CN103386260A - Method for synthesizing ZSM-5 molecular sieve membrane on alpha-Al2O3 carrier surface - Google Patents
Method for synthesizing ZSM-5 molecular sieve membrane on alpha-Al2O3 carrier surface Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 46
- 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 46
- 239000012528 membrane Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 31
- 229910052594 sapphire Inorganic materials 0.000 title abstract description 4
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 239000013078 crystal Substances 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 16
- 238000001338 self-assembly Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 239000010457 zeolite Substances 0.000 claims description 19
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims description 18
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 206010070834 Sensitisation Diseases 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000008313 sensitization Effects 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 5
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 241000080590 Niso Species 0.000 claims description 4
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 24
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 15
- 238000007747 plating Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000003826 tablet Substances 0.000 description 7
- 238000007654 immersion Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229940108928 copper Drugs 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XGZRAKBCYZIBKP-UHFFFAOYSA-L disodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[Na+] XGZRAKBCYZIBKP-UHFFFAOYSA-L 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229940059939 kayexalate Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
According to the invention, compact ZSM-5 molecular sieve membrane material is prepared on the surface of the carrier alpha-Al2O3 by chemical copper facing modification technology and single crystal seed layer self assembly technology. According to the invention, compact ZSM-5 molecular sieve membrane material is prepared by chemical copper facing surface modification and self assembly of polyelectrolyte layer upon layer taking low-cost alpha-Al2O3 as a carrier. By the invention, not only controllability of crystal seed assembly in the preparation process is improved, the technology is simple and easy for realization. The ZSM-5 molecular sieve membrane prepared by the invention can improve compactness of complete membrane effectively, and the prepared membrane is thin, which can effectively improve the efficiency of ZSM-5 in gas phase and liquid phase separation.
Description
Technical field
The present invention relates to a kind of molecular screen membrane and preparation method thereof, particularly a kind of ZSM-5 molecular sieve film and preparation method thereof.
Background technology
ZSM-5 molecular sieve, its vertical channel diameter is 0.53nm * 0.56nm, the zigzag channel diameter is 0.51nm * 0.55nm, this and industrial several material molecule kinetic diameter relatively more commonly used approach, have very wide application aspect separating at high temperature, chemical industry catalysis, section easily spreads its flourishing channel system within it, difficult obstruction provides may for molecule.
Molecular screen membrane generally is divided into without two types of support membrane and support membranes, and the carrier-free molecular screen membrane, due to frangible, is not easy to study application, and the molecular screen membrane in practical application normally is grown in molecular sieve on carrier and matrix.From carrier generally can be rough be divided into porous carrier, as Woelm Alumina, porous ceramics, porous stainless steel etc.
Porous α-Al
2O
3Carrier is a kind of take alpha-alumina powder as aggregate, through high temperature burn till, the inner ceramic material that forms the pore passage structure that communicates with each other in a large number and also connect with material surface.Because its raw material are cheap, preparation is simple, has the advantages such as higher mechanical strength, corrosion resistance, resistance to high temperature oxidation and resistance to sudden heating, is the most frequently used carrier material in present molecular screen membrane preparation.
The method for preparing at present the ZSM-5 molecular sieve film mainly is divided into two kinds: Vacuum-assisted method and carrier surface crystal seed diauxic growth film forming.For the Vacuum-assisted method method, can implant functional group by carrier surface, change the carrier surface micro-structural and regulate measures such as synthesizing the liquid composition, obtain height-oriented zeolite molecular sieve film; For carrier surface crystal seed diauxic growth film forming, can utilize covalent bond, ionic bond and intermolecular linkage effect, at carrier surface assembling zeolite molecular sieve crystal seed, preparation highly covers, structurally ordered molecular screen membrane.
