CN107029561A - A kind of preparation method of the MFI-type molecular screen membrane of h0h orientations - Google Patents
A kind of preparation method of the MFI-type molecular screen membrane of h0h orientations Download PDFInfo
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- CN107029561A CN107029561A CN201710312259.3A CN201710312259A CN107029561A CN 107029561 A CN107029561 A CN 107029561A CN 201710312259 A CN201710312259 A CN 201710312259A CN 107029561 A CN107029561 A CN 107029561A
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- mfi
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- molecular screen
- screen membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000013078 crystal Substances 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000002808 molecular sieve Substances 0.000 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 claims abstract description 46
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 238000003786 synthesis reaction Methods 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229920006317 cationic polymer Polymers 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 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
- 238000001354 calcination Methods 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 125000005131 dialkylammonium group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- -1 hydrocarbyl alkoxy silanes Chemical class 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- YRHAJIIKYFCUTG-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;bromide Chemical group [Br-].C=CC[N+](C)(C)CC=C YRHAJIIKYFCUTG-UHFFFAOYSA-M 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- LISZMWMCSIUBEJ-UHFFFAOYSA-N n,n-dimethylbutan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH+](C)C LISZMWMCSIUBEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001338 self-assembly Methods 0.000 abstract description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001282 iso-butane Substances 0.000 abstract description 4
- 235000013847 iso-butane Nutrition 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000004907 flux Effects 0.000 abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000000280 densification Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 27
- 238000002474 experimental method Methods 0.000 description 11
- 238000003618 dip coating Methods 0.000 description 9
- 230000012010 growth Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZBTYSPGRMHUEKZ-UHFFFAOYSA-N CC[Cl]CC Chemical compound CC[Cl]CC ZBTYSPGRMHUEKZ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HDITUCONWLWUJR-UHFFFAOYSA-N diethylazanium;chloride Chemical compound [Cl-].CC[NH2+]CC HDITUCONWLWUJR-UHFFFAOYSA-N 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
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprise the following steps：(1) short cylinder MFI-type molecular sieve nanosized seeds are prepared；(2) one layer of densification is prepared on porous supporting body by electric charge self assembly mode and there is the MFI crystal seed layers of orientation texture；(3) prepare to be formed with continuous fine and close hoh orientation MFI-type molecular screen membranes on the porous supporting body surface of crystallization by hydrothermal synthesis method again.The MFI-type molecular screen membrane of orientation texture can effectively reduce transport resistance, improve the permeation flux and selectivity of film.In separation normal butane/iso-butane (n C4H10/i‑C4H10), propylene/nitrogen (C3H6/N2) etc. mixed system when with good separating property.
Description
Technical field
The present invention relates to a kind of synthetic method of MFI-type molecular screen membrane, made under more particularly to a kind of low temperature synthesis condition
The method of standby height hoh orientation MFI-type molecular screen membranes.
Background technology
Membrane separation technique have the advantages that efficiently, energy-saving and environmental protection, obtained in fields such as chemical industry, food, medicine, environmental protection, metallurgy
To being increasingly widely applied.Molecular screen membrane is the focus of technical field of membrane research in recent years, prepare zero defect, performance it is stable,
The domestic and international core topic paid close attention to jointly is had become with the molecular screen membrane of high flux and high selectivity.Wherein MFI type is divided
Sub- sieve membrane (including Silicalite-1 and ZSM-5 molecular sieve film) is particularly subject to the concern of people.Main cause is MFI type molecule
Sifter device has the pore canal system structure that unique two kinds are cross-linked with each other, and one is the sinusoidal duct (0.51 × 0.55nm) of a direction of principal axis,
Another is the straight hole road (0.53 × 0.56nm) of b direction of principal axis.The duct of MFI-type molecular sieve and many common molecular diameter phases
Closely, can be for a variety of mixed systems of separation, such as admixture of gas, liquid mixture.In addition Silicalite-1 skeleton
Structure is free of Al, stable SiO4Tetrahedron causes Silicalite-1 type molecular screen membranes to have good hydrothermal stability and dredge
Aqueous and mechanical strength.
Under normal circumstances, relative to the molecular screen membrane of No yield point, the film layer crystal of the molecular screen membrane of orientation has height phase
The same direction of growth reduces the generation of intergranular defect, shows the superiority of uniqueness.In-situ synthesis is to prepare orientation molecule
One of simplest method of sieve membrane.Li et al. (Chemistry of Materials.2003,15 (14)：2687-2689.；
Journal of the American Chemical Society.2004,126 (13)：4122-4123.) in stainless steel electrode
Upper to be prepared for the MFI-type molecular screen membrane that high b axles are orientated by in-situ synthesis, synthesized film has good molecule to molecule
The effect of screening, has good application prospect in terms of sensor material.In-situ synthesis is although relatively easy, but to experiment
Condition and carrier material are more sensitive.Attempted when using in-situ synthesis in gold and the MFI type that synthesis b axles are orientated on platinum electrode
During molecular screen membrane, all end in failure.
