CN104340993A - Preparation method of SAPO-34 molecular sieve membrane - Google Patents
Preparation method of SAPO-34 molecular sieve membrane Download PDFInfo
- Publication number
- CN104340993A CN104340993A CN201310340692.XA CN201310340692A CN104340993A CN 104340993 A CN104340993 A CN 104340993A CN 201310340692 A CN201310340692 A CN 201310340692A CN 104340993 A CN104340993 A CN 104340993A
- Authority
- CN
- China
- Prior art keywords
- sapo
- molecular sieve
- silicon
- crystal seed
- xerogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 34
- 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 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract 2
- 230000015572 biosynthetic process Effects 0.000 claims description 31
- 238000003786 synthesis reaction Methods 0.000 claims description 30
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000003618 dip coating Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000443 aerosol Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- -1 silicon ester Chemical class 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000012452 mother liquor Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a preparation method of an SAPO-34 molecular sieve membrane. The preparation method comprises the following steps: 1) synthesizing an SAPO-34 molecular sieve seed crystal; 2) evenly coating a porous carrier with the molecular sieve seed crystal; 3) preparing a dry gel synthetic mother liquor of the molecular sieve membrane; 4) loading the dry gel synthetic mother liquor onto the porous carrier prepared in the step 2), and forming a dry gel layer after drying; 5) placing the porous carrier prepared in the step 4) in a reaction kettle, adding a solvent, and carrying out hydrothermal crystallization, wherein the solvent in a liquid state is not directly contacted with the dry gel layer; and 6) carrying out high temperature roasting, removing a template agent, and thus obtaining the SAPO-34 molecular sieve membrane. The SAPO-34 molecular sieve membrane is prepared by utilizing the dry gel method, consumption of the synthetic raw materials and the organic template agent is greatly reduced, the synthetic cost is lowered, and the environmental pollution is reduced; and moreover, the thickness of the prepared SAPO-34 molecular sieve membrane is greatly lowered, so that the mass transfer resistance is greatly reduced, and the penetration rate is improved.
Description
Technical field
The present invention relates to chemical field, particularly relate to the preparation method of SAPO-34 molecular screen membrane.
Background technology
Organic zeolite membrane prepares continuous, fine and close, the uniform molecular sieve of one deck on porous support and obtains.Due to organic zeolite membrane have that aperture is homogeneous, high temperature resistant, chemical resistance solvent and can the advantages such as ion-exchange be carried out, to be therefore separated and there is huge application potential in the field such as environment protection in membrane catalytic reaction, gas delivery, liquid infiltration vaporization.Such as, at CO
2remove field, there is due to membrane separation unit the advantages such as energy consumption is low, continuity operation, facility investment is low, volume is little, easy care, be therefore very applicable to high CO
2the harsh isolating environment of content.
At present, the method preparing organic zeolite membrane on porous support mainly contains Vacuum-assisted method method, two-step fabrication and dry gel method etc.
Vacuum-assisted method method is that porous support is directly put into synthesis mother liquid, under hydrothermal conditions, makes molecular sieve grow film forming at carrier surface.The method is simple to operate, but the quality of film is by various factors, needs repeatedly crystallization synthesis, makes molecular screen membrane thicker.
Two-step fabrication is by porous support seeded, then is placed in synthesis mother liquid situ hydrothermal crystallizing film forming.The method is the improvement to Vacuum-assisted method method.Application number be 200580008446.8 Chinese invention patent application disclose a kind of high-selectivity supported SAPO membranes, by make porous membrane upholder at least one surface contact with aged synthesis gel, prepare high-selectivity supported SAPO membranes.Application number be 200810050714.8 Chinese invention patent application disclose a kind of preparation method of SAPO-34 molecular screen membrane of selectively separating methane gas, adopt the method for crystal seed induction secondary synthesis to synthesize the SAPO-34 molecular screen membrane of separating methane gas.