Yoon
[1], by introduce polymine (PEI) between carrier and zeolite seed crystal, improve into bond strength Deng the people.[3-(2 in first utilization, the 3-glycidoxy) propyl group] trimethoxy silane (EP-TMS) modifies respectively A type (particle diameter 0.5 μ m) zeolite seed crystal and glass carrier is surperficial, make the epoxy radicals effect of the amido of PEI and glass, zeolite surface form amine-hydroxyl bond, the zeolite monofilm of assembling is strengthened with the adhesion on surface, after the 5min ultrasonic cleaning, the individual layer zeolite crystal comes off and is reduced to 7% from 80%.Yoon
[2]Also find Deng the people, the Silicalite-1 crystal seed can be assembled into platinum Pt, golden Au and the indium oxide-conductive carriers such as tin oxide ITO surface take PEI as connector, obtain b-axle aligned single-layer film, arrange closely, surface coverage is high, and adhesion is strong.Li
[3]The zeolite L crystal is assembled into-group modified glass, the quartzy carrier surface of OH by the complexation reaction between terpyridyl ligand and metal cation Deng the people.Wang
[4]Used polyelectrolyte kayexalate (Na Deng the people
+PSS
-) and diallyl dimethyl ammoniumchloride (PDDA
+Cl
-), the self assembly Silicalite-1 zeolite seed crystal (particle diameter 80nm, 300nm) layer by layer on the stainless steel carrier surface., because plane of crystal in alkaline solution is electronegative,, through alternating deposit, form the crystal layer that multilayer covers.Zhang Baoquan
[5]Use polyvinyl alcohol (PVA) to modify the Woelm Alumina surface, obtain smooth PVA film.Further use (3-chloropropyl) trimethoxy silane (CP-TMS) as bridging agent, by ultrasonic assembling, obtain b-axle orientation Silicalite-1 monofilm.The crystal coverage of rete is 100%, and intergranule is arranged closely.Zhang Baoquan
[6]At chitin modified porous α-Al
2O
3Synthesize the TS-1 crystal layer of the continuous b-axle orientation of individual layer on carrier surface, the combination between crystal and carrier is tight.If reaction extends to 48h, form the TS-1 film of multilayer b-axle orientation, thicknesses of layers is about 5 μ m.
That selects when support modification is studied at present, mostly is glass, stainless steel, metallic carrier.What wherein can be used as the diffusion barrier carrier only has a porous stainless steel carrier, and for preparation technology porous α simple, with low cost-Al
2O
3The research of carrier is less, and this is because α-Al
2O
3Carrier is inert material, and surface also is difficult to hydroxylating without hydroxyl, and the α-Al of compression molding
2O
3The carrier surface big rise and fall, the more difficult realization of the deposition of single crystal seed layer; And in order to improve the bond strength between zeolite crystal and carrier, often price is higher for the surfactant that support modification is used
Summary of the invention
The object of the invention is to solve above-mentioned the deficiencies in the prior art, provide a kind of at α-Al
2O
3ZSM-5 molecular sieve film that carrier surface is synthetic and preparation method thereof, the prepared ZSM-5 molecular sieve film of the present invention has improved the compactness of film forming effectively, and the thicknesses of layers of preparation is thin, and these characteristics can improve the efficiency of ZSM-5 in gas phase, liquid phase separation effectively.Preparation method of the present invention has not only improved the controllability of crystal seed assembling in the preparation process, and technique is simple, easily realizes.
For achieving the above object, the present invention by the following technical solutions.
A kind of at α-Al
2O
3The method of the synthetic ZSM-5 molecular sieve film of carrier surface comprises the following steps:
1, with porous α-Al
2O
3Electroless copper is carried out on surface: described porous α-Al
2O
3Fully react and carry out electroless copper in the mixed liquor of sulfur acid copper, nickel sulfate hexahydrate, sodium potassium tartrate tetrahydrate, formaldehyde, NaOH and sodium carbonate after alligatoring, sensitization, activation, washing successively.