Another main method for preparing orientating type molecular screen membrane is crystal seed method, repeats preparative relative to fabricated in situ
Method is higher.The quality of crystal seed coating has a significant impact to the height of the degree of orientation of film forming, therefore the technique of coating is most important.
Mintova et al. (Advanced Materials, 2010,13 (24)：1880-1883.) use spin-coating method i.e. by seed-solution
It is added drop-wise on carrier, by the high speed rotation of carrier so as to obtain MFI type crystal seed layer, this method is simple to operate but is only applicable to
Chip carrier, is industrially restricted.Yoon et al. (Advanced Materials, 2000,12 (15)；1114-1117.)
Crystal seed is coated in by supporting body surface using articulation agent, high-quality oriented seed crystal layer can be prepared, but this method is in grafting
Need to carry out in the organic solvents such as toluene with the process of bonding connection and need inert gas environment to be carried out under protecting, operate into
This height and it is unfavorable for environmental protection.In addition, Yoon et al. (Angewandte Chemie International
Edition.2007,46 (17)：3087-3090.) under the hydrogen bond action between molecular sieve and supporter, molecular sieve is placed on
The mode pressed with finger is set quickly to be prepared for the crystal seed layer of b axles orientation, this crystal seed layer for preparing orientation by hand on sheet glass
It can only prepare and can not industrially use on a large scale in smooth carrier surface.Recently, Wang Zheng et al. (Journal of
Materials Science, 2016,51 (6)：3257-3270.) high-quality crystalline substance is prepared using Langmuir-Blodgett methods
Layer is planted, i.e., crystal seed is distributed in organic solvent, is then injected into water, adjustment LB film balances slide cane extrusion speed, then
Supporter is slowly lifted out, but this method is only applicable to chip carrier, is not suitable for tubular carrier, especially tubulose
Carrier inner membrance is more inapplicable, it is difficult to industrialization generation.
What report was most at present is to prepare the method that b axles are orientated MFI-type molecular screen membrane.Patent CN 105800636A are provided
A kind of method, adds MFI-type molecular sieve in super-dilute synthetic fluid, and at 150-180 DEG C prepared by secondary growth method epitaxial growth
MFI-type molecular sieve without Luan Jing, prepares on chip supporter that the crystal seed layer being orientated with b axles is secondary to be closed using the molecular sieve
MFI-type molecular screen membrane is orientated into b axles.The A of patent CN 104891519 disclose one kind to be had by adding ammonium salt in Synthesis liquid
Effect ground suppresses Luan Jing and scribbles generation on the chip carrier of b axles oriented seed crystal layer, prepares b axle orientation MFI-type molecular screen membranes
Method.The A of patent CN 104556107 disclose a kind of by scribbling the chip of b axles oriented seed crystal layer under neutral synthesis condition
The method that b axle orientation MFI-type molecular screen membranes are prepared on carrier.Patent CN 102126736A pass through Control architecture agent tetrapropyl
The consumption of ammonium hydroxide prepares b axle orientation MFI-type molecular screen membranes on the chip carrier for scribbling b axles oriented seed crystal layer.With it is upper
State unlike patent, the A of patent CN 101643218 are heated there is provided a kind of microwave, and fabricated in situ b axles take on chip carrier
The method of tropism MFI-type molecular screen membrane.The A1 of patent US 2009291046 (2009142408 A2 of A, WO of CN 101585545,
A2 of EP 2297037 etc.) provide by friction or be squeezed in zeolite or zeolites point of the formation with different-thickness on base material
Son sieve crystal seed, the method that diauxic growth synthesizes b axle orientation MFI-type molecular screen membranes.The A of patent CN 1332114 provide one kind
With " double template " (double template that i.e. methenamine or derivatives thereof is constituted with normal chain alkyl amine or hydroxylation tetrapropyl ammonium) water
The method that thermal synthesis method prepares the MFI-type molecular screen membrane of b axles orientation.
The preparation method of the orientation MFI-type molecular screen membrane of above-mentioned disclosure is substantially to scribble the piece of b axles oriented seed crystal layer
Prepared on formula carrier, and be the MFI-type molecular screen membrane of b axle orientations.It is industrial that chip film largely limits its
Amplification application.
The content of the invention
The purpose of this method is to provide a kind of simple operations and the recursive MFI-type molecular sieve for preparing h0h orientations
The method of film, prepared height-oriented MFI-type molecular screen membrane has good separating property.
