CN105597839A - Preparation method of molecular sieve film cladding type catalyst - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 title abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000005253 cladding Methods 0.000 title abstract 3
- 238000009987 spinning Methods 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012528 membrane Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000012510 hollow fiber Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 8
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 45
- 239000013078 crystal Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 238000001802 infusion Methods 0.000 claims description 6
- 239000002121 nanofiber Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- -1 tetramethyl oxyammonia Chemical compound 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 9
- 239000000376 reactant Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 4
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000000926 separation method Methods 0.000 abstract 2
- 238000007873 sieving Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 239000001273 butane Substances 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B01J35/59—
-
- 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
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
Abstract
The invention discloses a preparation method of a molecular sieve film cladding type catalyst, and belongs to the field of catalysts. According to the preparation method, polyether sulfone resin and 1-methyl-2-pyrrolidinone are firstly used as raw materials; nanometer titanium dioxide powder is added in batches to obtain a spinning solution; the spinning solution is put into a high-voltage electrostatic spinning device to form a silicon dioxide hollow fiber material; the prepared catalyst is prepared into coating liquid; the coating liquid is coated on the hollow fiber material; then, the crystallization is performed. The preparation method has the advantages that a molecular sieving membrane with no defect and small thickness can be obtained; only smaller reactants and products which are sieved out can penetrate to enter the catalyst core; meanwhile, the two processes of separation and reaction are realized; the selectivity of the catalyst on reactants can be improved through a core shell structure formed through cladding; the active center loss of the catalyst is prevented; the catalyst and product separation is favorably realized.
Description
Technical field
The preparation method who the invention discloses a kind of molecular screen membrane coated catalyst, belongs to catalyst field.
Background technology
Molecular screen membrane has higher heat endurance, preferably chemical stability, corrosion resistance and with the biocompatibility of special material. If but will synthesize the molecular screen membrane of excellent performance, require has good compatibility between carrier and molecular sieve in building-up process, and tiny zeolite crystal or monocrystalline can be attached to carrier surface, the mutual film forming of epitaxial growth subsequently. Because part inert carrier exists hardly the effects such as, grafting fixed such as riveting, Van der Waals force, hydrogen bond or static, surface tension in building-up process with molecular sieve crystal seed, so that carrier surface can not be synthesized liquid wetting, thereby need to make improvement to conventional molecular screen membrane synthetic method.
In recent years, molecular screen membrane is as a kind of porous, inorganic membrane material, because it has stronger heat endurance and chemical stability, there is different acidity, close hydrophobicity performance and catalytic performance, in catalysis, absorption and the aspect such as separate and apply widely, its status is also more and more important, and the synthetic and preparation of its composite more and more obtains grinding the personnel's of making internal disorder or usurp concern. The core-shell catalyst that porous molecular screen film coated catalysts forms; due to the special porous of molecular sieve and catalytic performance and the combination of core catalyst; can embody and select shape function, there is again good defencive function, be in recent years membrane science field and catalytic field grind one of the focus that makes internal disorder or usurp.