2, the self assembly crystal seed method prepares the ZSM-5 molecular sieve film layer by layer:
(1) preparation of nano molecular sieve crystal seed
After the synthetic liquid of ZSM-5 is fully reacted, take out product and dry, obtain the molecular sieve seed particles; Be configured to crystal seed suspension with deionized water, stand-by;
Prepare respectively the pure water mixed solution of pure water mixed solution, polystyrolsulfon acid PSS of polymine PEI and diallyl dimethyl ammoniumchloride PDDA and sodium chloride nacl and mix the PDDA polyelectrolyte soak that is made into;
(2) self assembly crystal seed layer layer by layer
The carrier of the electroless copper of preparation in 1 is soaked respectively successively in PEI alcohol water mixed solution/PSS alcohol water mixed solution/PEI alcohol water mixed solution/PSS alcohol water mixed solution/PDDA polyelectrolyte soak/PSS alcohol water mixed solution/PDDA polyelectrolyte soak/molecular sieve crystal seed suspension, fully after reaction, take out carrier and dry;
(3) preparation of molecular screen membrane
Dried carrier in (2) is put into the synthetic liquid of ZSM-5, and fully reaction is rear and dry, makes described molecular sieve rete.
The synthetic liquid of preferred ZSM-5 is: TPAOH, ethyl orthosilicate, NaOH, absolute ethyl alcohol and deionized water are TPAOH:SiO according to mol ratio
2: H
2O:Na
2The Zeolite synthesis liquid that the ratio of O:EtOH=9:25:595:0.13:100 is made into.
The mixed solution that preferred described pure water mixed solution is absolute ethyl alcohol and deionized water, more preferably the volume ratio of absolute ethyl alcohol and deionized water is 1:1.
Further, described method comprises following concrete steps:
1. porous α-Al
2O
3The preparation of carrier
Batch mixing: with a certain amount of α-Al
2O
3Powder and water fully mix in mortar, preferred powder and water are 5:1 in mass ratio;
Granulation: the powder that will mix is poured in mould, is placed on granulation on tablet press machine; Preferably apply the pressure of 2MP, kept 1 minute;
After release, mortar is put in the compressing tablet taking-up broken into pieces, porphyrize; Preferably with the particle after 40 orders and 80 purpose sieves screening porphyrize, preferred particulates is greater than 80 orders and standby less than 40 purpose particles.
Compressing tablet: similar to granulation process, take the powder after above-mentioned screening, import in mould, be placed on tablet press machine, preferably apply 10MP pressure, pressurize 1min;
Calcining: the porous alumina carrier that presses is taken out, and drying at room temperature, put into Muffle furnace internal program intensification roasting.Preferred heating schedule is as follows:
After taking out, carrier boils cleaning, dry rear standby with deionized water; Preferably dry under 60 ℃.
2. porous α-Al
2O
3Electroless copper
Chemical-copper-plating process flow process: porous alumina carrier → washing → alligatoring → sensitization → activation → washing → chemical plating → washing → oven dry.
1) carrier pretreatment
Alligatoring: preferred 5% volume ratio hydrofluoric acid aqueous solution, soak 5min under room temperature.
Sensitization: preferred every 3g stannous chloride fully is dissolved in the 37.5wt% concentrated hydrochloric acid hydrochloric acid of 2ml, adds water to 100ml and dissolves, and filters, and soaks 5min under room temperature.
Activation: preferably in the 2g/L palladium bichloride, soak 5min under room temperature.
2) electroless copper: at every liter of sulfur acid copper CuSO
412g, nickel sulfate hexahydrate NiSO
46H
2O1.5g, sodium potassium tartrate tetrahydrate C
4O
6H
4KNa40g, formaldehyde HCHO20ml, NaOH NaOH8g and sodium carbonate Na
2CO
3In the mixed liquor of 2g, 40 ℃, plating 5～20min.
3. the self assembly crystal seed method prepares the ZSM-5 molecular sieve film layer by layer
(1) preparation of nano molecular sieve crystal seed
Be TPAOH:SiO with TPAOH, ethyl orthosilicate, NaOH, absolute ethyl alcohol and deionized water according to mol ratio
2: H
2O:Na
2The ratio of O:EtOH=9:25:595:0.13:100, be made into the synthetic liquid of crystal seed, and continuous stirring is fully reacted rear taking-up product; Take out after preferred 100 ℃ of Hydrothermal Synthesis 32h; Then use that deionized water rinsing is centrifugal obtains the molecular sieve seed particles to dry 12h under pH＜8,100 ℃.Take a certain amount of crystal seed, being made into mass fraction with deionized water is 1% crystal seed suspension, and ultrasonic being uniformly dispersed, with the NH of 0.1mol/L
4OH transfers pH to 9.5, and is stand-by.
