CN107008157A - A kind of molecular screen membranes of SAPO 56 and preparation method thereof - Google Patents
A kind of molecular screen membranes of SAPO 56 and preparation method thereof Download PDFInfo
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- CN107008157A CN107008157A CN201710252885.8A CN201710252885A CN107008157A CN 107008157 A CN107008157 A CN 107008157A CN 201710252885 A CN201710252885 A CN 201710252885A CN 107008157 A CN107008157 A CN 107008157A
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- sapo
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- 239000012528 membrane Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 241000269350 Anura Species 0.000 title abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 31
- 238000001354 calcination Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002808 molecular sieve Substances 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 claims description 16
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 16
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000012510 hollow fiber Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 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 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052863 mullite Inorganic materials 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical group CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 abstract 1
- -1 hexamethylene diamines Chemical class 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 235000012489 doughnuts Nutrition 0.000 description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000713 high-energy ball milling Methods 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000329 molecular dynamics simulation Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 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 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- 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
- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
-
- 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
- B01D69/04—Tubular membranes
- B01D69/043—Tubular membranes characterised by the tube diameter
-
- 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
- B01D69/06—Flat membranes
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D2053/221—Devices
- B01D2053/222—Devices with plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D2053/221—Devices
- B01D2053/223—Devices with hollow tubes
- B01D2053/224—Devices with hollow tubes with hollow fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
Abstract
Present invention relates particularly to a kind of molecular screen membranes of SAPO 56 and preparation method thereof.The method of the present invention is with N, N, N ', N ' tetramethyls 1,6 hexamethylene diamines are template machine, and aluminium isopropoxide is silicon source, and phosphoric acid is phosphorus source, Ludox is silicon source, prepares the molecular screen membranes of SAPO 56 in alumina support through hydrothermal synthesis method, and remove template machine in ozone system.The molecular screen membranes of SAPO 56 and its preparation method prepared is reports first, and activation film surface causes it all can is main improvement of the invention in methods such as removed template methods at low temperature in ozone environment.
Description
Technical field
The invention provides a kind of SAPO-56 molecular screen membranes and preparation method thereof, succeed first in Woelm Alumina support
SAPO-56 molecular screen membranes are prepared on body, belong to field of inorganic materials.
Background technology
Natural gas is the important energy source arranged side by side with oil, coal and chemical raw material.Carbon dioxide is natural gas（Effectively into
It is divided into methane）Major impurity gas, not only reduce the combustion heat value of natural gas, and gas pipeline made under moisture conditions
Into corrosion.CO is separated at present2Method mainly include machine amine absorbing and removing and organic UF membrane.Amine, which absorbs, has equipment investment
The problems such as high, bulky, absorbent regeneration high energy consumption.UF membrane has that energy consumption is low, continuity operation, equipment investment are low, body
The advantages of product small, easy care, but the phenomenons, shadow such as carbon is crisp easily occur in the presence of high carbon dioxide concentration and high-carbon hydrocarbon for organic film
Ring the separating property and stability of film.In recent years, inoranic membrane, particularly molecular screen membrane, by feat of good mechanical stability,
Corrosion resistance and higher heat endurance, to CO in natural gas2Processing have broad application prospects.Molecular screen membrane has equal
Even molecular scale duct and unique absorption property, it can using gas molecule diffusion coefficient difference and absorption property
Difference realizes separation.By selecting the molecular sieve with suitable aperture, diffusion of the gas with various molecule in molecular sieve pore passage
Coefficient can have the difference of several orders of magnitude, therefore can obtain high diffusion selectivity.Meanwhile, gas molecule is in molecular sieve
Selective absorption in crystal duct can also obtain higher selectivity.CO2Molecular dynamics a diameter of 0.33 nm, CH4's
A diameter of 0.38 nm of molecular dynamics, therefore the molecular screen membrane of aperture, such as DDR (0.36 × 0.44 nm), T-shaped (aperture
0.36 × 0.51 nm) and SAPO-34 (0.38 nm) etc., its aperture and CH4Gas Molecules Kinetics diameter is similar, and bigger
In CO2Gas Molecules Kinetics diameter, under molecule screening and competitive Adsorption synergy, these molecular screen membranes have higher
CO2/ CH4Separating property.
