CN102274705A - Method for preparing molecular sieve membrane catalytic reactor taking active carbon as carrier - Google Patents
Method for preparing molecular sieve membrane catalytic reactor taking active carbon as carrier Download PDFInfo
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- CN102274705A CN102274705A CN2011101104235A CN201110110423A CN102274705A CN 102274705 A CN102274705 A CN 102274705A CN 2011101104235 A CN2011101104235 A CN 2011101104235A CN 201110110423 A CN201110110423 A CN 201110110423A CN 102274705 A CN102274705 A CN 102274705A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 55
- 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 55
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008187 granular material Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001802 infusion Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing a molecular sieve membrane catalytic reactor taking active carbon as a carrier. The method comprises the following steps of: coating a layer of inorganic membrane on the surface of the carrier which is made of active carbon or active carbon loaded with active components, and putting the carrier coated with the inorganic membrane into molecular sieve synthetic liquid to perform hydrothermal crystallization treatment, so that a uniform and compact molecular sieve membrane is grown on the surface of the active carbon or the surface of the active carbon loaded with the active components. In the method, due to the adoption of an inorganic membrane layer, the continuous and compact molecular sieve membrane is formed on the carrier of the active carbon or the active carbon loaded with the active components; and with the inorganic membrane layer, the active carbon can be wrapped with a layer of continuous and compact molecular sieve membrane by one-time hydrothermal synthesis, and the inorganic membrane layer is dissolved partially in the synthetic process and participates in the crystallization process; and the compact molecular sieve membrane and the carrier of the active carbon or the active carbon loaded with the active components form the catalytic membrane reactor, so that the catalytic membrane reactor is expected to be applied in fields of adsorption, separation, catalysis and the like actually.
Description
Technical field
The present invention relates to a kind of is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon.
Background technology
Molecular screen membrane has a wide range of applications at gas absorption, separation and catalytic field, because the sieve effect of molecular screen membrane and the catalytic action that itself has, coat one deck molecular screen membrane on the traditional catalyst surface and can be combined into membrane reactor, this class membrane reactor is because the existence of molecular screen membrane, can by molecular screen membrane to reactant and product selectivity absorption, separate and catalytic process produces obviously influence, improve catalyst to the selectivity of reactant, to the tolerance of poisonous substance and the recycling number of times of catalyst.Active carbon is the catalyst carrier of a class extensive use, because its surface active groups is few, the adhesive force of crystal seed on active carbon is very weak during the molecular sieve water heat crystallization, though synthesis of molecular sieve has report on the sheet shaped activated carbon, almost be infeasible directly at activated carbon granule superficial growth molecular screen membrane; And to active carbon oxidant (hydrogen peroxide commonly used, sodium thiosulfate etc.), soda acid (nitric acid, NaOH, potassium hydroxide etc.) and carry out the coating of molecular screen membrane after the modification of high molecular polymer treated cation, it is not satisfactory to coat integrity degree and compactness.Is the problem that significant challenge and application are arranged at different activities charcoal carrier surface by even, a fine and close growth and the complete coating activated carbon granule of hydro-thermal synthetic realization molecular screen membrane.
At present, molecular screen membrane cladded type catalyst adopt before the growth molecular screen membrane carried out organic matter (as silane coupler or polymer cation) modification and crystal seed pre-coating method to carrier or catalyst more.Often need to use organic solvents such as benzene, toluene when using the organic matter modification, and coupling agent and polymer cation utilization rate are low, unstable in the high-temperature water thermal environment; Often need after the crystal seed precoating roasting strengthening the riveted joint between crystal seed and the carrier, different with silica, alumina support, on the active carbon after the precoating crystal seed again roasting cause crystal seed to come off on the contrary.Once the molecular screen membrane of the synthetic even compact of hydro-thermal does not appear in the newspapers as yet on active carbon.
Summary of the invention
The present invention is directed to the problem that is difficult for the fine and close molecular screen membrane of growth at activated carbon surface, providing a kind of is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon.