Configuration concentration is the PEI alcohol water mixed solution (PEI of 0.02g being dissolved in the mixed liquor of 5ml absolute ethyl alcohol and 5ml deionized water) of 2mg/ml and the PSS alcohol water mixed solution (preparing same PEI) of 2mg/ml respectively, and the NaCl of the PDDA of 1mg/ml and 0.1mol/L 1:1 mixing by volume is made into PDDA polyelectrolyte soak.
(2) self assembly crystal seed layer layer by layer
Soak in the carrier of electroless copper is respectively successively in above-mentioned solution, immersion is sequentially: carrier/PEI alcohol water mixed solution/PSS alcohol water mixed solution/PEI alcohol water mixed solution/PSS alcohol water mixed solution/PDDA polyelectrolyte soak/PSS alcohol water mixed solution/PDDA polyelectrolyte soak/molecular sieve crystal seed suspension, each step is soaked 20min, per step all will rinse with deionization after soaking, after having soaked crystal seed finally, change in drying box 80 ℃ after deionized water rinsing over to, dry 12h.
(3) preparation of molecular screen membrane
Be TPAOH:SiO with TPAOH, ethyl orthosilicate, NaOH, absolute ethyl alcohol and deionized water according to mol ratio
2: H
2O:Na
2The ratio of O:EtOH=9:25:595:0.13:100, be made into Zeolite synthesis liquid, after continuous stirring 24h, takes out after 180 ℃ of Hydrothermal Synthesis 48h, uses deionized water rinsing, and is dry under 100 ℃, obtains the molecular sieve rete.
Final step in preparation process (the 3rd step), the synthetic formula of liquid of other ZSM-5 also can prepare the ZSM-5 molecular sieve film.
Advantage of the present invention is: at α-Al
2O
3Carrier surface adopts the electroless copper technology to carry out modification, then adopts layer-by-layer at copper-plated α-Al
2O
3Carrier surface has prepared crystal seed layer, on the basis of above technology, has prepared fine and close, complete ZSM-5 molecular sieve film; α-Al
2O
3Carrier is with low cost, and electroless copper and layer-by-layer easily realize, the compactness of the ZSM-5 molecular sieve film of preparation is good, reduces and prepares the molecular screen membrane cost; With α-Al with low cost
2O
3, for carrier, by the chemical plating surface modification, with the method that the self assembly layer by layer of polyelectrolyte combines, prepare molecular screen membrane.Not only improved the controllability of crystal seed assembling in the preparation process, and technique is simple, easily realizes.
Description of drawings
Fig. 1 is the α-Al for preparing in the specific embodiment
2O
3Carrier surface adopts the ESEM sheet after electroless copper;
Fig. 2 is the stereoscan photograph of the ZSM-5 molecular sieve film for preparing in the specific embodiment;
Fig. 3 is the X-ray diffractogram of the ZSM-5 molecular sieve film for preparing in the specific embodiment;
Fig. 4 is the stereoscan photograph of the ZSM-5 molecular sieve film for preparing in the specific embodiment;
Fig. 5 is the α-Al for preparing in the specific embodiment
2O
3Carrier surface adopts the ESEM sheet after electroless copper;
Fig. 6 is the stereoscan photograph of the ZSM-5 molecular sieve film for preparing in the specific embodiment.
The specific embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.Following examples are that the present invention is further described, but do not limit the scope of the invention.