The molecular screen membrane with orientation texture is prepared on carrier can effectively reduce energy expenditure in transmitting procedure, improve
The permeation flux and selectivity of film, and the molecular screen membrane of more random orientation has better performance.The present invention is with nanometer short cylinder
Molecular sieve crystal surface is become positively charged lotus, passes through electric charge self assembly as crystal seed by MFI-type molecular sieve using cationic polymer
Mode prepares one layer of densification and the MFI crystal seed layers with orientation texture on negatively charged porous ceramic support, then passes through
The crystal seed layer of preparation prepares the MFI-type molecular screen membrane of height hoh orientations using hydrothermal synthesis method.MFI-type molecular sieve is in hoh
There is sinusoidal duct (0.51 × 0.55nm) on direction, and there are straight channels (0.53 × 0.56nm) on b direction of principal axis.Dividing
During from normal butane (0.47nm)/iso-butane (0.53nm) mixture, on hoh directions on less sinusoidal orifice throat ratio b direction of principal axis
Duct has more preferable duct screening function.
For achieving the above object, the technical solution adopted by the present invention is：
A kind of preparation method of the MFI-type molecular screen membrane of h0h orientations, comprises the following steps：
1) prepared by crystal seed：It is by each component mol ratio by silicon source, template (SDA) and water：SiO2∶SDA∶H2O=1:
(0.16~0.44): (10~30) mixing, the colloidal sol formed is fitted into reactor after 2~50 hours in stirring at normal temperature aging
Water-filling thermal response, synthesis temperature is 90~160 DEG C, and generated time is 12~96 hours, and reaction terminates rear product by centrifugation, water
Neutrality is washed till, dries, obtains a nanometer short cylinder MFI-type molecular sieve；
2) supporting body surface load crystal seed：After the nano MFI-type molecular sieve crystal that synthesis is obtained in step (1) is ground,
Appropriate crystal is added in water and is uniformly dispersed under ultrasound, the suspension of MFI-type molecular sieve is obtained, suspension gross mass is added
0.1~1% cationic polymer polydiene base dialkyl ammonium salt；By porous supporting body vertical immersion in MFI-type molecular sieve
Suspension in, then at the uniform velocity proposed with 0.5-5cm/min speed, dry, obtain a nanometer short cylinder crystal tiling open support
The MFI-type molecular sieve crystal seed layer for the orientation texture that body surface face is formed, seed layer thickness is about 0.1~3 μm；
3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss h0h orientations：Silicon source, template (SDA) and water are pressed into each group centimorgan
You are at ratio：SiO2∶SDA∶H2O=1: (0.05~0.5): (50~120) mixing, the colloidal sol formed stirs aging 2 at normal temperatures
The clear sol stablized for~10 hours；The porous supporting body for the seeding that step (2) is obtained is inserted in described colloidal sol,
Hydrothermal crystallizing 12~36 hours under the conditions of 80~155 DEG C, after reaction terminates, film is through rinsing, soaking, drying and calcination processing,
The MFI-type molecular screen membrane of h0h orientations is made.
In the inventive method, described silicon source is aliphatic group alkoxy silane, or aliphatic group alkoxy silane and four
The mixture of Ethoxysilane, Ludox or silester, aliphatic group alkoxy silane structure expression is：(CnH2n+1Or
CnH2n-1)x(CmH2m+1O)4-xSi, wherein n=5~20, m=1~4 and x=1~3, when silicon source is mixture, aliphatic group alkane
TMOS：The mol ratio of tetraethoxysilane, Ludox or silester is 1~10.
In this method of the present invention, described template be one kind in TPAOH, di-n-propylamine or cyclohexylamine or
It is several.
In this method of the present invention, the MFI-type molecular sieve crystal seed prepared by step (1) is the equal of 80~300nm diameter ranges
Even short cylinder crystal seed.
In this method of the present invention, step 2) described in the preferred perforated tubular supporter of porous supporting body, average pore size is about
0.1~10 μm, porosity is about 30~60%, and pipe external diameter is 8~20mm, 1~3mm of thickness of pipe wall.The porous supporting body is selected from
Aluminum oxide, mullite, cordierite or silica, its surface show electronegativity.
In this method of the present invention, step 2) described in mass concentration of the MFI-type molecular sieve crystal in suspension it is excellent
Elect 0.1~3% as.
Preferably, step (2) cationic polymer poly dialkylene dialkyl ammonium salt is selected from diallyl dimethyl bromine
Change ammonium, polydiene Butyldimethyl ammonium bromide, polydiene propyl group diethylammonium chloride or diallyl dimethyl ammoniumchloride.