Dry gel method is a kind of novel molecular sieve membrane synthetic method, the method is that xerogel mother liquor is evenly coated on porous support, dry formation xerogel layer, is then placed in the reactor containing a small amount of water, utilizes the saturation steam of deionized water to carry out hydrothermal crystallizing and forms molecular screen membrane.At present, dry gel method synthesis SAPO-34 molecular sieve has bibliographical information, and Hirota etc. adopt dry gel method synthesis SAPO-34 molecular sieve crystal, and average grain size is 75nm [Mater.Chem.Phys.123 (2010) 507].Chen etc. also adopt dry gel method to synthesize the high SAPO-34 molecular sieve of degree of crystallinity [Micropor.Macropor.Mater.123 (2009) 71].But not yet there is the bibliographical information of dry gel method synthesizing inorganic molecular screen membrane.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of SAPO-34 molecular screen membrane, and it can synthesize the larger SAPO-34 molecular screen membrane of flux, reduces synthesis cost, reduces environmental pollution, and contributes to synthesizing ultra-thin molecular screen membrane.
For solving the problems of the technologies described above, the preparation method of SAPO-34 molecular screen membrane of the present invention, comprises the following steps:
1) SAPO-34 molecular sieve crystal seed is synthesized;
2) SAPO-34 molecular sieve crystal seed is evenly coated onto on porous support;
3) the xerogel synthesis mother liquid of SAPO-34 molecular screen membrane is prepared;
4) xerogel synthesis mother liquid is loaded to step 2) on the porous support being coated with SAPO-34 molecular sieve crystal seed prepared, after drying, form xerogel layer;
5) porous support prepared by step 4) is placed in reactor, solubilizing agent, carries out hydrothermal crystallizing; Described solvent does not directly contact with xerogel layer when liquid state;
6) high-temperature roasting, removed template method, obtains SAPO-34 molecular screen membrane.
Above-mentioned steps 1) in, the synthetic method of SAPO-34 molecular sieve crystal seed is: join in tetraethyl ammonium hydroxide solution by aluminium source (as aluminum isopropylate, aluminium hydroxide, pure aluminum, aluminium salt, aluminum oxide or hydrated aluminum oxide etc.), after abundant hydrolysis, add silicon source (as silicon sol, silicon ester, silicon aerosol or water glass etc.) and phosphoric acid, stirring is spent the night, obtain crystal seed reaction solution, then heating crystallization 2 ~ 72 hours at 120 ~ 230 DEG C, obtains SAPO-34 molecular sieve crystal seed.Wherein, the better mol ratio of crystal seed reaction solution is: 1Al
2o
3: 1 ~ 2P
2o
5: 0.3 ~ 0.6SiO
2: 1 ~ 3 (TEA)
2o:55 ~ 150H
2o.
Above-mentioned steps 2) in, porous support can adopt single passage tubulose, hyperchannel tubulose, tabular or tubular fibre tubulose etc.The aperture of porous support is between 2 ~ 2000 nanometers.The material of porous support can be pottery, stainless steel, aluminum oxide, titanium dioxide, zirconium dioxide, silicon-dioxide, silicon carbide or silicon nitride etc.SAPO-34 molecular sieve crystal seed can be coated on porous support by modes such as brushing, dip-coating, spraying or spin coatings, and employing dip-coating, the ethanol solution concentration of SAPO-34 molecular sieve crystal seed should between 0.01 ~ 1wt%.
Above-mentioned steps 3) in, the compound method of xerogel synthesis mother liquid is: join in phosphoric acid solution by aluminium source (as aluminum isopropylate, aluminium hydroxide, pure aluminum, aluminium salt, aluminum oxide or hydrated aluminum oxide etc.), after abundant hydrolysis, add silicon source (such as silicon sol, silicon ester, silicon aerosol or water glass etc.) and tetraethyl ammonium hydroxide, stirring is spent the night, and obtains the xerogel synthesis mother liquid of SAPO-34 molecular screen membrane.The better mol ratio configuring the xerogel synthesis mother liquid obtained is: 1Al
2o
3: 1 ~ 2P
2o
5: 0.1 ~ 0.6SiO
2: 1 ~ 8TEAOH:30 ~ 1000H
2o.
Above-mentioned steps 4) in, xerogel synthesis mother liquid can be loaded on porous support by modes such as brushing, dip-coating, spraying or spin coatings.During dip-coating, porous support is flooded 1 second ~ 24 hours in xerogel synthesis mother liquid, then at room temperature ~ 120 DEG C dry 1 minute ~ 48 hours.The comparatively Jia Moer of the xerogel layer formed after dry consists of: 1Al
2o
3: 1 ~ 2P
2o
5: 0.1 ~ 0.6SiO
2: 1 ~ 8TEAOH:1 ~ 300H
2o.