Traditional α-the Al of Comparative Examples 1
2O
3The method of the synthetic ZSM-5 molecular sieve of carrier surface
α-Al with a 20g
2O
3Powder and 4g water fully mix in mortar; Take the powder that 4g mixes and pour in mould, be placed on tablet press machine, apply the pressure of 2MP, kept 1 minute; After release, mortar is put in the compressing tablet taking-up broken into pieces, porphyrize; With the particle after 40 orders and 80 purpose sieves screening porphyrize.Take the powder after the above-mentioned screening of 2.3g, import in mould, be placed on tablet press machine, apply 10MP pressure, pressurize 1min, prepare α-Al
2O
3Carrier, drying at room temperature 1 day, put into Muffle furnace internal program intensification roasting.Heating schedule is as follows:
α-Al
2O
3Carrier boils cleaning with deionized water after taking out, and is dry rear standby under 60 ℃.α-Al with above-mentioned preparation
2O
3Carrier is placed in Zeolite synthesis liquid, and synthetic liquid is that TPAOH, ethyl orthosilicate, sodium aluminate, absolute ethyl alcohol and deionized water are TPAOH:SiO according to mol ratio
2: H
2O:Na
2The proportional arrangement of O:EtOH=9:25:595:0.13:100, be wherein TPAOH 6.24g, ethyl orthosilicate 4.86g, sodium aluminate 0.0078g, absolute ethyl alcohol 0.36g, deionized water 54g.In teflon-lined stainless steel hydro-thermal still, take out after 180 ℃ of Hydrothermal Synthesis 48h, use deionized water rinsing, calcining, obtain with α-Al under 450 ℃
2O
3For the molecular screen membrane of carrier, as shown in Figure 1.Resulting ZSM-5 molecular sieve film is graininess, uncrosslinked rete, poor air-tightness.
Embodiment 2 is through the α-Al of electroless copper
2O
3The method of the synthetic ZSM-5 molecular sieve of carrier surface
α-Al
2O
3The carrier preparation method is with Comparative Examples 1
Chemical-copper-plating process:
α-Al2O3 carrier is through alligatoring: the 5% volume ratio hydrofluoric acid HF aqueous solution, soak 5min under room temperature.
Sensitization: 3g stannous chloride SnCl22H2O is dissolved in 37.5% concentrated hydrochloric acid of 2ml, then adds 100ml water, soaks 5min under room temperature.
Activation: soak 5min in the 2g/L of the 200ml palladium bichloride PdCl2 aqueous solution.
At every liter of sulfur acid copper CuSO
412g, nickel sulfate hexahydrate NiSO
46H
2O, 1.5g, sodium potassium tartrate tetrahydrate C
4O
6H
4KNa40g, formaldehyde HCHO20ml, NaOH NaOH8g and sodium carbonate Na
2CO
3In the mixed liquor of 2g, 40 ℃, plating 5min.Carrier pattern after electroless copper as shown in Figure 2.
Prepare respectively 3 kinds of polyelectrolyte solutions: the polymine PEI of 0.02g is dissolved in preparation PEI solution in 5ml absolute ethyl alcohol and 5ml deionized water, the polystyrolsulfon acid PSS of 0.02g is dissolved in preparation PSS solution in 5ml absolute ethyl alcohol and 5ml deionized water, the sodium chloride nacl of the diallyl dimethyl ammoniumchloride PDDA of 0.01g and 0.05g is dissolved in the 10ml deionized water.
The carrier of electroless copper is soaked respectively successively in above-mentioned three kinds of solution, order is PEI, PSS, PEI, PSS, PDDA, PSS, each step immersion of PDDA 20min, all will rinse with deionization after per step immersion.
Prepare again the nano molecular sieve seed particles, be TPAOH TPAOH according to mol ratio: ethyl orthosilicate TEOS: NaOH NaOH: the ratio of absolute ethyl alcohol EtOH: water=9:25:0.26:100:595, be made into the synthetic liquid of crystal seed, in teflon-lined stainless steel hydro-thermal still, take out after 100 ℃ of Hydrothermal Synthesis 32h, obtain the nano molecular sieve seed particles to dry 12h under pH＜8,100 ℃ centrifugal three times with deionized water rinsing, ESEM as shown in Figure 3.The crystal seed that takes 1g is made into crystal seed suspension in the 100ml deionized water, and ultrasonic being uniformly dispersed, with the NH of 0.1mol/L
4OH transfers pH to 9.5.The carrier that soaked 3 kinds of polyelectrolyte solutions is immersed in 20min in this crystal seed suspension, dried for standby after taking out.