Summary of the invention
The technical problem that the present invention mainly solves: for current molecular screen membrane preparation process there is defect, the thickness of film is large, resistance to elevated temperatures is poor, and molecular screen membrane is coated on catalyst or carrier, blocked up molecular screen membrane has hindered the problem of the selective and diffusion of product, a kind of preparation method of molecular screen membrane coated catalyst is provided, the present invention is first raw material with polyethersulfone resin and methyl pyrrolidone, add nano titanium dioxide powder to obtain spinning solution in batches, spinning solution is put into high-voltage electrostatic spinning device and form silica hollow fiber material, the catalyst making is made to coating liquid, and be coated on hollow fiber material, after crystallization, the present invention can obtain zero defect, the molecular screen membrane that thickness is little, filtering out less reactant and product could see through and enter catalyst kernel, realize simultaneously and separating and two processes of reaction, it is selective to reactant that coated formation nucleocapsid structure can increase catalyst, prevent catalyst active center's loss, and be conducive to separating of catalyst and product.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
(1) taking 10～20g aluminium isopropoxide is dissolved in 100～200mL distilled water, put into water-bath, be heated to 60～80 DEG C, drip successively the sodium hydroxide solution that 10～15mL concentration is 0.02mol/L, tetramethyl oxyammonia solution and the 5～8mL Ludox that 5～10mL concentration is 0.5mol/L, be placed on oscillating reactions 12～24h on shaking table, filter to obtain solid product;
(2) get 10～15g solid product and put into planetary ball mill, put into the corundum abrading-ball that 20～30 particle diameters are 10mm, set the revolution of ball mill card contrary with ball grinder sense of rotation, and speed ratio is 1:2, exchange rotation direction every 5min, with revolution speed ball milling 1～2h of 500～600r/min, the powder that ball milling is obtained is that 1:10 adds in deionized water by solid-to-liquid ratio, after high speed dispersion agent disperses, makes crystal seed suspension;
(3) take 3～5g alumina powder and cross the screen cloth that aperture is 1～2mm, screen out the excessive alumina particle of particle, with moving into baking oven after ultrasonic cleaning instrument ultrasonic cleaning 20～30min, at 105～110 DEG C, be dried to constant weight, put it into mass concentration and be in 5% nickel nitrate solution, put into vortex oscillation instrument, with the power of 10～20W, after rate oscillation dipping 1～2h of 100～300rmp/min, filter, filter residue is put into Muffle furnace, be warming up to 400～500 DEG C of high-temperature calcination 3～4h, obtain catalyst;
(4) 30～50g polyethersulfone resin is added in 200～300mL methyl pyrrolidone, be placed on and on magnetic stirrer, stir 2～3h it is fully dissolved, speed of agitator is 500～600r/min, under stirring, divide and add 10～20g nano titanium dioxide powder 3～5 times again, continue to stir 20～24h and make spinning solution;
(5) the above-mentioned spinning solution making is put into high-voltage electrostatic spinning device hopper, start HV generator, spinning solution is extruded and sprayed by spinning nozzle with infusion pump, the spinning solution jet formation nanofiber that is cured of ejection, orderly is arranged on collecting board, forms silica hollow fiber material;
(6) will make catalyst is that 1:10 adds in crystal seed suspension by solid-to-liquid ratio, put into rotary evaporator, be warming up to 60～70 DEG C, revolve and boil off except moisture until suspension vol becomes 2/3 of original volume, obtain thickness crystal seed coating liquid, it is manually coated on the above-mentioned silica hollow fiber material making, coating thickness is 2～3mm, be placed in insulating box, at 80～90 DEG C, after crystallization 3～5h, obtain a kind of molecular screen membrane coated catalyst.
Described spinning jet curing be the aqueous solution that is made into as 5:1 in mass ratio using sulfuric acid and sodium sulphate as coagulating bath, spinning jet is solidified.
Application process of the present invention: the present invention is made to molecular screen membrane coated catalyst, can be applied in exhaust fume catalytic processing, for example, catalyst after coated can be for the selective oxidation of butane and CO gas, can complete catalysts oxidation CO, CO and O at 500～800 DEG C2Can enter molecular sieve pore passage and catalyst reacts, and normal butane substantially can not contact with catalyst can not be oxidized, be 99.2～99.6% at 50～90 DEG C of catalyst to the conversion ratio of CO.
The invention has the beneficial effects as follows:
(1) the present invention can obtain zero defect, molecular screen membrane that thickness is little, filters out less reactant and product and could see through and enter catalyst kernel, realizes simultaneously and separating and two processes of reaction;
(2) can to increase catalyst selective to reactant for the coated nucleocapsid structure forming of the present invention, prevents that catalyst active center runs off, and be conducive to separating of catalyst and product.
