CN115055162A - Preparation method of zeolite molecular sieve adsorption material - Google Patents
Preparation method of zeolite molecular sieve adsorption material Download PDFInfo
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- CN115055162A CN115055162A CN202210704292.1A CN202210704292A CN115055162A CN 115055162 A CN115055162 A CN 115055162A CN 202210704292 A CN202210704292 A CN 202210704292A CN 115055162 A CN115055162 A CN 115055162A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 97
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 92
- 239000010457 zeolite Substances 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 85
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 21
- 239000006255 coating slurry Substances 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000013329 compounding Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910021389 graphene Inorganic materials 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000004014 plasticizer Substances 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 150000007522 mineralic acids Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 239000012798 spherical particle Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000011363 dried mixture Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- TYRGSDXYMNTMML-UHFFFAOYSA-N propyl hydrogen sulfate Chemical compound CCCOS(O)(=O)=O TYRGSDXYMNTMML-UHFFFAOYSA-N 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims 4
- 239000002912 waste gas Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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Abstract
The invention discloses a preparation method of a zeolite molecular sieve adsorption material, which comprises the steps of preparing a hydrothermal-inorganic acid modified mixture, preparing a zeolite molecular sieve carrier, preparing catalyst coating slurry, coating the catalyst coating slurry, calcining the catalyst coating slurry at high temperature and the like. The invention has good adsorption capacity and catalytic reduction capacity and can realize better waste gas treatment effect. In addition, the catalyst coating slurry can be coated with SiO before being uniformly coated on the surface of the zeolite molecular sieve carrier 2 ‑TiO 2 ‑ZrO 2 And (4) compounding the sol.
Description
Technical Field
The invention relates to the technical field of waste gas adsorption materials, in particular to a preparation method of a zeolite molecular sieve adsorption material.
Background
Zeolite molecular sieves are hydrates of crystalline aluminosilicates, in which the molecular sieve crystals have many micropores of different diameters, and the molecular sieve is capable of adsorbing molecules smaller than its pore size to the inside, while excluding molecules larger than its pore size from its cavity, and thus performing a sieving function. Zeolite molecular sieves have excellent ion exchange adsorption properties and the like, and have been widely used in the fields of chemical industry and the like, such as industrial waste gas treatment. However, the adsorption of the existing zeolite molecular sieve still needs to be enhanced, and the waste gas treatment effect is not ideal.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a zeolite molecular sieve adsorbing material.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of a zeolite molecular sieve adsorption material comprises the following steps:
(1) putting a zeolite molecular sieve and graphene into deionized water with the mass being 10-20 times of that of the zeolite molecular sieve and the graphene, mixing the mixture and putting the mixture into an autoclave, uniformly stirring the mixture at the temperature of 150-200 ℃ while stirring, filtering and drying the mixture, putting the dried mixture into a ball mill, ball-milling the mixture for 60-70 minutes, adding the mixture and inorganic acid with the concentration of 10-12% into a reaction kettle, uniformly stirring the mixture at the temperature of 25-35 ℃ while stirring, subsequently filtering the mixture in the reaction kettle, washing the mixture with deionized water, and drying the mixture to obtain a hydrothermal-inorganic acid modified mixture;
(2) adding a binder and a plasticizer into the hydrothermal-inorganic acid modified mixture, processing the mixture into strip-shaped or spherical particles in a strip extrusion or rolling ball forming mode, and carrying out high-temperature heat treatment on the strip-shaped or spherical particles in protective gas at 400-550 ℃ for 60-120 minutes to obtain a zeolite molecular sieve carrier;
(3) weighing Cu/Al 2 O 3 Dissolving the mixed solution into deionized water, adding nitrate containing noble metals Pt and Pd into another deionized water for dilution, mixing the diluted two solutions with each other to obtain a mixed solution, then ball-milling the mixed solution by using a ball mill, and adjusting the pH value, the viscosity and the solid content of the mixed solution after ball milling to obtain catalyst coating slurry;
(4) uniformly coating the catalyst coating slurry on the surface of the zeolite molecular sieve carrier prepared in the step (2), and placing in the air for airing;
(5) and (3) putting the zeolite molecular sieve carrier which is dried in the air and has the catalyst coating formed on the surface into an oven for drying, transferring the zeolite molecular sieve carrier into a muffle furnace for high-temperature calcination at 800-850 ℃, and cooling to room temperature to obtain the zeolite molecular sieve adsorbing material.