Be TPAOH according to mol ratio: the ratio of ethyl orthosilicate: sodium aluminate: absolute ethyl alcohol: water=9:25:0.13:100:595 is made into Zeolite synthesis liquid.With the α-Al after above-mentioned immersion
2O
3Carrier is placed in Zeolite synthesis liquid, in teflon-lined stainless steel hydro-thermal still, takes out after 180 ℃ of Hydrothermal Synthesis 48h, uses deionized water rinsing, and calcining, obtain with α-Al under 450 ℃
2O
3For the molecular screen membrane of carrier, as shown in Figure 3.Prepared ZSM-5 molecular sieve film, densification, evenly.X-ray diffractogram shows that also prepared molecular screen membrane is the ZSM-5 film, as shown in Figure 4.
With 25 ℃ of test nitrogen N of foam flowmeter room temperature
2By the flow of this rete, both sides differential pressure of membrane is 0.1MPa, its N
2Permeability is 5.9 * 10
-5Mols
-1M
-2Pa
-1.And this ZSM-5 film is to CO
2The passing through of gas do not have selective, shows the ZSM-5 rete free of pinholes, free from flaw of this technique preparation, continuously, and has high gas flux.
Embodiment 3 is through the α-Al of electroless copper
2O
3The method of the synthetic ZSM-5 molecular sieve of carrier surface
α-Al
2O
3The carrier preparation method is with Comparative Examples 1
Chemical-copper-plating process is with embodiment 2
At every liter of sulfur acid copper CuSO
412g, nickel sulfate hexahydrate NiSO
46H
2O, 1.5g, sodium potassium tartrate tetrahydrate C
4O
6H
4KNa40g, formaldehyde HCHO20ml, NaOH NaOH8g and sodium carbonate Na
2CO
3In the mixed liquor of 2g, 40 ℃, 10 minutes min of plating.Carrier pattern after electroless copper as shown in Figure 5.
Electroless copper α-Al
2O
3Carrier soaking technology in polyelectrolyte solution is 4-propyl bromide with embodiment 2 with mol ratio: the ratio of ethyl orthosilicate: sodium aluminate: water=10:150:1:10000 is made into Zeolite synthesis liquid.With the α-Al after above-mentioned immersion
2O
3Carrier is placed in Zeolite synthesis liquid, in teflon-lined stainless steel hydro-thermal still, takes out after 180 ℃ of Hydrothermal Synthesis 48h, uses deionized water rinsing, and calcining, obtain with α-Al under 450 ℃
2O
3For the molecular screen membrane of carrier, as shown in Figure 6.Prepared ZSM-5 molecular sieve film, densification, evenly.
Claims (7)
1. one kind at α-Al
2O
3The method of the synthetic ZSM-5 molecular sieve film of carrier surface comprises the following steps:
(1), with porous α-Al
2O
3Electroless copper is carried out on surface: described porous α-Al
2O
3Fully react and carry out electroless copper in the mixed liquor of sulfur acid copper, nickelous sulfate, sodium potassium tartrate tetrahydrate, formaldehyde, NaOH and sodium carbonate after alligatoring, sensitization, activation, washing successively;
(2), the self assembly crystal seed method prepares the ZSM-5 molecular sieve film layer by layer:
A. the preparation of nano molecular sieve crystal seed
After the synthetic liquid of ZSM-5 is fully reacted, take out product and dry, obtain the molecular sieve seed particles; Be configured to crystal seed suspension with deionized water, stand-by;
Prepare respectively the pure water mixed solution of pure water mixed solution, polystyrolsulfon acid PSS of polymine PEI and diallyl dimethyl ammoniumchloride PDDA and NaCl and mix the PDDA polyelectrolyte soak that is made into; Described pure water mixed solution is the mixed solution of second alcohol and water;
B. self assembly crystal seed layer layer by layer
The carrier of the electroless copper of preparation in (1) is soaked respectively successively in PEI alcohol water mixed solution, PSS alcohol water mixed solution, PEI alcohol water mixed solution, PSS alcohol water mixed solution, PDDA polyelectrolyte soak, PSS alcohol water mixed solution, PDDA polyelectrolyte soak and molecular sieve crystal seed suspension, fully after reaction, take out carrier and dry;
C. the preparation of molecular screen membrane
Dried carrier in b is put into the synthetic liquid of ZSM-5, and fully reaction is rear and dry, makes described molecular screen membrane.
