst has a characteristic peak between 30 and 70 degrees, and the large response value indicates that Co is3O4Successfully loaded on the surface of the stainless steel metal fiber. ZIF-67/PSSF in FIG. 3 represents the microfiber composite MOFs film material prepared in step (3) of example 1, and example 1 in FIG. 3 represents the paper-like gradient porous microfiber composite Co prepared by calcining example 1 at 350 ℃3O4Catalyst, example 2 in FIG. 3 shows the paper-like gradient porous microfiber composite Co prepared by calcining example 2 at 450 ℃3O4Catalyst, example 3 in FIG. 3 shows the paper-like gradient porous microfiber composite Co prepared by calcining example 3 at 550 ℃3O4A catalyst.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. Paper-like gradient porous microfiber composite Co3O4The preparation method of the MOFs template of the catalyst is characterized by comprising the following steps:
(1) adding an adhesive and microfibers into water, uniformly mixing to obtain slurry, making into sheets, drying to obtain a carrier precursor, heating the carrier precursor in an inert atmosphere, and sintering to obtain a paper-like sintered fiber carrier;
(2) soaking the paper-like sintered fiber carrier in the step (1) in a solution of 3-aminopropyltriethoxysilane, heating to perform a solvothermal reaction, cooling to room temperature, taking out the paper-like sintered fiber carrier, cleaning, and drying to obtain a modified paper-like sintered fiber carrier;
(3) soaking the modified paper-shaped sintered fiber carrier in the step (2) in a seed crystal growth solution, taking out, and drying to obtain a paper-shaped sintered microfiber carrier for depositing MOFs seed crystals; soaking the paper-shaped sintered microfiber carrier with the deposited MOFs crystal seeds in a secondary growth solution, heating to perform solvothermal reaction, taking out, and drying to obtain a microfiber composite MOFs membrane material;
(4) heating the microfiber composite MOFs membrane material obtained in the step (3) for calcination, and cooling to room temperature to obtain the paper-like gradient porous microfiber composite Co3O4A catalyst.
2. The paper-like gradient porous microfiber composite Co of claim 13O4The MOFs template preparation method of the catalyst is characterized in that the adhesive in the step (1) is more than one of cellulose and thermosetting resin; the micro fiber is more than one of ceramic fiber, glass fiber and metal fiber, and the diameter of the micro fiber is 4-10 μm; the mass ratio of the adhesive to the microfibers is 1: (1-8); the mass ratio of the microfibers to water is 200-400: 1 g/ml.
3. The paper-like gradient porous microfiber composite Co of claim 13O4The preparation method of the MOFs template of the catalyst is characterized in that the drying temperature in the step (1) is 110-150 ℃, and the drying time is 0.5-2 h.
4. The paper-like gradient porous microfiber composite Co of claim 13O4The MOFs template preparation method of the catalyst is characterized in that the sintering treatment temperature in the step (1) is 600-1400 ℃, and the sintering treatment time is 10-20 min; the inert atmosphere is nitrogen, argon or helium.
5. The paper-like gradient porous microfiber composite Co of claim 13O4The MOFs template preparation method of the catalyst is characterized in that in the solution of the 3-aminopropyl triethoxysilane in the step (2), the concentration of the 3-aminopropyl triethoxysilane is 1-5 wt%; the temperature of the solvothermal reaction is 50-150 ℃, and the solvothermal reaction time is 6-24 h.
6. The paper-like gradient porous microfiber composite Co of claim 13O4MOFs template preparation method of catalystThe method is characterized in that the seed crystal growth solution in the step (3) is a mixed solution formed by uniformly mixing metal ions, organic ligands and water; the metal ion is Co2+The organic ligand is 2-methylimidazole; the molar ratio of the metal ions to the organic ligands is 1: (40-80); the mass ratio of the metal ions to the water is 1: (1000-2000); and (4) soaking the modified paper-shaped sintered fiber carrier in the seed crystal growth solution for 4-12 h.
7. The paper-like gradient porous microfiber composite Co of claim 13O4The preparation method of the MOFs template of the catalyst is characterized in that the secondary growth liquid in the step (3) is a mixed solution formed by uniformly mixing metal ions, organic ligands and an organic solvent; the metal ion is Co2+The organic ligand is 2-methylimidazole; the molar ratio of the metal ions to the organic ligands is 1: (4-20); the mass ratio of the metal ions to the organic solvent is 1: (1000-2000); the organic solvent is an ethanol solvent or a methanol solvent; the temperature of the solvothermal reaction in the step (3) is 50-150 ℃, and the solvothermal reaction time is 12-36 h.
8. The paper-like gradient porous microfiber composite Co of claim 13O4The MOFs template preparation method of the catalyst is characterized in that the calcination treatment temperature in the step (4) is 300-550 ℃, and the calcination treatment atmosphere is air atmosphere; the time of the calcination treatment is 1-4 h; the rate of temperature rise is 1-5 ℃/min.
9. Paper-like gradient porous microfiber composite Co prepared by the MOFs template preparation method of any one of claims 1 to 83O4A catalyst.
10. The paper-like gradient porous microfiber composite Co of claim 93O4Use of a catalyst in the catalytic combustion of VOCs.
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