Preferably, in the step (1), the zeolite molecular sieve has a diameter of 50 to 80 meshes, and the graphene has a diameter of 60 to 100 meshes.
Preferably, in the step (1), the solid-liquid mass ratio of the mixture obtained by drying and ball milling to the hydrochloric acid is 1: 5-8.
Preferably, in step (1), the inorganic acid is HCl or HNO 3 Or H 2 SO 4 。
Preferably, the binder is polyvinyl butyral, chitosan, epoxy resin or cellulose, and the content of the binder is 10-20% of the total mass of the zeolite molecular sieve and the graphene.
Preferably, the plasticizer is glycerol or ethyl methyl sulfuric acid, and the content of the plasticizer is 5-8% of the total mass of the zeolite molecular sieve and the graphene.
Preferably, the protective gas is nitrogen.
Preferably, in the step (3), the mixed solution is ball-milled by a ball mill until the fineness D90 is 8 to 20 um.
In the step (3), nitric acid or acetic acid can be adopted to adjust the pH value of the mixed solution to control the pH value between 3 and 5, and deionized water is added to adjust the solid content of the catalyst coating slurry to control the solid content between 40 and 50 percent.
Preferably, the Cu/Al 2 O 3 The preparation method comprises the following steps:
pouring aluminum oxide into a copper nitrate solution by adopting an isometric impregnation method, impregnating for a preset time, heating and drying in a water bath, drying and calcining to obtain Cu/Al 2 O 3 。
Preferably, before the catalyst coating slurry is uniformly coated on the surface of the zeolite molecular sieve support prepared in the step (2), the surface of the zeolite molecular sieve support is further coated with SiO 2 -TiO 2 -ZrO 2 Composite sol of said SiO 2 -TiO 2 -ZrO 2 The preparation method of the composite sol comprises the following steps:
nano TiO is mixed with 2 Powder and ZrO 2 Stirring the powder in deionized water, and then adding HNO with the concentration of 2-8% 3 To obtain nano TiO 2 -ZrO 2 Compounding sol;
mixing nano SiO 2 Adding the powder into nano TiO 2 -ZrO 2 Stirring the composite sol, and heating to 60-80 ℃ to obtain SiO 2 -TiO 2 -ZrO 2 And (4) compounding the sol.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention has good adsorption capacity and catalytic reduction capacity and can realize better waste gas treatment effect. Meanwhile, the invention can carry out hydrothermal-inorganic acid modification on the zeolite molecular sieve, and can dissolve Al ions in the hydrothermal modified zeolite molecular sieve out through the inorganic acid, so that fillers in silica tetrahedrons of the zeolite molecular sieve are reduced, the diameter of pores is increased, pollutants in waste gas can easily enter, and the adsorption capacity is greatly improved.
2. The graphene provided by the invention has the advantages of low cost, large specific surface area, good adsorption performance, high physical and chemical stability and low mass density, can be used for adsorbing waste gas, prolongs the service life of the zeolite molecular sieve carrier, and is beneficial to improving the adhesion performance of a catalyst coating.
3. The invention innovatively coats a catalyst coating, Cu/Al, on the surface of a zeolite molecular sieve carrier 2 O 3 Can be used as a load matrix of noble metals Pt and Pd, is uniformly loaded on a zeolite molecular sieve carrier, and can well play a role in catalyzing waste gas pollutants.