In this method of the present invention, step 2) coated by electric charge self assembly effect using dip-coating (Dip-coating) mode
Crystal seed, adds cationic polymer polydiene base dialkyl ammonium salt and causes the MFI-type molecular sieve surface in suspension to carry positive electricity
Lotus, after the porous supporting body vertical immersion of aobvious electronegativity, branch can be laid in by electric charge self assembly by nanometer short cylinder crystal
Support body surface, forms the MFI-type molecular sieve crystal seed layer of orientation texture.
Preferably, step 2) described in crystal seed layer be laid in porous supporting body surface for 1-2 layers of short cylinder MFI type crystal,
Seed layer thickness is controlled in 100~500nm.
Preferably, calcining heat is 300~700 DEG C in step (3)；Calcination time is 3~48 hours, heating and cooling speed
Rate is 0.1~3 DEG C/min.
MFI-type molecular screen membrane prepared by the inventive method has height hoh preferred orientations, and preferred orientation degree (CPO) is
70~100%.
Beneficial effects of the present invention：
The preparation method of the MFI-type molecular screen membrane of the h0h orientations of the present invention, using the MFI-type molecular sieve of nanometer short cylinder,
Acted on by electric charge self assembly, load the crystal seed layer for obtaining that there is orientation on porous supporting body using dip coating manner, and be adapted to
Crystal seed is coated in the inside and outside wall of tubular support；Prepared again through secondary hydro-thermal method by regulating and controlling synthesis condition with height
The MFI-type molecular screen membrane of hoh oriented growths.The MFI-type molecular screen membrane of the inventive method synthesis, separates normal butane/iso-butane
(n-/i-C4H10) mixed gas when, can reach selectivity is 29, and the infiltration rate of normal butane is 3.1 × 10-7mol(m2 s
Pa)-1(=926GPU), (test condition is 60 DEG C and 0.05Mpa to the tubulose MFI-type molecular screen membrane reported higher than current document
Pressure difference).Also there is very high infiltration rate when separating propylene/nitrogen mixture, selectivity is significantly larger than Knudsen diffusion.
The preparation method step of this method is simple, and repeatability preferably, and can prepare h0h orientations on tubular support
MFI-type molecular screen membrane, the prospect with industrialization development.
Brief description of the drawings
Fig. 1 is the MFI-type molecular sieve crystal (Silicalite-1 molecular sieves) and MFI-type molecular sieve prepared in embodiment 1
X-ray diffraction (XRD) figure of film；
Fig. 2 is SEM (SEM) figure of the MFI-type molecular sieve crystal prepared in embodiment 1；
Fig. 3 is tubular support crystal seed coating procedure schematic diagram in embodiment 1；
Fig. 4 is the surface SEM figures of the crystal seed layer of alumina support surface preparation in embodiment 1；
Fig. 5 is the MFI-type molecular screen membrane surface SEM figures of alumina support surface preparation in embodiment 1；
Fig. 6 is the MFI-type molecular screen membrane section SEM figures of alumina support surface preparation in embodiment 1；
Fig. 7 is the XRD of the No yield point MFI-type molecular screen membrane prepared on alumina support surface in comparative example 1 and 2.
Embodiment
Technical solutions according to the invention are further described in detail below by specific embodiment, but are necessary
Point out that following examples are served only for the description to the content of the invention, do not constitute limiting the scope of the invention.
Embodiment 1
A kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprises the following steps：
(1) prepared by crystal seed：By silicon source octadecyl trimethoxysilane, template TPAOH (TPAOH) and
Water is by each component mol ratio：SiO2∶SDA∶H2Mixed under the conditions of O=1: 0.2: 19.2, the colloidal sol formed is stirred at room temperature always
The colloidal sol clarified after changing 6 hours.Then colloidal sol is transferred in inner liner of reaction kettle, fills kettle, sealed, be put into 140 DEG C of baking
Static hydrothermal crystallization is synthesized 48 hours in case.Reaction terminates rear product by the ultrasonic disperse that repeatedly centrifuges, adds water until being washed to
Neutrality, obtains the nanometer short cylinder MFI-type molecular sieve of uniform-dimension, drying for standby.
(2) supporting body surface load crystal seed：After the nano MFI-type molecular sieve crystal that synthesis is obtained in step (1) is ground,
Add appropriate crystal to be uniformly dispersed in water and under ultrasound, be made into the suspension for the MFI-type molecular sieve for accounting for gross mass 0.2%,
0.5% cationic polymer diallyl dimethyl ammonium bromide of suspension gross mass is added in suspension so that point
Son sieve surface carries positive charge；Then crystal seed is coated using dip-coating (Dip-coating) mode by electric charge self assembly effect, will
Show the tubular porous aluminum oxide vertical immersion of electronegativity in the suspension of MFI-type molecular sieve, then with 2cm/min speed at the uniform velocity
Propose, dry, nanometer short cylinder crystal is laid on supporter by electric charge self assembly, form the MFI type point of orientation texture
Son sieve crystal seed layer, seed layer thickness is about 0.4 μ m-thick, is dried or oven drying.