2. the method for claim 1, wherein the synthetic liquid of described ZSM-5 is: TPAOH, ethyl orthosilicate, NaOH, absolute ethyl alcohol and deionized water are TPAOH:SiO according to mol ratio
2: H
2O:Na
2The Zeolite synthesis liquid that the ratio of O:EtOH=9:25:595:0.13:100 is made into.
3. the method for claim 1, wherein porous α-Al in step 1
2O
3The concrete preparation process of carrier is:
Batch mixing: with α-Al
2O
3Powder and water fully mix in mortar;
Granulation: the powder that will mix is poured in mould, is placed on granulation on tablet press machine;
After release, mortar is put in the compressing tablet taking-up broken into pieces, porphyrize;
Compressing tablet: similar to granulation process, the powder after porphyrize is imported in mould, be placed on compressing tablet on tablet press machine;
Calcining: the porous alumina carrier that presses is taken out, and drying at room temperature, put into Muffle furnace internal program intensification roasting; After taking out, carrier boils cleaning, dry rear standby with deionized water.
4. the method for claim 1, wherein porous α-Al in step (1)
2O
3The concrete operation step of Electroless copper is:
1) carrier pretreatment
With carrier successively through alligatoring, sensitization and activation;
2) electroless copper: with pretreated carrier at every liter of sulfur acid copper CuSO
412g, nickel sulfate hexahydrate NiSO
46H
2O1.5g, sodium potassium tartrate tetrahydrate C
4O
6H
4KNa40g, formaldehyde HCHO20ml, NaOH NaOH8g and sodium carbonate Na
2CO
3Fully reaction in the mixed liquor of 2g.
5. the method for claim 1, wherein in step (2) respectively configuration concentration be the PEI alcohol water mixed solution of 2mg/ml and the PSS alcohol water mixed solution of 2mg/ml, described pure water mixed solution consists of for 1:1 by volume absolute ethyl alcohol and deionized water; The NaCl of the PDDA of 1mg/ml and 0.1mol/L 1:1 mixing by volume is made into PDDA polyelectrolyte soak.
6. method as claimed in claim 2, wherein the concrete operations of step c are: with TPAOH, ethyl orthosilicate, NaOH, absolute ethyl alcohol and deionized water, according to mol ratio, be TPAOH:SiO
2: H
2O:Na
2The ratio of O:EtOH=9:25:595:0.13:100, be made into Zeolite synthesis liquid, after continuous stirring 24h, takes out after 180 ℃ of Hydrothermal Synthesis 48h, uses deionized water rinsing, and is dry under 100 ℃, obtains the molecular sieve rete.
7. one kind at α-Al
2O
3The ZSM-5 molecular sieve film that carrier surface is synthetic, is characterized in that described molecular screen membrane is by the described method preparation of claim 1-6.
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| CN104846371A (en) * | 2015-05-13 | 2015-08-19 | 吉林大学 | Method for preparing molecular sieve coating layer on surface of medical magnesium alloy |
| CN105289323A (en) * | 2015-11-10 | 2016-02-03 | 浙江大学 | Method for preparing high performance silicalite zeolite membrane |
| CN106283187A (en) * | 2015-05-29 | 2017-01-04 | 武汉理工大学 | A kind of ordered big hole-mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline with opal structural and synthetic method thereof |
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| CN104846371A (en) * | 2015-05-13 | 2015-08-19 | 吉林大学 | Method for preparing molecular sieve coating layer on surface of medical magnesium alloy |
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| CN108283942A (en) * | 2017-01-10 | 2018-07-17 | 中国石油化工股份有限公司 | Modified alpha-alumina supports and preparation method thereof and silver catalyst and application |
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| CN112624141A (en) * | 2019-10-08 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of MFI molecular sieve membrane |
| CN112624141B (en) * | 2019-10-08 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of MFI molecular sieve membrane |
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