4. Before the catalyst coating slurry is uniformly coated on the surface of the zeolite molecular sieve carrier, the zeolite molecular sieve carrier can be coated with SiO 2 -TiO 2 -ZrO 2 The composite sol can enhance the connection strength between the zeolite molecular sieve carrier and the catalyst coating, so that the coating is not easy to fall off, and TiO 2 Can be deposited on graphene, and increases TiO 2 ZrO purifying effect on exhaust gas pollutants 2 Has catalytic effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a zeolite molecular sieve adsorption material comprises the following steps:
(1) putting a zeolite molecular sieve and graphene into deionized water with the mass being 10 times that of the zeolite molecular sieve and the graphene, mixing the mixture and putting the mixture into a high-pressure kettle, uniformly stirring the mixture at the temperature of 150 ℃ while stirring, filtering and drying the mixture, putting the dried mixture into a ball mill, ball-milling the mixture for 60 minutes, adding the mixture and inorganic acid with the concentration of 10% into a reaction kettle, uniformly stirring the mixture and the inorganic acid with the temperature of 25 ℃ while stirring, subsequently filtering the mixture in the reaction kettle, washing the mixture by using the deionized water, and drying the mixture to obtain a hydrothermal-inorganic acid modified mixture;
(2) adding a binder and a plasticizer into the hydrothermal-inorganic acid modified mixture, processing the mixture into strip-shaped or spherical particles in a strip extrusion or rolling ball forming mode, and carrying out high-temperature heat treatment on the strip-shaped or spherical particles at 400 ℃ in protective gas for 60 minutes to obtain a zeolite molecular sieve carrier;
(3) weighing Cu/Al 2 O 3 Dissolving the mixed solution into deionized water, adding nitrate containing noble metals Pt and Pd into the other deionized water for dilution, mixing the diluted two solutions with each other to obtain a mixed solution, then ball-milling the mixed solution by using a ball mill, and adjusting the pH value, viscosity and solid content of the mixed solution after ball milling to obtain catalyst coating slurry;
(4) uniformly coating the catalyst coating slurry on the surface of the zeolite molecular sieve carrier prepared in the step (2), and placing in the air for airing;
(5) and (3) putting the zeolite molecular sieve carrier which is dried and provided with the catalyst coating on the surface into an oven for drying, transferring into a muffle furnace for high-temperature calcination at 800 ℃, and cooling to room temperature to obtain the zeolite molecular sieve adsorbing material.
In the step (1), the diameter of the zeolite molecular sieve is 50 meshes, and the diameter of the graphene is 60 meshes.
In the step (1), the solid-liquid mass ratio of the mixture obtained by drying and ball milling to the hydrochloric acid is 1: 5.
In step (1), the inorganic acid is HCl.
The binder is polyvinyl butyral, and the content of the binder is 10% of the total mass of the zeolite molecular sieve and the graphene.
The plasticizer is glycerol, and the content of the plasticizer is 5% of the total mass of the zeolite molecular sieve and the graphene.
The protective gas is nitrogen.
In step (3), the mixed solution was ball-milled with a ball mill until fineness D90 was 8 um.
The Cu/Al 2 O 3 The preparation method comprises the following steps:
pouring aluminum oxide into a copper nitrate solution by adopting an isometric impregnation method, impregnating for a preset time, heating and drying in a water bath, drying and calcining to obtain Cu/Al 2 O 3 。
Example 2
A preparation method of a zeolite molecular sieve adsorption material comprises the following steps:
(1) putting a zeolite molecular sieve and graphene into deionized water 15 times of the mass of the zeolite molecular sieve and the graphene, mixing the mixture and putting the mixture into a high-pressure kettle, uniformly stirring the mixture at the temperature of 180 ℃ while stirring, filtering and drying the mixture, putting the dried mixture into a ball mill, ball-milling the mixture for 65 minutes, adding the mixture and inorganic acid with the concentration of 11% into a reaction kettle, uniformly stirring the mixture and the inorganic acid with the temperature of 30 ℃ while stirring, subsequently filtering the mixture in the reaction kettle, washing the mixture by using the deionized water, and drying the mixture to obtain a hydrothermal-inorganic acid modified mixture;
(2) adding a binder and a plasticizer into the hydrothermal-inorganic acid modified mixture, processing the mixture into strip-shaped or spherical particles in a strip extrusion or rolling ball forming mode, and carrying out high-temperature heat treatment on the strip-shaped or spherical particles at 500 ℃ in protective gas for 100 minutes to obtain a zeolite molecular sieve carrier;
(3)weighing Cu/Al 2 O 3 Dissolving the mixed solution into deionized water, adding nitrate containing noble metals Pt and Pd into another deionized water for dilution, mixing the diluted two solutions with each other to obtain a mixed solution, then ball-milling the mixed solution by using a ball mill, and adjusting the pH value, the viscosity and the solid content of the mixed solution after ball milling to obtain catalyst coating slurry;
(4) uniformly coating the catalyst coating slurry on the surface of the zeolite molecular sieve carrier prepared in the step (2), and placing in the air for airing;
(5) and putting the zeolite molecular sieve carrier which is dried in the air and has the catalyst coating formed on the surface into an oven for drying, transferring into a muffle furnace for high-temperature calcination at 820 ℃, and cooling to room temperature to obtain the zeolite molecular sieve adsorbing material.