Above-mentioned steps 5) in, the temperature of hydrothermal crystallizing is 120 ~ 230 DEG C, and crystallization time is 2 ~ 72 hours, is preferably 4 ~ 7 hours.Solvent can use the mixture of water, ammoniacal liquor, xerogel synthesis mother liquid, organic solvent or above-mentioned solvent, and consumption is every milliliter of reactor volume solubilizing agent 0.001 ~ 0.1 gram.Solvent does not directly contact with xerogel layer when liquid state, but when high temperature crystallization, the steam produced after solvent evaporation directly can contact with xerogel layer.
The present invention first forms one deck xerogel on porous support, again gel coat is converted into SAPO-34 molecular screen membrane, the SAPO-34 molecular screen membrane flux synthesized by this dry gel method is large, thickness is thin (can be low to moderate 1 microns), thus resistance to mass transfer is little, rate of permeation is high, can be used for CO
2-CH
4, CO
2-H
2, CO
2-N
2deng the separation of mixed gas; In addition, the synthesis material consumed in building-up process and organic formwork agent less, therefore can also reduce synthesis cost, reduce environmental pollution.
Accompanying drawing explanation
Fig. 1 is in embodiment 1, the XRD(X ray diffraction of the powdered product of Polycondensation Reactor and Esterification Reactor) collection of illustrative plates.This collection of illustrative plates composes consistent with the XRD figure of the SAPO-34 molecular sieve of standard, do not have stray crystal.
Fig. 2 is the surface (a) of SAPO-34 molecular screen membrane and the SEM(scanning electronic microscope of section (b) of embodiment 1 preparation) photo.From (a) photo, carrier surface is covered completely by the square crystal of sheet, crosslinked good between crystal.From (b) photo, the thickness of film is comparatively even, is about 5 microns.
Fig. 3 is the surface of SAPO-34 molecular screen membrane and the SEM photo of section of embodiment 2 preparation.From (a) photo, carrier surface is covered completely by cubic crystal, and crystallographic dimension is 1 micron, is cross-linked and still can between crystal.From (b) photo, the thickness of film is comparatively even, is about 50 microns.
Fig. 4 is the surface of SAPO-34 molecular screen membrane and the SEM photo of section of embodiment 3 preparation.From (a) and (b) photo, carrier surface is covered completely by the square crystal of sheet, and crystallographic dimension is 100 nanometer ~ 1 micron, crosslinked good between crystal.From (c) photo, the thickness of film is comparatively even, is about 20 microns.
Fig. 5 is the surperficial SEM photo of SAPO-34 molecular screen membrane after supersound process prepared by embodiment 3.As can be seen from SEM photo, supersound process eliminates the loose crystal of carrier surface.After ultrasonic, the thickness of film is significantly reduced to 1 microns.
Embodiment
Understand more specifically for having technology contents of the present invention, feature and effect, now by reference to the accompanying drawings, details are as follows:
Embodiment 1
Step 1, adds 2.46g deionized water in 31.13g tetraethyl ammonium hydroxide solution (TEAOH, 35wt%), then takes 7.56g aluminum isopropylate and join in previous solu, stirring at room temperature 2-3 hour; Then drip 1.665g silicon sol (40wt%), stir 1 hour; Last slowly dropping 8.53g phosphoric acid solution (H
3pO
4, 85wt%), stirring is spent the night.Adopt microwave heating, crystallization 7 hours at 180 DEG C.After product takes out, centrifugal, washing, dries, obtains SAPO-34 molecular sieve crystal seed.
Step 2, choose aperture be the porous ceramic pipe of 5nm as carrier, carrier two ends envelope glaze, clean dry after, outside surface Teflon tap seals, and SAPO-34 molecular sieve crystal seed is brushed the internal surface of vitrified pipe.
Step 3,9.07 grams of aluminum isopropylates are joined in 5.12 grams of phosphoric acid solutions (85wt%) and 16.33 grams of deionized waters, after abundant hydrolysis, add 1.00 grams of silicon sol (40wt%) and 16.35 grams of tetraethyl ammonium hydroxides (35wt%) successively, stirring is spent the night, obtain the xerogel synthesis mother liquid of molecular screen membrane, its mol ratio is: 1Al
2o
3: 1P
2o
5: 0.3SiO
2: 1TEAOH:77H
2o.