SAPO-56 molecular sieves have AFX types topological structure and three-dimensional 8 membered ring channels communicated, and its pore size is 0.34
× 0.36 nm, between CO2（0.33 nm）And CH4（0.38 nm）Between.Absorption test shows SAPO-56 molecular sieves to CO2Inhale
It is attached to reach 5.46 mmol/g (273 K, 101 kPa), apparently higher than other small pore moleculars such as SAP0-34 molecular sieves
Sieve.SAPO-56 molecular sieve pore passages size is less than above-mentioned molecular sieve simultaneously, therefore, and SAP0-56 molecular sieves are in separation CO2The bodies of/CH 4
Substantially high preferred absorption and molecule sieving actoion can be shown when being【Cheung O, Liu Q, Bacsik Z, Hedin
N, Microporous and Mesoporous Materials, 2012,156,90-96；Bacsik Z, Cheung O,
Vasiliev P, Hedin N, Applied Energy, 2016,162,613-621】, still, not yet have successfully synthesize at present
The report of SAPO-56 molecular screen membranes.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the SAPO-56 molecular screen membranes of Woelm Alumina support, we
It is owned by France in the aluminium silicophosphate type SAPO-56 molecular screen membranes for proposing to prepare densification first on porous alumina carrier.
The first aspect of the invention：
A kind of SAPO-56 molecular screen membranes, include selection separating layer and supporter, and selection separating layer is overlying on the surface of supporter；
Described selection separating layer is made up of fine and close SAPO-56 molecular sieves；Described supporting layer is made up of porous ceramics.
The configuration of described supporter is selected from chip, tubular type or hollow fiber form.
Number of channels inside the supporter of described hollow fiber form is 1~6, and external diametrical extent is 2~6mm, internal
Channel diameter scope is 0.3~1.5mm.
The thickness of the supporter of described chip is 1~10mm.
External diameter preferably 4~20mm of described tubular type supporter, internal diameter preferably 1~12mm.
One in the preferred carborundum of material, diatomite, mullite, aluminum oxide, zirconium oxide or the titanium oxide of porous ceramics
Plant or several mixing.
The second aspect of the invention：
A kind of preparation method of SAPO-56 molecular screen membranes, comprises the following steps：
1st step, ball-milling treatment is carried out to SAPO-56 molecular sieves using high energy ball mill, stand-by as crystal seed；
2nd step, crystal seed is added water and is configured to suspension, adds thickener, after being well mixed, as crystal seed liquid；Again by drying
Porous ceramic support immersion crystal seed liquid in, carry out Best-Effort request, after taking-up, drying；Again by calcining, obtain being loaded with crystalline substance
The supporter planted；
3rd step, the supporter for being loaded with crystal seed is placed in film Synthesis liquid, carries out Hydrothermal Synthesiss, after taking-up, drying, then smelly
Calcined under oxygen environment, obtain SAPO-56 molecular screen membranes.
In the 1st described step, ball milling refers to the fine powder that SAPO-56 molecular sieves are broken for 50nm~2 μm, more preferably
0.3μm。
In the 2nd described step, concentration of the crystal seed in suspension is 0.5~1wt%, concentration of the thickener in crystal seed liquid
It is 0.02~0.1wt%.
In the 2nd described step, thickener is hydroxypropyl cellulose（HPC）.
In the 2nd described step, the preferred carborundum of material, diatomite, mullite, aluminum oxide, the oxygen of porous ceramic support
Change one or several kinds of mixing in zirconium or titanium oxide；The configuration of described supporter is selected from chip, tubular type or hollow
Fiber type.
In the 2nd described step, dry porous ceramic support is first passed through in distilled water plus ultrasonically treated mistake.
In the 2nd described step, the parameter of calcination process is：440~460 DEG C of 6~10h of calcining.
In the 3rd described step, in film Synthesis liquid silicon source, phosphorus source, silicon source, template be according to mol ratio be Al2O3：P2O5：
SiO2：Template：H2O=0.8：（0.8~1.2）：（0.5~0.7）：（1.8~2.2）：（45~55）Proportional arrangement；More preferably
Ratio be 0.8：1.0：0.6：2：50.
Described template is N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine（TMHD）.
In the 3rd described step, the parameter of Hydrothermal Synthesiss is：180~220 are warming up to 0.8~1.2 DEG C/min speed
DEG C, 40~50h is incubated, then 20~30 DEG C are cooled to 0.8~1.2 DEG C/min speed.
In the 3rd described step, calcining refers in ozone environment with 180~220 DEG C of 25~30h of calcining.
The third aspect of the invention：
SAPO-56 molecular screen membranes are in CO2/CH4Application in gas separation.
Described application, refers to improve CO2/CH4CO in gas separation2Permeability and CO2/CH4Separation selectivity.