(3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss height h0h orientations：By silicon source octadecyl trimethoxysilane,
Template TPAOH and water are by each component mol ratio：SiO2∶SDA∶H2O=1: 0.12: 60 mixing, are formed
The clear sol that colloidal sol is stablized for 6 hours in stirring aging at normal temperatures；The open support for the seeding that step (2) is obtained
Body is inserted in described colloidal sol, hydrothermal crystallizing 30 hours under the conditions of 140 DEG C, after reaction completely, and film is through rinsing, immersion, dry,
And calcined 6 hours at 550 DEG C, heating rate of temperature fall is 1 DEG C/min, and the MFI-type molecular screen membrane of height h0h orientations is made.
MFI-type molecular sieve crystal XRD characterization results are as shown in b in Fig. 1 made from step (1), with MFI-type molecular sieve standard
Collection of illustrative plates (a in Fig. 1) is complied fully with, and is pure phase MFI type crystal.
Fig. 2 schemes for the SEM of the molecular sieve crystal of synthesis.The MFI type of synthesis is in short cylinder, and individual particle diameter is in 160nm
Left and right.
Step (2) is using dip-coating (Dip-coating) mode in tubular porous oxidation aluminium surface coating crystal seed, and Fig. 3 is many
Hole the dip-coating of supporter crystal seed (Dip-coating) process schematic, porous supporting body is vertical with can rate controlling under mechanical pulling machine
Rate is at the uniform velocity lifted.Fig. 4 shows the surface Electronic Speculum that one layer of MFI-type molecular sieve crystal seed is deposited on tabular alumina porous supporting body
Figure, crystal seed is close in supporting body surface, and supporting body surface is all covered by crystal seed.
Fig. 5 shows the surface microstructure of the MFI-type molecular screen membrane synthesized on tabular alumina porous supporting body, can
To find out the crystal of column in film surface compact growth, film layer is very fine and close and very smooth.
Fig. 6 shows the section microstructure of the MFI-type molecular screen membrane synthesized on tabular alumina porous supporting body, film
Layer growth is continuous fine and close, and thickness is about 8 μm.
C in the XRD such as Fig. 1 of the MFI-type molecular screen membrane of synthesis, as seen from the figure except faint [020] peak,
Remaining [101], [102], [501], [303], [104], [503], [305] are the peaks in h0h directions, show synthesized film
It is orientated for h0h.
In order to preferably represent degree of orientation that the preferred orientation of sample grows, disclosed document (Langmuir.30
(2014)4531-4534；J.Mater.Sci.51(2016)3257-3270；Microporous Mesoporous Mater.28
(1999) 185-194.) define preferred orientation degree CPO (crystallographic preferred orientation)：
I in formulasAnd IpRepresent the diffracted intensity with reference to sample and test specimens diffraction maximum respectively because [303] of sample and
[020] diffraction maximum is not overlapping and has higher intensity, and we calculate CPO values from both, then CPO[303]/[020]Size
Then represent Degree of Preferred Orientation of the film layer crystal along h0h.CPO[303]/[020]=1 represents that preferably all crystal are selected along h0h
Especially it is orientated；
CPO[303]/[020]=0.50 represents to belong to h0h orientations；CPO[303]/[020]=0.75 represents to belong to high h0h orientations
's；CPO[303]/[020]=0 represents that crystal is random growth No yield point.The MFI-type molecular screen membrane for being computed synthesizing in embodiment 1
CPO[303]/[020]=0.97, the crystal for showing in film layer 97% is to be orientated preferential growth along h0h, with very high orientation
Property.
The gas separating property of film can by equimolar than n-/i-C4H10Mixed gas tests separating property, with gas
Transmitance P and separation factor SF two parameters are represented.Wherein, gas permeation rate P represents to pass through under unit interval, unit pressure
The gas gross of per membrane area, unit is mol/ (m2s Pa)；
P=N/ (A × t × △ P)
Separation factor SF is used for the height of evaluated for film separative efficiency, such as following formula
In formula, (y1/y2)p、(y1/y2)fThe ratio of components of per-meate side and feed side normal butane and iso-butane is represented respectively, is tested
Method uses purge gass method.
The film (M1) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Embodiment 2
A kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprises the following steps：
(1) prepared by crystal seed：Preparation process is identical with the step of embodiment 1 (1), the difference is that template (SDA) is equimolar
Tetrapropyl hydrogenation ammonium and di-n-propylamine mixture, each component mol ratio is in colloidal sol：SiO2∶SDA∶H2O=1: 0.4: 30；
Hydrothermal Synthesiss 36 hours at 160 DEG C.