The present invention is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon, it is characterized in that may further comprise the steps:
(1) active carbon or load are had after the active carbon washes clean of active component 50 ~ 140
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process, spraying process or chemical vapour deposition technique to apply one deck inoranic membrane, 30 ~ 90 at the activated carbon surface that active carbon or load through step (1) processing have active component
oC is dry down, is warming up to 250 ~ 600 then in nitrogen atmosphere
oDrop to room temperature behind C roasting 2 ~ 10h, heating rate and rate of temperature fall all are controlled at 0.2～5
oC/min;
(3) in the synthetic liquid of active carbon immersion molecular sieve that active carbon that is coated with inoranic membrane that step (2) is obtained or load have active component, the autoclave ageing 20min ~ 8h that packs into then is again in 70 ~ 190
oC crystallization 2 ~ 120h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=1:0 ~ 0.8:0 ~ 1.5:0 ~ 8:0 ~ 4.0:10 ~ 2000;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Among the present invention, described active carbon can be wood activated charcoal or active carbon from coal.Its shape can be graininess, cylindrical, spherical, sheet or fibrous.
Among the present invention, described inoranic membrane can be aluminium oxide, silica or titanium oxide.Can to add mass fraction in aluminium oxide, silica or titanium oxide be that 0.2% ~ 10% polyvinyl alcohol, mass fraction are that 0.2% ~ 10% polyethylene glycol or mass fraction are 0.2% ~ 10% polypropylene glycol in order to improve filming performance.
Among the present invention, load on active component on the active carbon and can be among Pt, Pd, Ru, Rh, Cu and the Ni one or more.
Being coated in active carbon or load among the present invention has the inoranic membrane thickness of the activated carbon surface of active component to control by applying number of times and coating time.
Do not having to be difficult to the fine and close molecular-sieve film catalytic reactor of growth on the active carbon of inorganic film, the molecular-sieve film catalytic reactor of the inventive method preparation, use inorganic film to help on absorbent charcoal carrier, forming continuously, fine and close molecular screen membrane, inorganic film not only can make active carbon through the synthetic fine and close continuous molecular screen membrane of one deck that just can coat of hydro-thermal, and inorganic film is partly dissolved and participates in crystallization process in building-up process, fine and close molecular screen membrane and active carbon or load have the absorbent charcoal carrier of active component to be combined into catalytic film reactor, are expected in absorption, separate, catalytic field obtains practical application.
Description of drawings
Fig. 1 is the SEM figure of the activated carbon granule of alumina-coated among the embodiment 1.
Fig. 2 is the SEM figure of the synthetic molecular-sieve film catalytic reactor of embodiment 1.
The specific embodiment
The present invention will be further described below in conjunction with drawings and Examples.
(1) just granular size is 120 after 20 ~ 40 purpose active carbons wash 7 times with distilled water
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process to apply one deck pellumina, 70 at the activated carbon surface of handling through step (1)
oC is dry down, is warming up to 500 then in nitrogen atmosphere
oDrop to room temperature behind the C roasting 4h, heating rate and rate of temperature fall all are controlled at 2
oC/min; The SEM figure of the activated carbon granule of alumina-coated sees Fig. 1;
(3) active carbon that is coated with pellumina that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 2h that packs into then is again in 175
oC crystallization 48h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=1:0:0.2:4:0.5:200;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor, as shown in Figure 2, has coated the fine and close continuous molecular screen membrane of one deck at activated carbon surface as seen from the figure.
Embodiment 2
(1) just granular size be 1.0cm active carbon with after the distilled water washing 5 times 140
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process to apply one deck pellumina, 90 at the activated carbon surface of handling through step (1)
oC is dry down, is warming up to 400 then in nitrogen atmosphere
oDrop to room temperature behind the C roasting 6h, heating rate and rate of temperature fall all are controlled at 3
oC/min;
(3) active carbon that is coated with pellumina that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 5h that packs into then is again in 170
oC crystallization 48h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=1:0.02:0.15:4:0.1:200;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Embodiment 3
(1) just granular size is 90 after 20 ~ 40 purpose active carbons wash 4 times with distilled water
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process to apply one deck silicon oxide film, 50 at the activated carbon surface of handling through step (1)
oC is dry down, is warming up to 350 then in nitrogen atmosphere
oDrop to room temperature behind the C roasting 2h, heating rate and rate of temperature fall all are controlled at 2.5
oC/min;
(3) active carbon that is coated with silicon oxide film that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 3h that packs into then is again in 170
oC crystallization 24h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=1:0:3:4:1.2:100;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Embodiment 4
(1) just granular size is 90 after 20 ~ 40 purpose active carbons wash 4 times with distilled water
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process to apply one deck silicon oxide film, 60 at the activated carbon surface of handling through step (1)