Beneficial effect
Nanoscale SAPO-56 molecular sieves after the present invention is handled using high-energy ball milling are induced as crystal seed, in Hydrothermal Synthesiss
In prepare fine and close flawless SAPO-56 molecular screen membranes, and lived at low temperature using special atmosphere or outfield ancillary technique
Change SAPO-56 molecular screen membranes so that template machine TMHD removing can so solve template machine removing without carrying out at high temperature
There is situation about coming off with support body layer in film layer when thoroughly even calcining heat is not too high, can avoid the cracking and crystalline substance of film layer
Between defect formation, improve the quality of film, prepare fine and close SAPO-56 molecular screen membranes.
Brief description of the drawings
Fig. 1 is the SEM for the SAPO-56 molecular sieves that the particle diameter without high-energy ball milling processing is 20 μm（SEM）
Figure.
Fig. 2 is the SEM for the SAPO-56 molecular sieves that the particle diameter handled through high energy ball mill is 0.3 μm
（SEM）Figure.
Fig. 3 is the XRD diffraction curve phenograms for the SAPO-56 molecular screen membranes prepared in embodiment 1.
Fig. 4 is the SAPO-56 for inducing synthesis in embodiment 1 for 0.3 μm of the crystal seed handled through high energy ball mill with particle diameter
The surface Scanning Electron microscope of molecular screen membrane（SEM）Macrostructure figure.
Fig. 5 is the SAPO-56 for inducing synthesis in embodiment 1 for 0.3 μm of the crystal seed handled through high energy ball mill with particle diameter
The surface Scanning Electron microscope of molecular screen membrane（SEM）Micro-structure diagram.
Fig. 6 is the SAPO-56 for inducing synthesis in embodiment 1 for 0.3 μm of the crystal seed handled through high energy ball mill with particle diameter
The cross-sectional scanning electron microscope of molecular screen membrane（SEM）Micro-structure diagram.
Fig. 7 is the cross-sectional scanning electron microscope for the SAPO-56 molecular screen membranes that reference examples 1 are synthesized（SEM）Microstructure
Figure.
Fig. 8 be reference examples it is 2-in-1 into SAPO-56 molecular screen membranes cross-sectional scanning electron microscope（SEM）Microstructure
Figure.
Fig. 9 is the cross-sectional scanning electron microscope for the SAPO-56 molecular screen membranes that reference examples 3 are synthesized（SEM）Microstructure
Figure.
Figure 10 is the cross-sectional scanning electron microscope for the SAPO-56 molecular screen membranes that reference examples 4 are synthesized（SEM）Microstructure
Figure.
Figure 11 is the cross-sectional scanning electron microscope for the SAPO-56 molecular screen membranes that reference examples 5 are synthesized（SEM）Microstructure
Figure.
Embodiment
The present invention successfully prepares SAPO-56 molecular screen membranes on porous supporting body first, and supporter here is
It is made up of porous ceramics, the selection separating layer being made up of SAPO-56 molecular screen membranes is covered with its surface.Here supporter
Configuration be not particularly limited, chip, tubular type or hollow fiber form can be selected from.
For the configuration of supporter, there is no particular limitation, in some embodiments, in the supporter of hollow fiber form
The number of channels in portion can be 1~6, and external diametrical extent is preferably 2~6mm, inner passage diameter scope is preferably 0.3~
1.5mm；The thickness of the supporter of described chip is preferably 1~10mm；The external diameter preferably 4 of described tubular type supporter~
20mm, internal diameter preferably 1~12mm.
For the material of porous ceramic support, it is not particularly limited, the material that its material can be selected includes：Oxidation
Aluminium, zirconium oxide, magnesia, silica, titanium oxide, cerium oxide, yittrium oxide, the oxide material such as barium titanate；Cordierite, many aluminium
The combined oxidation species material such as andalusite, forsterite, steatite, sialon, zircon, ferrite；Silicon nitride, nitridation
The nitride-based materials such as aluminium；The carbon compound material such as carborundum；The hydroxide composition material such as hydroxyapatite；The elements such as carbon, silicon
Class material；Or the two or more inorganic composite materials containing them etc..Natural minerals can also be used（Clay, clay pit
Thing, grog, silica sand, pottery stone, feldspar, white sand）Or blast-furnace slag, flying dust etc., preferably carborundum, diatomite, mullite, oxidation
One or several kinds of mixing in aluminium, zirconium oxide or titanium oxide.