(2) supporting body surface load crystal seed：Process is identical with the step of embodiment 1 (2).The difference is that seed-solution is quality
Fraction is 0.05% suspension, adds 0.5% cationic polymer polydiene propyl group diethyl chlorine of suspension gross mass
Change ammonium.
(3) molecular screen membrane is synthesized：Preparation process is identical with the step of embodiment 1 (3), the difference is that aging is stirred 4 hours, closes
It it is 130 DEG C into temperature, the reaction time is 36 hours.
The film (M2) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Embodiment 3
A kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprises the following steps：
(1) prepared by crystal seed：Preparation process is identical with the step of embodiment 1 (1).
(2) supporting body surface load crystal seed：Process is identical with the step of embodiment 1 (2).The difference is that seed-solution is quality
Fraction is 0.2% suspension.Porous supporting body is at the uniform velocity proposed with 0.4cm/min speed.
(3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss height h0h orientations：Preparation process and the step of embodiment 1 (3) phase
Together, unlike silicon source be tetraethoxysilane, template be equimolar than tetrapropyl oxyammonia and hexamethylene mixing
Thing, aging is stirred 12 hours, and synthesis temperature is 145 degree, 24 hours time.
The film (M3) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Embodiment 4
A kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprises the following steps：
(1) prepared by crystal seed：Preparation process is identical with the step of embodiment 1 (1), the difference is that silicon source is tetraethoxysilane,
Template be equimolar than tetrapropyl oxyammonia and hexamethylene mixture, be by each component mol ratio：SiO2∶SDA∶H2O
=1: 0.16: 12 mixing.When stirring aging 10, crystallization is synthesized 72 hours.
(2) supporting body surface load crystal seed：Process is identical with the step of embodiment 1 (2).The difference is that adding the total matter of suspension
0.2% cationic polymer diallyl dimethyl ammoniumchloride of amount.
(3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss height h0h orientations：The difference is that silicon source is tetraethoxysilane,
Template be equimolar than tetrapropyl oxyammonia and hexamethylene mixture.
The film (M4) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Embodiment 5
A kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprises the following steps：
(1) prepared by crystal seed：Preparation process is identical with the step of embodiment 1 (1), the difference is that silicon source is equimolar hexadecane
The mixture of ethyl triethoxy silicane alkane and Ludox, each component mol ratio is：SiO2∶SDA∶H2O=1: 0.3: 25.
(2) supporting body surface load crystal seed：Process is identical with the step of embodiment 1 (2).The difference is that adding the total matter of suspension
0.8% cationic polymer diallyl dimethyl ammoniumchloride of amount.
(3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss height h0h orientations：Preparation process and the step of embodiment 1 (3) phase
Together, silicon source unlike is the mixture of equimolar hexadecyl and Ludox.
The film (M5) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Embodiment 6
A kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprises the following steps：
(1) prepared by crystal seed：Preparation process is identical with the step of embodiment 1 (1), the difference is that silicon source is dodecyl trimethoxy
The mixture of base silane and tetraethoxysilane, mol ratio is 2: 1.
(2) supporting body surface load crystal seed：Preparation process is identical with the step of embodiment 1 (2).
(3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss height h0h orientations：Preparation process and the step of embodiment 1 (3) phase
Together, silicon source is the mixture of dodecyltrimethoxysilane and tetraethoxysilane unlike, and mol ratio is 2: 1.
The film (M6) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Embodiment 7
A kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprises the following steps：
(1) prepared by crystal seed：Preparation process is identical with the step of embodiment 1 (1).
(2) supporting body surface load crystal seed：Process is identical with the step of embodiment 1 (2).
(3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss height h0h orientations：Preparation process and the step of embodiment 1 (3) phase
Together.Each component mol ratio is in the colloidal sol that difference is：SiO2∶SDA∶H2O=1: 0.12: 60.
The film (M7) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Embodiment 8
A kind of preparation method of the MFI-type molecular screen membrane of height h0h orientations, comprises the following steps：
(1) prepared by crystal seed：Preparation process is identical with the step of embodiment 1 (1).
(2) supporting body surface load crystal seed：Process is identical with the step of embodiment 1 (2).
(3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss height h0h orientations：：Preparation process and the step of embodiment 1 (3) phase
Together, synthesis temperature unlike is 120 DEG C.
The film (M8) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Comparative example 1
A kind of preparation method of MFI-type molecular screen membrane, comprises the following steps：
(1) prepared by micron order crystal seed：Silicon source Ludox, template TPAOH (TPAOH) and water are pressed into each group
Point mol ratio is：SiO2∶SDA∶H2Mixed under the conditions of O=1: 0.2: 60, after aging is stirred at room temperature 6 hours in the colloidal sol formed
Obtain clarifying Synthesis liquid.Then colloidal sol is transferred in inner liner of reaction kettle, fills kettle, sealing is put into Static Water in 180 DEG C of baking oven
Thermal crystallisation is synthesized 48 hours.Reaction terminate rear product by repeatedly centrifuging, the ultrasonic disperse that adds water, be washed to neutrality, drying for standby.