In the step (1), the diameter of the zeolite molecular sieve is 70 meshes, and the diameter of the graphene is 80 meshes.
In the step (1), the solid-liquid mass ratio of the mixture obtained by drying and ball milling to hydrochloric acid is 1: 7.
In the step (1), the inorganic acid is HNO 3 。
The binder is epoxy resin, and the content of the binder is 15% of the total mass of the zeolite molecular sieve and the graphene.
The plasticizer is ethyl methyl sulfuric acid, and the content of the plasticizer is 7% of the total mass of the zeolite molecular sieve and the graphene.
The protective gas is nitrogen.
In step (3), the mixed solution was ball-milled with a ball mill until fineness D90 was 15 um.
The Cu/Al 2 O 3 The preparation method comprises the following steps:
pouring aluminum oxide into a copper nitrate solution by adopting an isometric impregnation method, impregnating for a preset time, heating and drying in a water bath, drying and calcining to obtain Cu/Al 2 O 3 。
Example 3
A preparation method of a zeolite molecular sieve adsorption material comprises the following steps:
(1) putting a zeolite molecular sieve and graphene into deionized water with the mass being 20 times that of the zeolite molecular sieve and the graphene, mixing the mixture and putting the mixture into a high-pressure kettle, uniformly stirring the mixture at the temperature of 200 ℃ while stirring, filtering and drying the mixture, putting the dried mixture into a ball mill, ball-milling the mixture for 70 minutes, adding the mixture and inorganic acid with the concentration of 12% into a reaction kettle, uniformly stirring the mixture and the inorganic acid with the temperature of 35 ℃ while stirring, subsequently filtering the mixture in the reaction kettle, washing the mixture by using the deionized water, and drying the mixture to obtain a hydrothermal-inorganic acid modified mixture;
(2) adding a binder and a plasticizer into the hydrothermal-inorganic acid modified mixture, processing the mixture into strip-shaped or spherical particles in a strip extrusion or rolling ball forming mode, and carrying out high-temperature heat treatment on the strip-shaped or spherical particles at 550 ℃ in protective gas for 120 minutes to obtain a zeolite molecular sieve carrier;
(3) weighing Cu/Al 2 O 3 Dissolving the mixed solution into deionized water, adding nitrate containing noble metals Pt and Pd into another deionized water for dilution, mixing the diluted two solutions with each other to obtain a mixed solution, then ball-milling the mixed solution by using a ball mill, and adjusting the pH value, the viscosity and the solid content of the mixed solution after ball milling to obtain catalyst coating slurry;
(4) uniformly coating the catalyst coating slurry on the surface of the zeolite molecular sieve carrier prepared in the step (2), and placing in the air for airing;
(5) and (3) putting the zeolite molecular sieve carrier which is dried in the air and has the catalyst coating formed on the surface into an oven for drying, transferring into a muffle furnace for high-temperature calcination at 850 ℃, and cooling to room temperature to obtain the zeolite molecular sieve adsorbing material.
In the step (1), the diameter of the zeolite molecular sieve is 80 meshes, and the diameter of the graphene is 100 meshes.
In the step (1), the solid-liquid mass ratio of the mixture obtained by drying and ball milling to the hydrochloric acid is 1: 8.
In the step (1), the inorganic acid is H 2 SO 4 。
The binder is cellulose, and the content of the binder is 20% of the total mass of the zeolite molecular sieve and the graphene.
The plasticizer is glycerol, and the content of the plasticizer is 8% of the total mass of the zeolite molecular sieve and the graphene.
The protective gas is nitrogen.
In step (3), the mixed solution was ball-milled with a ball mill until fineness D90 was 20 um.