Embodiment 1
From four-way aluminum oxide doughnut supporter（Diameter 3.8mm, four-way is evenly distributed in section, and channel diameter is about
1mm）, supporter is placed in distilled water ultrasound 20 minutes, cleaning, drying.Supporter is put into concentration for 1wt%SAPO-56（+
0.125wt%HPC）In crystal seed liquid, the SAPO-56 crystal seed sizes handled through high energy ball mill are about 0.3 μm, using Best-Effort request
Mode, by aluminum oxide four-way doughnut supporter be placed in crystal seed liquid impregnate 10s after take out, be put into 60 DEG C of baking ovens dry
Dry 4h, is then placed in Muffle furnace after 450 DEG C of calcining 8 h removings HPC, obtains being loaded with the supporter of crystal seed；
By boehmite, phosphoric acid, Ludox, TMHD using mol ratio as Al2O3：P2O5：SiO2：TMHD：H2O=0.8：1.0：
0.6：2：50 proportional arrangement film synthesis mother liquid, is put into the supporter of load crystal seed, is heated up in an oven with 1 DEG C/min speed
To 200 DEG C, 48h is incubated, then 25 DEG C are cooled to 1 DEG C/min speed, supporter is taken out, and keeps in ozone environment 200
DEG C calcining 28h, obtain product doughnut SAPO-56 molecular screen membranes.
Reference examples 1
From four-way aluminum oxide doughnut supporter, supporter is placed in ultrasound 20 minutes, cleaning, drying in distilled water.Will
Supporter is put into concentration for 1wt%SAPO-56（+0.125wt%HPC）In crystal seed liquid, the SAPO-56 handled through high energy ball mill is brilliant
It is about 0.3 μm to plant size, by the way of Best-Effort request, and aluminum oxide four-way doughnut supporter is placed in crystal seed liquid and soaked
Taken out after stain 10s, be put into 60 DEG C of baking ovens and dry 4h, be then placed in Muffle furnace after 450 DEG C of calcining 8h removings HPC, born
It is loaded with the supporter of crystal seed；
By boehmite, phosphoric acid, Ludox, TMHD using mol ratio as Al2O3：P2O5：SiO2：TMHD：H2O=0.8：1.0：
0.6：2：40 proportional arrangement film synthesis mother liquid, is put into the supporter of load crystal seed, is heated up in an oven with 1 DEG C/min speed
To 200 DEG C, 48h is incubated, then 25 DEG C are cooled to 1 DEG C/min speed, supporter is taken out, and keeps in ozone environment 200
DEG C calcining 28h, obtain product doughnut SAPO-56 molecular screen membranes.
Reference examples 2
From four-way aluminum oxide doughnut supporter, supporter, which is placed in 0.1mol/L NaOH weak caustic solutions, soaks 10h,
Cleaning, drying.Supporter is put into concentration for 1wt%SAPO-56（+0.125wt%HPC）In crystal seed liquid, handled through high energy ball mill
SAPO-56 crystal seed sizes be about 0.3 μm, by the way of Best-Effort request, aluminum oxide four-way doughnut supporter is put
Impregnate after 10s and take out in crystal seed liquid, be put into 60 DEG C of baking ovens and dry 4h, be then placed in 450 DEG C of calcining 8h removings in Muffle furnace
After HPC, obtain being loaded with the supporter of crystal seed；
By boehmite, phosphoric acid, Ludox, TMHD using mol ratio as Al2O3：P2O5：SiO2：TMHD：H2O=0.8：1.0：
0.6：2：50 proportional arrangement film synthesis mother liquid, is put into the supporter of load crystal seed, in an oven with 1 DEG C/min speed liter
Temperature is incubated 48h to 200 DEG C, then is cooled to 25 DEG C with 1 DEG C/min speed, takes out supporter, and kept in ozone environment
200 DEG C of calcining 28h, obtain product doughnut SAPO-56 molecular screen membranes.
Reference examples 3
From four-way aluminum oxide doughnut supporter, supporter is placed in ultrasound 20 minutes, cleaning, drying in distilled water.Will
Supporter is put into concentration for 1wt%SAPO-56（+0.125wt%HPC）In crystal seed liquid, the SAPO-56 handled through high energy ball mill is brilliant
It is about 0.3 μm to plant size, by the way of Best-Effort request, and aluminum oxide four-way doughnut supporter is placed in crystal seed liquid and soaked
Taken out after stain 10s, be put into 60 DEG C of baking ovens and dry 4h, be then placed in Muffle furnace after 450 DEG C of calcining 8h removings HPC, born
It is loaded with the supporter of crystal seed；
By boehmite, phosphoric acid, Ludox, TMHD using mol ratio as Al2O3：P2O5：SiO2：TMHD：H2O=0.8：1.0：
0.6：2：50 proportional arrangement film synthesis mother liquid, is put into the supporter of load crystal seed, in an oven with 1 DEG C/min speed liter
Temperature is incubated 24h to 200 DEG C, then is cooled to 25 DEG C with 1 DEG C/min speed, takes out supporter, and kept in ozone environment