(2) supporting body surface load crystal seed：Preparation process is identical with the step of embodiment 1 (2), the difference is that being suspended in crystal seed
Without cationic polymer in liquid.
(3) molecular screen membrane is synthesized：Preparation process is identical with the step of embodiment 1 (3), the difference is that synthesis temperature is 170 DEG C.
Step (1) obtains MFI-type molecular sieve seed sized for 5 μm.Step (2) prepare MFI-type molecular sieve crystal seed layer and
MFI-type molecular screen membrane prepared by step (3) is random orientation.The XRD of the MFI-type molecular screen membrane of preparation is as shown in fig. 7, almost institute
Some characteristic peaks are all shown, without obvious orientation attributes.
The film (M9) of preparation is used for 60 DEG C, n-/i-C4H10(50/50) gas separating property sign, gas are carried out in system
Separating experiment the results are shown in Table 1.
Comparative example 2
A kind of preparation method of MFI-type molecular screen membrane, comprises the following steps：
(1) prepared by crystal seed：Preparation process is identical with the step of embodiment 1 (1).
(2) supporting body surface load crystal seed：Crystal seed coating is carried out using infriction, by MFI type prepared in step (1)
Molecular sieve crystal is coated 2 minutes in supporting body surface by mechanical force repeatedly using hairbrush.Again by cotton swab unnecessary
Crystal seed is wiped.
(3) molecular screen membrane is synthesized：Preparation process is identical with the step of embodiment 1 (3), the difference is that synthesis temperature is 190 DEG C.
MFI-type molecular screen membrane prepared by MFI-type molecular sieve crystal seed layer and step (3) prepared by step (2) is random orientation.
The XRD of the MFI-type molecular sieve of preparation is as shown in fig. 7, almost all of characteristic peak is all shown, without obvious orientation attributes.
The film (M10) of preparation in 60 DEG C, n-/i-C4H10 (50/50) system for carrying out gas separating property sign, gas
Body separating experiment the results are shown in Table 1.
N-/i-C4H10 (50/50) separating property (60 DEG C, feed pressure is 0.05Mpa) of the MFI-type molecular screen membrane of table 1.
Claims (10)
1. a kind of preparation method of the MFI-type molecular screen membrane of h0h orientations, it is characterised in that comprise the following steps：
1) prepared by crystal seed：It is by each component mol ratio by silicon source, template SDA and water：SiO2∶SDA∶H2O=1: (0.16~
0.44): (10~30) mixing, the colloidal sol formed is fitted into reactor after 2~50 hours in stirring at normal temperature aging carries out hydro-thermal
Reaction, synthesis temperature is 90~160 DEG C, and generated time is 12~96 hours, during reaction terminates rear product by centrifugation, being washed to
Property, dry, obtain a nanometer short cylinder MFI-type molecular sieve；
2) supporting body surface load crystal seed：After the nano MFI-type molecular sieve crystal that synthesis is obtained in step (1) is ground, in water
It is middle to add appropriate crystal and be uniformly dispersed under ultrasound, the suspension of MFI-type molecular sieve is obtained, suspension gross mass is added
0.1~1% cationic polymer polydiene base dialkyl ammonium salt；By porous supporting body vertical immersion in MFI-type molecular sieve
In suspension, then at the uniform velocity proposed with 0.5-5cm/min speed, dried, obtain a nanometer short cylinder crystal tiling porous supporting body
The MFI-type molecular sieve crystal seed layer for the orientation texture that surface is formed, seed layer thickness is 0.1~3 μm；
3) MFI-type molecular screen membrane of secondary Hydrothermal Synthesiss h0h orientations：Silicon source, template SDA and water are pressed into each component mol ratio
For：SiO2∶SDA∶H2O=1: (0.05~0.5): (50~120) mixing, the colloidal sol formed stirs aging 2~10 at normal temperatures
The clear sol that hour is stablized；The porous supporting body for the seeding that step (2) is obtained is inserted in described colloidal sol, in 80
Hydrothermal crystallizing 12~36 hours under the conditions of~155 DEG C, after reaction terminates, film is through rinsing, soaking, drying and calcination processing, is made
The MFI-type molecular screen membrane of h0h orientations.