Detailed description of the invention
First taking 10～20g aluminium isopropoxide is dissolved in 100～200mL distilled water, put into water-bath, be heated to 60～80 DEG C, drip successively the sodium hydroxide solution that 10～15mL concentration is 0.02mol/L, tetramethyl oxyammonia solution and the 5～8mL Ludox that 5～10mL concentration is 0.5mol/L, be placed on oscillating reactions 12～24h on shaking table, filter to obtain solid product; Get 10～15g solid product and put into planetary ball mill, put into the corundum abrading-ball that 20～30 particle diameters are 10mm, set the revolution of ball mill card contrary with ball grinder sense of rotation, and speed ratio is 1:2, exchange rotation direction every 5min, with revolution speed ball milling 1～2h of 500～600r/min, the powder that ball milling is obtained is that 1:10 adds in deionized water by solid-to-liquid ratio, after high speed dispersion agent disperses, makes crystal seed suspension; Take 3～5g alumina powder and cross the screen cloth that aperture is 1～2mm, screen out the excessive alumina particle of particle, with moving into baking oven after ultrasonic cleaning instrument ultrasonic cleaning 20～30min, at 105～110 DEG C, be dried to constant weight, put it into mass concentration and be in 5% nickel nitrate solution, put into vortex oscillation instrument, with the power of 10～20W, after rate oscillation dipping 1～2h of 100～300rmp/min, filter, filter residue is put into Muffle furnace, be warming up to 400～500 DEG C of high-temperature calcination 3～4h, obtain catalyst; 30～50g polyethersulfone resin is added in 200～300mL methyl pyrrolidone, be placed on and on magnetic stirrer, stir 2～3h it is fully dissolved, speed of agitator is 500～600r/min, under stirring, divide and add 10～20g nano titanium dioxide powder 3～5 times again, continue to stir 20～24h and make spinning solution; The spinning solution making is put into high-voltage electrostatic spinning device hopper, start HV generator, spinning solution is extruded and sprayed by spinning nozzle with infusion pump, the spinning solution jet of the ejection formation nanofiber that is cured, orderly is arranged on collecting board, forms silica hollow fiber material; To make catalyst is that 1:10 adds in crystal seed suspension by solid-to-liquid ratio, put into rotary evaporator, be warming up to 60～70 DEG C, revolve and boil off except moisture until suspension vol becomes 2/3 of original volume, obtain thickness crystal seed coating liquid, it is manually coated on the above-mentioned silica hollow fiber material making, coating thickness is 2～3mm, be placed in insulating box, at 80～90 DEG C, after crystallization 3～5h, obtain a kind of molecular screen membrane coated catalyst.
Described spinning jet curing be the aqueous solution that is made into as 5:1 in mass ratio using sulfuric acid and sodium sulphate as coagulating bath, spinning jet is solidified.
Example 1
First taking 10g aluminium isopropoxide is dissolved in 100mL distilled water, put into water-bath, be heated to 60 DEG C, drip successively the sodium hydroxide solution that 10mL concentration is 0.02mol/L, tetramethyl oxyammonia solution and the 5mL Ludox that 5mL concentration is 0.5mol/L, be placed on oscillating reactions 12h on shaking table, filter to obtain solid product; Get 10g solid product and put into planetary ball mill, put into the corundum abrading-ball that 20 particle diameters are 10mm, set the revolution of ball mill card contrary with ball grinder sense of rotation, and speed ratio is 1:2, exchange rotation direction every 5min, with the revolution speed ball milling 1h of 500r/min, the powder that ball milling is obtained is that 1:10 adds in deionized water by solid-to-liquid ratio, after high speed dispersion agent disperses, makes crystal seed suspension; Take 3g alumina powder and cross the screen cloth that aperture is 1mm, screen out the excessive alumina particle of particle, with moving into baking oven after ultrasonic cleaning instrument ultrasonic cleaning 20min, at 105 DEG C, be dried to constant weight, put it into mass concentration and be in 5% nickel nitrate solution, put into vortex oscillation instrument, with the power of 10W, after the rate oscillation dipping 1h of 100rmp/min, filter, filter residue is put into Muffle furnace, be warming up to 400 DEG C of high-temperature calcination 3h, obtain catalyst; 30g polyethersulfone resin is added in 200mL methyl pyrrolidone, be placed on and on magnetic stirrer, stir 2h it is fully dissolved, speed of agitator is 500r/min, then divides and add 10g nano titanium dioxide powder 3 times under stirring, continues to stir 20h and makes spinning solution; The spinning solution making is put into high-voltage electrostatic spinning device hopper, start HV generator, spinning solution is extruded and sprayed by spinning nozzle with infusion pump, the spinning solution jet of the ejection formation nanofiber that is cured, orderly is arranged on collecting board, forms silica hollow fiber material; To make catalyst is that 1:10 adds in crystal seed suspension by solid-to-liquid ratio, put into rotary evaporator, be warming up to 60 DEG C, revolve and boil off except moisture until suspension vol becomes 2/3 of original volume, obtain thickness crystal seed coating liquid, it is manually coated on the above-mentioned silica hollow fiber material making, coating thickness is 2mm, be placed in insulating box, at 80 DEG C, after crystallization 3h, obtain a kind of molecular screen membrane coated catalyst.