Step 4, the porous support being coated with SAPO-34 molecular sieve crystal seed step 2 prepared is dipped in 2h in xerogel synthesis mother liquid, take out, at room temperature dry 10min, is then placed in the reactor of 100ml, add 1ml deionized water, at 220 DEG C, hydrothermal crystallizing 5h, washing, drying, obtains SAPO-34 molecular screen membrane.
Step 5, the SAPO-34 molecular screen membrane pipe vacuum baking 4h at 400 DEG C step 4 obtained, removed template method (intensification and rate of temperature fall are 1K/min), then carries out CO
2/ CH
4gas delivery is tested.
CO
2/ CH
4gas delivery test condition: temperature 20 DEG C, barometric point 102.4kPa, gas feed rate is 4000mL/min, mole consists of 50/50%.The gas flow of per-meate side is measured with soap film flowmeter; The gas composition of per-meate side is analyzed with gas chromatograph (Shimadzu-2014C).
The calculation formula of gas permeability: p=V/ (S*P).Wherein, V is infiltration gas (CO
2or CH
4) flow, unit mol/s, S are membrane area, unit m
2; P is the pressure difference of film pipe feeding side and per-meate side, unit Pa.
Separation selectivity calculation formula: f=p
cO2/ p
cH4, i.e. CO
2with CH
4the ratio of rate of permeation.
Gas delivery test result is as shown in table 1, under 4.0MPa, and the CO of this SAPO-34 molecular screen membrane pipe
2rate of permeation be 7.63 × 10
-7mol/ (m
2sPa), CO
2/ CH
4separation selectivity be 6; At 0.2 mpa, its CO
2rate of permeation be 23.3 × 10
-7mol/ (m
2sPa), CO
2/ CH
4separation selectivity be 16.
The CO of the SAPO-34 molecular screen membrane pipe of table 1 embodiment 1
2/ CH
4gas delivery test result
Embodiment 2
Be with the difference of example 1: in step 4, the dipping time of porous support in xerogel synthesis mother liquid being coated with SAPO-34 molecular sieve crystal seed is 10min.All the other steps are identical with embodiment 1.
The gas delivery test result of the SAPO-34 molecular screen membrane pipe of preparation is as shown in table 2, under 4.0MPa, and its CO
2rate of permeation be 6.69 × 10
-7mol/ (m
2sPa), CO
2/ CH
4separation selectivity be 4; At 0.2 mpa, its CO
2rate of permeation be 22.2 × 10
-7mol/ (m
2sPa), CO
2/ CH
4separation selectivity be 12.
The CO of the SAPO-34 molecular screen membrane pipe of table 2 embodiment 2
2/ CH
4gas delivery test result
Embodiment 3
Be with the difference of embodiment 1: in the Hydrothermal Synthesis of step 4, the amount of the deionized water of interpolation is 2ml.All the other steps are identical with embodiment 1.
The gas delivery test result of the SAPO-34 molecular screen membrane pipe of preparation is as shown in table 3, under 4.0MPa, and its CO
2rate of permeation be 2.33 × 10
-7mol/ (m
2sPa), CO
2/ CH
4separation selectivity be 11; At 0.2 mpa, its CO
2rate of permeation be 8.05 × 10
-7mol/ (m
2sPa), CO
2/ CH
4separation selectivity be 43.
The CO of the SAPO-34 molecular screen membrane of table 3 embodiment 3
2/ CH
4gas delivery test result
After this SAPO-34 molecular screen membrane pipe of supersound process, the loose crystals on porous support surface is removed, and the thickness of film is significantly reduced to 1 microns, as shown in Figure 5.
Embodiment 4
Be with the difference of embodiment 1: in step 4, the dipping time of porous support in xerogel synthesis mother liquid being coated with SAPO-34 molecular sieve crystal seed is 10min; In Hydrothermal Synthesis, the amount of the deionized water of interpolation is 3ml.All the other steps are identical with embodiment 1.
The CO of the SAPO-34 molecular screen membrane pipe of preparation
2/ CH
4gas delivery test result is as shown in table 4.Under 4.0MPa, its CO
2rate of permeation be 3.95 × 10
-7mol/ (m
2sPa), CO
2/ CH
4separation selectivity be 10; Under 2MPa, its CO
2rate of permeation be 4.61 × 10
-7mol/ (m
2sPa), CO
2/ CH
4separation selectivity be 30.