oC is dry down, is warming up to 550 then in nitrogen atmosphere
oDrop to room temperature behind the C roasting 2h, heating rate and rate of temperature fall all are controlled at 2.5
oC/min;
(3) active carbon that is coated with silicon oxide film that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 2h that packs into then is again in 70
oC crystallization 6h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=1:1:0:0:50:1000;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Embodiment 5
(1) just granular size is 80 after 20 ~ 40 purpose active carbons wash 5 times with distilled water
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process to apply one deck pellumina, 60 at the activated carbon surface of handling through step (1)
oC is dry down, is warming up to 550 then in nitrogen atmosphere
oDrop to room temperature behind the C roasting 4h, heating rate and rate of temperature fall all are controlled at 2.5
oC/min;
(3) active carbon that is coated with pellumina that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 4h that packs into then is again in 170
oC crystallization 24h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=1:0:0.17:0:0.1:120;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Embodiment 6
(1) be 85 with granular size after 20 ~ 40 purpose active carbons wash 4 times with distilled water
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process to apply one deck pellumina, 60 at the activated carbon surface of handling through step (1)
oC is dry down, is warming up to 500 then in nitrogen atmosphere
oDrop to room temperature behind the C roasting 4h, heating rate and rate of temperature fall all are controlled at 1.5
oC/min;
(3) active carbon that is coated with pellumina that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 4h that packs into then is again in 90
oC crystallization 10h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=5:1:0:0:30:1000;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Embodiment 7
(1) just the particle diameter size be 0.6 mm spheric active carbon with after the distilled water washing 6 times 90
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process to apply one deck silica inoranic membrane, 60 at the activated carbon surface of handling through step (1)
oC is dry down, is warming up to 500 then in nitrogen atmosphere
oDrop to room temperature behind the C roasting 4h, heating rate and rate of temperature fall all are controlled at 1.0
oC/min;
(3) active carbon that is coated with silicon oxide film that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 4h that packs into then is again in 175
oC crystallization 24h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=1:0:0.9:2:0:2000;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Embodiment 8
(1) be 90 with granular size after 20 ~ 40 purpose active carbons wash 4 times with distilled water
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process to apply one deck aluminium oxide inoranic membrane, 70 at the activated carbon surface of handling through step (1)
oC is dry down, is warming up to 500 then in nitrogen atmosphere
oDrop to room temperature behind the C roasting 4h, heating rate and rate of temperature fall all are controlled at 1.0
oC/min;
(3) active carbon that is coated with pellumina that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 2.5h that packs into then is again in 170
oC crystallization 12h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:NaOH:EtOH:H
2O=10:0:1.6:2:40: 1600;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Embodiment 9
(1) be 140 with granular size after 20 ~ 40 purpose active carbons wash 4 times with distilled water
oC is oven dry down, places the drier cooling standby;
(2) adopting infusion process impregnating effect mark on the active carbon of handling through step (1) is that 0.5% Pd forms the Pd/C catalyst, and surface-coated one deck aluminium oxide inoranic membrane then is 140
oC is dry down, is warming up to 500 in the nitrogen atmosphere
oDrop to room temperature behind the C roasting 4h, heating rate and rate of temperature fall all are controlled at 1.0
oC/min;
(3) active carbon of the coating active component that step (2) is obtained immerses in the synthetic liquid of molecular sieve, and the autoclave ageing 2.5h that packs into then is again in 170
oC crystallization 24h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:NaOH:EtOH:H
2O=10:0:1.2:2.4:40:1200;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
Claims (6)
1. one kind is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon, it is characterized in that may further comprise the steps:
(1) active carbon or load are had after the active carbon washes clean of active component 50 ~ 140
oC is oven dry down, places the drier cooling standby;
(2) adopt infusion process, spraying process or chemical vapour deposition technique to apply one deck inoranic membrane, 30 ~ 90 at the activated carbon surface that active carbon or load through step (1) processing have active component
oC is dry down, is warming up to 250 ~ 600 then in nitrogen atmosphere
oDrop to room temperature behind C roasting 2 ~ 10h, heating rate and rate of temperature fall all are controlled at 0.2～5
oC/min;
(3) in the synthetic liquid of active carbon immersion molecular sieve that active carbon that is coated with inoranic membrane that step (2) is obtained or load have active component, the autoclave ageing 20min ~ 8h that packs into then is again in 70 ~ 190
oC crystallization 2 ~ 120h obtains the fine and close activated carbon granule that coats of molecular screen membrane, and the mol ratio of the synthetic liquid of molecular sieve consists of SiO
2: Al
2O
3: TPaOH:EtOH:NaOH:H
2O=1:0 ~ 0.8:0 ~ 1.5:0 ~ 8:0 ~ 4.0:10 ~ 2000;
(4) cooling autoclave filters the product that obtains, wash, dry, and obtains the molecular-sieve film catalytic reactor.