Described spinning jet curing be the aqueous solution that is made into as 5:1 in mass ratio using sulfuric acid and sodium sulphate as coagulating bath, spinning jet is solidified.
The present invention is made to molecular screen membrane coated catalyst, can be applied to during exhaust fume catalytic processes, for example, catalyst after coated can be for the selective oxidation of butane and CO gas, can complete catalysts oxidation CO, CO and O at 500～800 DEG C2Can enter molecular sieve pore passage and catalyst reacts, and normal butane substantially can not contact with catalyst can not be oxidized, be 99.2% at 50 DEG C of catalyst to the conversion ratio of CO.
Example 2
First taking 15g aluminium isopropoxide is dissolved in 150mL distilled water, put into water-bath, be heated to 70 DEG C, drip successively the sodium hydroxide solution that 13mL concentration is 0.02mol/L, tetramethyl oxyammonia solution and the 6mL Ludox that 7mL concentration is 0.5mol/L, be placed on oscillating reactions 18h on shaking table, filter to obtain solid product; Get 13g solid product and put into planetary ball mill, put into the corundum abrading-ball that 25 particle diameters are 10mm, set the revolution of ball mill card contrary with ball grinder sense of rotation, and speed ratio is 1:2, exchange rotation direction every 5min, with the revolution speed ball milling 1.5h of 550r/min, the powder that ball milling is obtained is that 1:10 adds in deionized water by solid-to-liquid ratio, after high speed dispersion agent disperses, makes crystal seed suspension; Take 4g alumina powder and cross the screen cloth that aperture is 1.5mm, screen out the excessive alumina particle of particle, with moving into baking oven after ultrasonic cleaning instrument ultrasonic cleaning 25min, at 108 DEG C, be dried to constant weight, put it into mass concentration and be in 5% nickel nitrate solution, put into vortex oscillation instrument, with the power of 15W, after the rate oscillation dipping 1.5h of 200rmp/min, filter, filter residue is put into Muffle furnace, be warming up to 450 DEG C of high-temperature calcination 3.5h, obtain catalyst; 40g polyethersulfone resin is added in 250mL methyl pyrrolidone, be placed on and on magnetic stirrer, stir 2.5h it is fully dissolved, speed of agitator is 550r/min, then divides and add 15g nano titanium dioxide powder 4 times under stirring, continues to stir 22h and makes spinning solution; The spinning solution making is put into high-voltage electrostatic spinning device hopper, start HV generator, spinning solution is extruded and sprayed by spinning nozzle with infusion pump, the spinning solution jet of the ejection formation nanofiber that is cured, orderly is arranged on collecting board, forms silica hollow fiber material; To make catalyst is that 1:10 adds in crystal seed suspension by solid-to-liquid ratio, put into rotary evaporator, be warming up to 65 DEG C, revolve and boil off except moisture until suspension vol becomes 2/3 of original volume, obtain thickness crystal seed coating liquid, it is manually coated on the above-mentioned silica hollow fiber material making, coating thickness is 2.5mm, be placed in insulating box, at 85 DEG C, after crystallization 3～5h, obtain a kind of molecular screen membrane coated catalyst.
Described spinning jet curing be the aqueous solution that is made into as 5:1 in mass ratio using sulfuric acid and sodium sulphate as coagulating bath, spinning jet is solidified.