The CO of the SAPO-34 molecular screen membrane of table 4 embodiment 4
2/ CH
4gas delivery test result
Claims (12)
- The preparation method of 1.SAPO-34 molecular screen membrane, is characterized in that, step comprises:1) SAPO-34 molecular sieve crystal seed is synthesized;2) SAPO-34 molecular sieve crystal seed is evenly coated onto on porous support;3) the xerogel synthesis mother liquid of SAPO-34 molecular screen membrane is prepared;4) xerogel synthesis mother liquid is loaded to step 2) on the porous support being coated with SAPO-34 molecular sieve crystal seed prepared, after drying, form xerogel layer;5) porous support prepared by step 4) is placed in reactor, solubilizing agent, carries out hydrothermal crystallizing; Described solvent does not directly contact with xerogel layer when liquid state;6) high-temperature roasting, removed template method, obtains SAPO-34 molecular screen membrane.
- 2. method according to claim 1, it is characterized in that, step 1), the synthesis step of SAPO-34 molecular sieve crystal seed comprises: joined in aluminium source in tetraethyl ammonium hydroxide solution, fully after hydrolysis, adds silicon source and phosphoric acid, stir, obtain crystal seed reaction solution, then heating crystallization, obtain SAPO-34 molecular sieve crystal seed; Described aluminium source comprises aluminum isopropylate, aluminium hydroxide, pure aluminum, aluminium salt, aluminum oxide, hydrated aluminum oxide; Described silicon source comprises silicon sol, silicon ester, silicon aerosol, water glass.
- 3. method according to claim 2, is characterized in that, step 1), and the mol ratio of described crystal seed reaction solution is: 1Al 2o 3: 1 ~ 2P 2o 5: 0.3 ~ 0.6SiO 2: 1 ~ 3 (TEA) 2o:55 ~ 150H 2o.
- 4. method according to claim 1, it is characterized in that, step 2), the shape of porous support comprises single passage tubulose, hyperchannel tubulose, tabular, tubular fibre tubulose, material comprises pottery, stainless steel, aluminum oxide, titanium dioxide, zirconium dioxide, silicon-dioxide, silicon carbide, silicon nitride, and aperture is 2 ~ 2000 nanometers.
- 5. method according to claim 1, is characterized in that, step 2), the coating method of molecular sieve crystal seed comprises brushing, dip-coating, spraying, spin coating; When adopting dip-coating, the ethanol solution concentration of SAPO-34 molecular sieve crystal seed is 0.01 ~ 1wt%.
- 6. method according to claim 1, is characterized in that, step 3), preparation steps comprises: join in phosphoric acid solution by aluminium source, fully after hydrolysis, adds silicon source and tetraethyl ammonium hydroxide, stir, obtain the xerogel synthesis mother liquid of SAPO-34 molecular screen membrane; Described aluminium source comprises aluminum isopropylate, aluminium hydroxide, pure aluminum, aluminium salt, aluminum oxide, hydrated aluminum oxide; Described silicon source comprises silicon sol, silicon ester, silicon aerosol, water glass.
- 7. method according to claim 6, is characterized in that, step 3), and the mol ratio of described xerogel synthesis mother liquid is: 1Al 2o 3: 1 ~ 2P 2o 5: 0.1 ~ 0.6SiO 2: 1 ~ 8TEAOH:30 ~ 1000H 2o.
- 8. method according to claim 7, is characterized in that, step 4), described xerogel layer mole consist of 1Al 2o 3: 1 ~ 2P 2o 5: 0.1 ~ 0.6SiO 2: 1 ~ 8TEAOH:1 ~ 300H 2o.
- 9. method according to claim 1, is characterized in that, step 4), and method xerogel synthesis mother liquid being loaded to porous support comprises dip coating, spraying method, spin-coating method; When adopting dip coating, porous support flood 1 second ~ 24 hours in xerogel synthesis mother liquid, then drying 1 minute ~ 48 hours at room temperature ~ 120 DEG C.
- 10. method according to claim 1 and 2, is characterized in that, crystallization temperature is 120 ~ 230 DEG C, and crystallization time is 2 ~ 72 hours.