2. according to the method described in claim 1, it is characterised in that described silicon source is aliphatic group alkoxy silane, or fat
Fat hydrocarbyl alkoxy silanes and the mixture of tetraethoxysilane, Ludox or silester, aliphatic group alkoxy silane knot
Structure expression formula is：(CnH2n+1Or CnH2n-1)x(CmH2m+1O)4-xSi, wherein n=5~20, m=1~4 and x=1~3；Work as silicon source
During for mixture, aliphatic group alkoxy silane：The mol ratio of tetraethoxysilane, Ludox or silester is 1~10.
3. according to the method described in claim 1, it is characterised in that described template is TPAOH, di-n-propylamine
Or the one or more in cyclohexylamine.
4. according to the method described in claim 1, it is characterised in that in step (1), prepared MFI-type molecular sieve crystal seed is
The uniform short cylinder crystal seed of 80~300nm diameter ranges.
5. preparation method according to claim 1, it is characterised in that step 2) described in porous supporting body be perforated tubular
Supporter, average pore size is about 0.1~10 μm, and porosity is about 30~60%, and pipe external diameter is 8~20mm, 1~3mm of thickness of pipe wall.
6. preparation method according to claim 1, it is characterised in that the porous supporting body be selected from aluminum oxide, mullite,
Cordierite or silica.
7. preparation method according to claim 1, it is characterised in that in step (2), crystal seed layer is 1-2 layers of short cylinder MFI
Type crystal is laid in supporting body surface, and seed layer thickness is controlled in 100~500nm.
8. preparation method according to claim 1, it is characterised in that in step (2), the MFI-type molecular sieve crystal exists
Mass concentration in suspension is 0.1~3%.
9. preparation method according to claim 1, it is characterised in that in step (2), described cationic polymer poly- two
Alkenyl dialkyl ammonium salt is selected from diallyl dimethyl ammonium bromide, polydiene Butyldimethyl ammonium bromide, polydiene propyl group two
Ethyl ammonium chloride or diallyl dimethyl ammoniumchloride.
10. preparation method according to claim 1, it is characterised in that prepared MFI-type molecular screen membrane has hoh excellent
First it is orientated, preferred orientation degree is 70~100%.
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| CN108636128A (en) * | 2018-05-14 | 2018-10-12 | 南京工业大学 | A kind of method that microwave heating method quickly prepares h0h orientation MFI-type molecular screen membranes |
| CN108726524A (en) * | 2018-07-11 | 2018-11-02 | 南昌工程学院 | The technique that MFI-type molecular screen membrane is prepared using the method for heat treatment seed layer |
| CN110627491A (en) * | 2019-09-29 | 2019-12-31 | 天津大学 | Synthesis method of molecular sieve membrane with sandwich structure and application of membrane |
| CN114669201A (en) * | 2022-03-09 | 2022-06-28 | 南京工业大学 | Preparation method of composite SSZ-13/MFI molecular sieve membrane |
| CN116808847A (en) * | 2023-07-27 | 2023-09-29 | 大连理工大学 | Preparation method of ultrathin oriented W-MFI zeolite membrane for efficiently separating butane isomers |
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| CN108579449A (en) * | 2018-05-14 | 2018-09-28 | 南京工业大学 | A kind of method of the high silicon SSZ-13 molecular screen membranes of Fast back-projection algorithm |
| CN108636128A (en) * | 2018-05-14 | 2018-10-12 | 南京工业大学 | A kind of method that microwave heating method quickly prepares h0h orientation MFI-type molecular screen membranes |
| CN108579449B (en) * | 2018-05-14 | 2019-12-17 | 南京工业大学 | Method for rapidly synthesizing high-silicon SSZ-13 molecular sieve membrane |
| CN108636128B (en) * | 2018-05-14 | 2020-02-21 | 南京工业大学 | Method for rapidly preparing h0h oriented MFI type molecular sieve membrane by microwave heating method |
| CN108726524A (en) * | 2018-07-11 | 2018-11-02 | 南昌工程学院 | The technique that MFI-type molecular screen membrane is prepared using the method for heat treatment seed layer |
| CN110627491A (en) * | 2019-09-29 | 2019-12-31 | 天津大学 | Synthesis method of molecular sieve membrane with sandwich structure and application of membrane |
| CN110627491B (en) * | 2019-09-29 | 2022-05-17 | 天津大学 | Synthesis method of molecular sieve membrane with sandwich structure and application of membrane |
| CN114669201A (en) * | 2022-03-09 | 2022-06-28 | 南京工业大学 | Preparation method of composite SSZ-13/MFI molecular sieve membrane |
| CN116808847A (en) * | 2023-07-27 | 2023-09-29 | 大连理工大学 | Preparation method of ultrathin oriented W-MFI zeolite membrane for efficiently separating butane isomers |
| CN116808847B (en) * | 2023-07-27 | 2024-04-12 | 大连理工大学 | Preparation method of ultrathin oriented W-MFI zeolite membrane for efficiently separating butane isomers |
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