The present invention is made to molecular screen membrane coated catalyst, can be applied to during exhaust fume catalytic processes, for example, catalyst after coated can be for the selective oxidation of butane and CO gas, can complete catalysts oxidation CO, CO and O at 650 DEG C2Can enter molecular sieve pore passage and catalyst reacts, and normal butane substantially can not contact with catalyst can not be oxidized, be 99.4% at 70 DEG C of catalyst to the conversion ratio of CO.
Example 3
First taking 20g aluminium isopropoxide is dissolved in 200mL distilled water, put into water-bath, be heated to 80 DEG C, drip successively the sodium hydroxide solution that 15mL concentration is 0.02mol/L, tetramethyl oxyammonia solution and the 8mL Ludox that 10mL concentration is 0.5mol/L, be placed on oscillating reactions 24h on shaking table, filter to obtain solid product; Get 15g solid product and put into planetary ball mill, put into the corundum abrading-ball that 30 particle diameters are 10mm, set the revolution of ball mill card contrary with ball grinder sense of rotation, and speed ratio is 1:2, exchange rotation direction every 5min, with the revolution speed ball milling 2h of 600r/min, the powder that ball milling is obtained is that 1:10 adds in deionized water by solid-to-liquid ratio, after high speed dispersion agent disperses, makes crystal seed suspension; Take 5g alumina powder and cross the screen cloth that aperture is 2mm, screen out the excessive alumina particle of particle, with moving into baking oven after ultrasonic cleaning instrument ultrasonic cleaning 30min, at 110 DEG C, be dried to constant weight, put it into mass concentration and be in 5% nickel nitrate solution, put into vortex oscillation instrument, with the power of 20W, after the rate oscillation dipping 2h of 300rmp/min, filter, filter residue is put into Muffle furnace, be warming up to 500 DEG C of high-temperature calcination 4h, obtain catalyst; 50g polyethersulfone resin is added in 300mL methyl pyrrolidone, be placed on and on magnetic stirrer, stir 3h it is fully dissolved, speed of agitator is 600r/min, then divides and add 20g nano titanium dioxide powder 5 times under stirring, continues to stir 24h and makes spinning solution; The spinning solution making is put into high-voltage electrostatic spinning device hopper, start HV generator, spinning solution is extruded and sprayed by spinning nozzle with infusion pump, the spinning solution jet of the ejection formation nanofiber that is cured, orderly is arranged on collecting board, forms silica hollow fiber material; To make catalyst is that 1:10 adds in crystal seed suspension by solid-to-liquid ratio, put into rotary evaporator, be warming up to 70 DEG C, revolve and boil off except moisture until suspension vol becomes 2/3 of original volume, obtain thickness crystal seed coating liquid, it is manually coated on the above-mentioned silica hollow fiber material making, coating thickness is 2～3mm, be placed in insulating box, at 90 DEG C, after crystallization 5h, obtain a kind of molecular screen membrane coated catalyst.
Described spinning jet curing be the aqueous solution that is made into as 5:1 in mass ratio using sulfuric acid and sodium sulphate as coagulating bath, spinning jet is solidified.
The present invention is made to molecular screen membrane coated catalyst, can be applied to during exhaust fume catalytic processes, for example, catalyst after coated can be for the selective oxidation of butane and CO gas, can complete catalysts oxidation CO, CO and O at 800 DEG C2Can enter molecular sieve pore passage and catalyst reacts, and normal butane substantially can not contact with catalyst can not be oxidized, be 99.6% at 90 DEG C of catalyst to the conversion ratio of CO.