- 11. methods according to claim 10, is characterized in that, crystallization time is 4 ~ 7 hours.
- 12. methods according to claim 1, is characterized in that, step 5), and described solvent comprises the mixture of water, ammoniacal liquor, xerogel synthesis mother liquid, organic solvent or above-mentioned solvent; The consumption of solvent is 0.001 ~ 0.1 grams per milliliter reactor volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310340692.XA CN104340993A (en) | 2013-08-06 | 2013-08-06 | Preparation method of SAPO-34 molecular sieve membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310340692.XA CN104340993A (en) | 2013-08-06 | 2013-08-06 | Preparation method of SAPO-34 molecular sieve membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104340993A true CN104340993A (en) | 2015-02-11 |
Family
ID=52497534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310340692.XA Pending CN104340993A (en) | 2013-08-06 | 2013-08-06 | Preparation method of SAPO-34 molecular sieve membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104340993A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948073A (en) * | 2016-04-25 | 2016-09-21 | 中国科学院上海高等研究院 | Preparation method of SAPO-34 molecular sieve |
| CN106185983A (en) * | 2016-07-29 | 2016-12-07 | 中国科学院上海高等研究院 | The solvent-free method preparing SAPO 18 or SAPO 34 molecular sieve |
| CN107746065A (en) * | 2017-12-06 | 2018-03-02 | 武汉工程大学 | A kind of method for preparing the molecular screen membrane of high-performance SAPO 34 |
| CN109663509A (en) * | 2019-01-18 | 2019-04-23 | 中国科学院上海高等研究院 | A kind of preparation method of multi-stage porous SAPO-34 molecular screen membrane |
| CN110683559A (en) * | 2019-08-22 | 2020-01-14 | 上海工程技术大学 | Green synthesis method of ultrathin SSZ-13 molecular sieve membrane |
| CN111013404A (en) * | 2019-11-26 | 2020-04-17 | 上海工程技术大学 | Rapid and economical synthesis method of ultrathin MFI molecular sieve membrane |
| CN112744828A (en) * | 2019-10-31 | 2021-05-04 | 上海工程技术大学 | Ultrathin molecular sieve membrane and preparation method thereof |
| CN114634188A (en) * | 2020-12-15 | 2022-06-17 | 南京工业大学 | Preparation method of oriented SAPO-34 molecular sieve membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011072215A1 (en) * | 2009-12-11 | 2011-06-16 | The Regents Of The University Of Colorado | High-flux sapo-34 membranes for co2/ch4 separations |
| CN102336414A (en) * | 2011-06-29 | 2012-02-01 | 同济大学 | Method for preparing high quality SAPO-34 zeolite membrane by clear sol method |
| CN103086395A (en) * | 2013-01-18 | 2013-05-08 | 浙江大学 | Preparation method of SAPO series molecular sieve membrane with metal oxide as carrier |
-
2013
- 2013-08-06 CN CN201310340692.XA patent/CN104340993A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011072215A1 (en) * | 2009-12-11 | 2011-06-16 | The Regents Of The University Of Colorado | High-flux sapo-34 membranes for co2/ch4 separations |
| CN102336414A (en) * | 2011-06-29 | 2012-02-01 | 同济大学 | Method for preparing high quality SAPO-34 zeolite membrane by clear sol method |
| CN103086395A (en) * | 2013-01-18 | 2013-05-08 | 浙江大学 | Preparation method of SAPO series molecular sieve membrane with metal oxide as carrier |
Non-Patent Citations (1)
| Title |
|---|
| YUICHIRO HIROTA ET AL.: "Dry gel conversion synthesis of SAPO-34 nanocrystals", 《MATER. CHEM. PHYS.》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948073A (en) * | 2016-04-25 | 2016-09-21 | 中国科学院上海高等研究院 | Preparation method of SAPO-34 molecular sieve |
| CN106185983A (en) * | 2016-07-29 | 2016-12-07 | 中国科学院上海高等研究院 | The solvent-free method preparing SAPO 18 or SAPO 34 molecular sieve |
| CN107746065A (en) * | 2017-12-06 | 2018-03-02 | 武汉工程大学 | A kind of method for preparing the molecular screen membrane of high-performance SAPO 34 |
| CN109663509A (en) * | 2019-01-18 | 2019-04-23 | 中国科学院上海高等研究院 | A kind of preparation method of multi-stage porous SAPO-34 molecular screen membrane |