2. according to claim 1 is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon, it is characterized in that described active carbon is wood activated charcoal, active carbon from coal or asphalt based active carbon.
3. according to claim 1 and 2 is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon, and the shape that it is characterized in that active carbon is graininess, cylindrical, spherical, sheet or fibrous.
4. according to claim 1 is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon, it is characterized in that described inoranic membrane is aluminium oxide, silica or titanium oxide.
5. according to claim 4 is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon, it is characterized in that in aluminium oxide, silica or titanium oxide adding mass fraction and be 0.2% ~ 10% polyvinyl alcohol, mass fraction and be 0.2% ~ 10% polyethylene glycol or mass fraction and be 0.2% ~ 10% polypropylene glycol.
6. according to claim 1 is the preparation method of the molecular-sieve film catalytic reactor of carrier with the active carbon, it is characterized in that loading on active component on the active carbon and be among Pt, Pd, Ru, Rh, Cu and the Ni one or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104338550A (en) * | 2014-09-10 | 2015-02-11 | 江苏金聚合金材料有限公司 | Preparation method of catalyst used in dilute nitric acid treating and alkyl nitrite generating |
| CN116443831A (en) * | 2023-03-22 | 2023-07-18 | 礼思(上海)材料科技有限公司 | Method for producing lithium salt from salt lake |
| CN117065723A (en) * | 2023-09-20 | 2023-11-17 | 湖南浩润科技有限公司 | Desulfurizing agent and preparation method thereof |
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| US20030228969A1 (en) * | 2002-06-11 | 2003-12-11 | Junhang Dong | Method for synthesizing zeolite membranes |
| CN1663677A (en) * | 2004-12-21 | 2005-09-07 | 南京大学 | Active carbon material for selective adsorption of nitrosamine and its preparation method |
| CN1795971A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | High performance molecular sieve membrane of silicon by using ceramics of silicon dioxide as carrier, and preparation method |
| CN1966131A (en) * | 2005-11-15 | 2007-05-23 | 浙江师范大学 | Granular type integral membrane reactor for catalysis-separation and its synthesis method |
| CN101003012A (en) * | 2006-12-27 | 2007-07-25 | 中国科学院成都有机化学有限公司 | Method for producing novel catalytic film reactor |
| CN101342496A (en) * | 2008-08-25 | 2009-01-14 | 陕西师范大学 | Preparation method for zirconium-silicon molecular sieve catalytic active membrane |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030228969A1 (en) * | 2002-06-11 | 2003-12-11 | Junhang Dong | Method for synthesizing zeolite membranes |
| CN1663677A (en) * | 2004-12-21 | 2005-09-07 | 南京大学 | Active carbon material for selective adsorption of nitrosamine and its preparation method |
| CN1795971A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | High performance molecular sieve membrane of silicon by using ceramics of silicon dioxide as carrier, and preparation method |
| CN1966131A (en) * | 2005-11-15 | 2007-05-23 | 浙江师范大学 | Granular type integral membrane reactor for catalysis-separation and its synthesis method |
| CN101003012A (en) * | 2006-12-27 | 2007-07-25 | 中国科学院成都有机化学有限公司 | Method for producing novel catalytic film reactor |
| CN101342496A (en) * | 2008-08-25 | 2009-01-14 | 陕西师范大学 | Preparation method for zirconium-silicon molecular sieve catalytic active membrane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104338550A (en) * | 2014-09-10 | 2015-02-11 | 江苏金聚合金材料有限公司 | Preparation method of catalyst used in dilute nitric acid treating and alkyl nitrite generating |
| CN116443831A (en) * | 2023-03-22 | 2023-07-18 | 礼思(上海)材料科技有限公司 | Method for producing lithium salt from salt lake |
| CN117065723A (en) * | 2023-09-20 | 2023-11-17 | 湖南浩润科技有限公司 | Desulfurizing agent and preparation method thereof |
| CN117065723B (en) * | 2023-09-20 | 2024-03-12 | 湖南浩润科技有限公司 | Desulfurizing agent and preparation method thereof |
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