Claims (2)
1. a preparation method for molecular screen membrane coated catalyst, is characterized in that concrete preparation process is:
(1) taking 10～20g aluminium isopropoxide is dissolved in 100～200mL distilled water, put into water-bath, be heated to 60～80 DEG C, drip successively the sodium hydroxide solution that 10～15mL concentration is 0.02mol/L, tetramethyl oxyammonia solution and the 5～8mL Ludox that 5～10mL concentration is 0.5mol/L, be placed on oscillating reactions 12～24h on shaking table, filter to obtain solid product;
(2) get 10～15g solid product and put into planetary ball mill, put into the corundum abrading-ball that 20～30 particle diameters are 10mm, set the revolution of ball mill card contrary with ball grinder sense of rotation, and speed ratio is 1:2, exchange rotation direction every 5min, with revolution speed ball milling 1～2h of 500～600r/min, the powder that ball milling is obtained is that 1:10 adds in deionized water by solid-to-liquid ratio, after high speed dispersion agent disperses, makes crystal seed suspension;
(3) take 3～5g alumina powder and cross the screen cloth that aperture is 1～2mm, screen out the excessive alumina particle of particle, with moving into baking oven after ultrasonic cleaning instrument ultrasonic cleaning 20～30min, at 105～110 DEG C, be dried to constant weight, put it into mass concentration and be in 5% nickel nitrate solution, put into vortex oscillation instrument, with the power of 10～20W, after rate oscillation dipping 1～2h of 100～300rmp/min, filter, filter residue is put into Muffle furnace, be warming up to 400～500 DEG C of high-temperature calcination 3～4h, obtain catalyst;
(4) 30～50g polyethersulfone resin is added in 200～300mL methyl pyrrolidone, be placed on and on magnetic stirrer, stir 2～3h it is fully dissolved, speed of agitator is 500～600r/min, under stirring, divide and add 10～20g nano titanium dioxide powder 3～5 times again, continue to stir 20～24h and make spinning solution;
(5) the above-mentioned spinning solution making is put into high-voltage electrostatic spinning device hopper, start HV generator, spinning solution is extruded and sprayed by spinning nozzle with infusion pump, the spinning solution jet formation nanofiber that is cured of ejection, orderly is arranged on collecting board, forms silica hollow fiber material;
(6) will make catalyst is that 1:10 adds in crystal seed suspension by solid-to-liquid ratio, put into rotary evaporator, be warming up to 60～70 DEG C, revolve and boil off except moisture until suspension vol becomes 2/3 of original volume, obtain thickness crystal seed coating liquid, it is manually coated on the above-mentioned silica hollow fiber material making, coating thickness is 2～3mm, be placed in insulating box, at 80～90 DEG C, after crystallization 3～5h, obtain a kind of molecular screen membrane coated catalyst.
2. the preparation method of a kind of molecular screen membrane coated catalyst according to claim 1, is characterized in that: described spinning jet curing be the aqueous solution that is made into as 5:1 in mass ratio using sulfuric acid and sodium sulphate as coagulating bath, spinning jet is solidified.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278368A (en) * | 2016-08-15 | 2017-01-04 | 北京大学深圳研究生院 | A kind of composite molecular sieve film and its preparation method and application |
| CN108905970A (en) * | 2018-07-23 | 2018-11-30 | 山东建筑大学 | The preparation method and application of cadmium adsorbent is removed based on the modified water body of clinoptilolite |
| CN109056116A (en) * | 2018-07-05 | 2018-12-21 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of nickel acid lanthanum load nickel oxide fiber |
| CN113174002A (en) * | 2021-04-26 | 2021-07-27 | 上海化工研究院有限公司 | Ultrahigh molecular weight polyethylene catalyst, and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278368A (en) * | 2016-08-15 | 2017-01-04 | 北京大学深圳研究生院 | A kind of composite molecular sieve film and its preparation method and application |
| CN109056116A (en) * | 2018-07-05 | 2018-12-21 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of nickel acid lanthanum load nickel oxide fiber |
| CN108905970A (en) * | 2018-07-23 | 2018-11-30 | 山东建筑大学 | The preparation method and application of cadmium adsorbent is removed based on the modified water body of clinoptilolite |
| CN108905970B (en) * | 2018-07-23 | 2021-02-26 | 山东建筑大学 | Preparation method and application of clinoptilolite modification-based water body cadmium removal adsorbent |
| CN113174002A (en) * | 2021-04-26 | 2021-07-27 | 上海化工研究院有限公司 | Ultrahigh molecular weight polyethylene catalyst, and preparation method and application thereof |
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