| CN109663509B (en) * | 2019-01-18 | 2022-01-21 | 中国科学院上海高等研究院 | Preparation method of hierarchical pore SAPO-34 molecular sieve membrane |
| CN110683559A (en) * | 2019-08-22 | 2020-01-14 | 上海工程技术大学 | Green synthesis method of ultrathin SSZ-13 molecular sieve membrane |
| CN112744828A (en) * | 2019-10-31 | 2021-05-04 | 上海工程技术大学 | Ultrathin molecular sieve membrane and preparation method thereof |
| CN112744828B (en) * | 2019-10-31 | 2022-10-14 | 上海工程技术大学 | Ultrathin molecular sieve membrane and preparation method thereof |
| CN111013404A (en) * | 2019-11-26 | 2020-04-17 | 上海工程技术大学 | Rapid and economical synthesis method of ultrathin MFI molecular sieve membrane |
| CN111013404B (en) * | 2019-11-26 | 2022-08-26 | 上海工程技术大学 | Rapid and economical synthesis method of ultrathin MFI molecular sieve membrane |
| CN114634188A (en) * | 2020-12-15 | 2022-06-17 | 南京工业大学 | Preparation method of oriented SAPO-34 molecular sieve membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104340993A (en) | Preparation method of SAPO-34 molecular sieve membrane | |
| CN104355316A (en) | Preparation method for SAPO-34 molecular sieve membrane | |
| CN102794115B (en) | Preparation method of metal organic framework ZIF-8 (zero insert force-9) film | |
| CN105797594B (en) | A kind of thermally grown method of simple solvent prepares the metal organic framework nanometer chip film of oriented growth | |
| CN102350229B (en) | Metal element modified ZSM-5 molecular sieve composite membrane as well as preparation method and application thereof | |
| CN102311124B (en) | Method for preparing Silicalite-1/ZSM-5 composite molecular sieve | |
| Tian et al. | Synthesis of a SAPO-34 membrane on macroporous supports for high permeance separation of a CO 2/CH 4 mixture | |
| CN106492651A (en) | A kind of preparation of 66 series membranes of metallic organic framework UiO and the method for separating methyl alcohol/MTBE mixtures | |
| CN101920170B (en) | High-flux molecular-sieve alcohol permselective membrane and preparation method thereof | |
| CN108031300A (en) | Zeolite film composite | |
| Mao et al. | Enhanced gas separation through well-intergrown MOF membranes: seed morphology and crystal growth effects | |
| CN104150504B (en) | A kind of preparation method of SAPO-34 molecular screen membrane | |
| CN105879708B (en) | A kind of method for preparing the metal organic framework films of Co ZIF 67 using not homologous zinc oxide film induction | |
| CN102489183A (en) | Metal-organic framework (MOF) material for permeating and separating gases and preparation method thereof | |
| CN110683559A (en) | Green synthesis method of ultrathin SSZ-13 molecular sieve membrane | |
| Kong et al. | In situ fabrication of high-permeance ZIF-8 tubular membranes in a continuous flow system | |
| CN103896300A (en) | Preparation method of high-performance SAPO (silicoaluminophosphate)-34 molecular sieve membrane | |
| CN111056560B (en) | Economic synthesis method of ultrathin SSZ-13 molecular sieve membrane | |
| CN104906964B (en) | Preparation method for syntehsizing high-performance NaA molecular sieve membrane through seed self-self assembly supported support body | |
| CN101318665B (en) | Method for preparing high-performance Y type molecular sieve film and application of the same in organic mixture separation | |
| CN105921033A (en) | Method for preparing CHA molecular sieve membrane in clean liquid | |
| CN102225314A (en) | Method for synthesizing molecular sieve membrane | |
| Wu et al. | Seeded growth of high-performance ZIF-8 membranes in thick wall autoclaves assisted by modulator | |
| CN112191111A (en) | Ionic liquid/metal organic framework ZIF-8 composite membrane and preparation method and application thereof | |
| CN104058426B (en) | The method that temperature-switching method prepares the molecular screen membranes of SAPO 34 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150211 |
|
| RJ01 | Rejection of invention patent application after publication |