The Cu/Al 2 O 3 The preparation method comprises the following steps:
pouring aluminum oxide into a copper nitrate solution by adopting an isometric impregnation method, impregnating for a preset time, heating and drying in a water bath, drying and calcining to obtain Cu/Al 2 O 3 。
Example 4
A preparation method of a zeolite molecular sieve adsorption material comprises the following steps:
(1) putting a zeolite molecular sieve and graphene into deionized water with the mass being 18 times that of the zeolite molecular sieve and the graphene, mixing the mixture and putting the mixture into a high-pressure kettle, uniformly stirring the mixture at the temperature of 160 ℃ while stirring, filtering and drying the mixture, putting the dried mixture into a ball mill, ball-milling the mixture for 70 minutes, adding the mixture and inorganic acid with the concentration of 12% into a reaction kettle, uniformly stirring the mixture and the inorganic acid with the temperature of 28 ℃ while stirring, subsequently filtering the mixture in the reaction kettle, washing the mixture by using the deionized water, and drying the mixture to obtain a hydrothermal-inorganic acid modified mixture;
(2) adding a binder and a plasticizer into the hydrothermal-inorganic acid modified mixture, processing the mixture into strip-shaped or spherical particles in a strip extrusion or rolling ball forming mode, and carrying out high-temperature heat treatment on the strip-shaped or spherical particles at 500 ℃ in protective gas for 120 minutes to obtain a zeolite molecular sieve carrier;
(3) weighing Cu/Al 2 O 3 Dissolving the mixed solution into deionized water, adding nitrate containing noble metals Pt and Pd into another deionized water for dilution, mixing the diluted two solutions with each other to obtain a mixed solution, then ball-milling the mixed solution by using a ball mill, and adjusting the pH value, the viscosity and the solid content of the mixed solution after ball milling to obtain catalyst coating slurry;
(4) coating the surface of a zeolite molecular sieve carrier with SiO 2 -TiO 2 -ZrO 2 Compounding sol;
(5) uniformly coating the catalyst coating slurry on the surface of the zeolite molecular sieve carrier prepared in the step (5), and placing in the air for airing;
(6) and (3) putting the zeolite molecular sieve carrier which is dried in the air and has the catalyst coating formed on the surface into an oven for drying, transferring into a muffle furnace for high-temperature calcination at 800 ℃, and cooling to room temperature to obtain the zeolite molecular sieve adsorbing material.
In the step (1), the diameter of the zeolite molecular sieve is 60 meshes, and the diameter of the graphene is 80 meshes.
In the step (1), the solid-liquid mass ratio of the mixture obtained by drying and ball milling to the hydrochloric acid is 1: 5-8.
In step (1), the inorganic acid is HCl.
The binder is chitosan, and the content of the binder is 15% of the total mass of the zeolite molecular sieve and the graphene.
The plasticizer is glycerol, and the content of the plasticizer is 6% of the total mass of the zeolite molecular sieve and the graphene.
The protective gas is nitrogen.
In step (3), the mixed solution was ball-milled with a ball mill until fineness D90 was 12 um.
The Cu/Al 2 O 3 The preparation method comprises the following steps:
pouring aluminum oxide into a copper nitrate solution by adopting an isometric impregnation method, impregnating for a preset time, heating and drying in a water bath, drying and calcining to obtain Cu/Al 2 O 3 。
The SiO 2 -TiO 2 -ZrO 2 The preparation method of the composite sol comprises the following steps:
mixing nanometer TiO 2 Powder and ZrO 2 Stirring the powder in deionized water, and then adding HNO with the concentration of 2-8% 3 To obtain nano TiO 2 -ZrO 2 Compounding sol;
mixing nano SiO 2 Adding the powder into nano TiO 2 -ZrO 2 Stirring in composite solStirring and heating to 60-80 ℃ to obtain SiO 2 -TiO 2 -ZrO 2 And (4) compounding the sol.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the zeolite molecular sieve adsorption material is characterized by comprising the following steps of:
(1) putting a zeolite molecular sieve and graphene into deionized water with the mass being 10-20 times of that of the zeolite molecular sieve and the graphene, mixing the mixture and putting the mixture into an autoclave, uniformly stirring the mixture at the temperature of 150-200 ℃ while stirring, filtering and drying the mixture, putting the dried mixture into a ball mill, ball-milling the mixture for 60-70 minutes, adding the mixture and inorganic acid with the concentration of 10-12% into a reaction kettle, uniformly stirring the mixture at the temperature of 25-35 ℃ while stirring, subsequently filtering the mixture in the reaction kettle, washing the mixture with deionized water, and drying the mixture to obtain a hydrothermal-inorganic acid modified mixture;
(2) adding a binder and a plasticizer into the hydrothermal-inorganic acid modified mixture, processing the mixture into strip-shaped or spherical particles in a strip extrusion or rolling ball forming mode, and carrying out high-temperature heat treatment on the strip-shaped or spherical particles in protective gas at 400-550 ℃ for 60-120 minutes to obtain a zeolite molecular sieve carrier;
(3) weighing Cu/Al 2 O 3 Dissolving the mixed solution into deionized water, adding nitrate containing noble metals Pt and Pd into another deionized water for dilution, mixing the diluted two solutions with each other to obtain a mixed solution, then ball-milling the mixed solution by using a ball mill, and adjusting the pH value, the viscosity and the solid content of the mixed solution after ball milling to obtain catalyst coating slurry;
(4) uniformly coating the catalyst coating slurry on the surface of the zeolite molecular sieve carrier prepared in the step (2), and placing in the air for airing;
(5) and (3) putting the zeolite molecular sieve carrier which is dried in the air and has the catalyst coating formed on the surface into an oven for drying, transferring the zeolite molecular sieve carrier into a muffle furnace for high-temperature calcination at 800-850 ℃, and cooling to room temperature to obtain the zeolite molecular sieve adsorbing material.
2. The preparation method of a zeolite molecular sieve adsorbing material according to claim 1, wherein in the step (1), the diameter of the zeolite molecular sieve is 50-80 meshes, and the diameter of the graphene is 60-100 meshes.
3. The preparation method of a zeolite molecular sieve adsorbing material according to claim 1, wherein in the step (1), the solid-liquid mass ratio of the mixture obtained by drying and ball milling to hydrochloric acid is 1: 5-8.
4. A method for preparing a zeolite molecular sieve adsorbent material according to claim 1, wherein in step (1), said inorganic acid is HCl, HNO 3 Or H 2 SO 4 。
5. The preparation method of a zeolite molecular sieve adsorbing material according to claim 1, wherein the binder is polyvinyl butyral, chitosan, epoxy resin or cellulose, and the content of the binder is 10-20% of the total mass of the zeolite molecular sieve and graphene.
6. The preparation method of a zeolite molecular sieve adsorbing material according to claim 1, wherein the plasticizer is glycerol or ethylmethyl sulfuric acid, and the content of the plasticizer is 5-8% of the total mass of the zeolite molecular sieve and graphene.
7. A method of preparing a zeolitic molecular sieve adsorbent material according to claim 1, characterized in that said protective gas is nitrogen.
8. A preparation method of a zeolite molecular sieve adsorbing material according to claim 1, wherein in the step (3), the mixed solution is ball-milled by a ball mill until the fineness D90 is 8-20 um.
9. A method for preparing a zeolitic molecular sieve adsorbent material according to claim 1, characterized in that said Cu/Al is 2 O 3 The preparation method comprises the following steps:
pouring aluminum oxide into a copper nitrate solution by adopting an isometric impregnation method, impregnating for a preset time, heating and drying in a water bath, drying and calcining to obtain Cu/Al 2 O 3 。
10. The method for preparing a zeolite molecular sieve adsorbent material according to claim 1, wherein the surface of the zeolite molecular sieve support prepared in step (2) is further coated with SiO before the catalyst coating slurry is uniformly coated on the surface of the zeolite molecular sieve support 2 -TiO 2 -ZrO 2 Composite sol of said SiO 2 -TiO 2 -ZrO 2 The preparation method of the composite sol comprises the following steps:
mixing nanometer TiO 2 Powder and ZrO 2 Stirring the powder in deionized water, and then adding HNO with the concentration of 2-8% 3 To obtain nano TiO 2 -ZrO 2 Compounding sol;
mixing nano SiO 2 Adding the powder into nano TiO 2 -ZrO 2 Stirring the composite sol, and heating to 60-80 ℃ to obtain SiO 2 -TiO 2 -ZrO 2 And (4) compounding the sol.
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