200 DEG C of calcining 28h, obtain product doughnut SAPO-56 molecular screen membranes.
Reference examples 4
From four-way aluminum oxide doughnut supporter, supporter is placed in ultrasound 20 minutes, cleaning, drying in distilled water.Will
Supporter is put into concentration for 1wt%SAPO-56（+0.125wt%HPC）In crystal seed liquid, the SAPO-56 without high energy ball mill processing
Crystal seed size is about 15 μm, by the way of Best-Effort request, and aluminum oxide four-way doughnut supporter is placed in crystal seed liquid
Impregnate and taken out after 10s, be put into 60 DEG C of baking ovens and dry 4h, be then placed in Muffle furnace after 450 DEG C of calcining 8h removings HPC, obtain
It is loaded with the supporter of crystal seed；
By boehmite, phosphoric acid, Ludox, TMHD using mol ratio as Al2O3：P2O5：SiO2：TMHD：H2O=0.8：1.0：
0.6：2：50 proportional arrangement film synthesis mother liquid, is put into the supporter of load crystal seed, in an oven with 1 DEG C/min speed liter
Temperature is incubated 48h to 200 DEG C, then is cooled to 25 DEG C with 1 DEG C/min speed, takes out supporter, and kept in ozone environment
200 DEG C of calcining 28h, obtain product doughnut SAPO-56 molecular screen membranes.
Reference examples 5
From four-way aluminum oxide doughnut supporter, supporter is placed in ultrasound 20 minutes, cleaning, drying in distilled water.Will
Supporter is put into concentration for 1wt%SAPO-56（+0.125wt%HPC）In crystal seed liquid, the SAPO-56 handled through high energy ball mill is brilliant
It is about 0.3 μm to plant size, by the way of Best-Effort request, and aluminum oxide four-way doughnut supporter is placed in crystal seed liquid and soaked
Taken out after stain 10s, be put into 60 DEG C of baking ovens and dry 4h, be then placed in Muffle furnace after 450 DEG C of calcining 8h removings HPC, born
It is loaded with the supporter of crystal seed；
By boehmite, phosphoric acid, Ludox, TMHD using mol ratio as Al2O3：P2O5：SiO2：TMHD：H2O=0.8：1.0：
0.6：2：50 proportional arrangement film synthesis mother liquid, is put into the supporter of load crystal seed, is heated up in an oven with 1 DEG C/min speed
To 200 DEG C, 48h is incubated, then 25 DEG C are cooled to 1 DEG C/min speed, supporter, and 550 DEG C of the holding in Muffle furnace is taken out
3h is calcined, product doughnut SAPO-56 molecular screen membranes are obtained.
Gas separation test is carried out to the film prepared by the various embodiments described above as follows：At 25 DEG C, four-way doughnut
The charging of SAPO-56 molecular screen membrane components is CO2/CH4Mol ratio is 1:1 mixed gas, feed side pressure 0.1MPa, infiltration
Side is atmospheric pressure.Per-meate side flow is measured with soap bubble flowmeter, and per-meate side gas is constituted by Shimadzu gas-chromatography（GC-2014）Survey
.
The preparation condition and gas separating resulting of SAPO-56 molecular screen membranes synthesized by embodiment 1 and reference examples 1~the 5 such as institute of table 1
Show.
Table 1
Table 1 is shown, according to the SAPO-56 molecular screen membranes of the preparation of embodiment 1, its separation selectivity highest, CO2Flux also highest；
The content of the synthesis mother liquid reclaimed water of reference examples 1 is reduced, and Synthesis liquid concentration becomes big so that the molecular screen membrane of supporting body surface generation is not
Uniform compact, its CO2Permeability and CO2/CH4Selection separation property it is also poor, its surface Electronic Speculum SEM photograph is as shown in Figure 7.It is right
Supporter is pre-processed with 0.1mol/L NaOH weak caustic solutions in 2 as usual, test result indicates that effect is with distillation water process
Carrier is good, its CO2Permeability and CO2/CH4Selection separation property be also inferior to embodiment 1, its surface Electronic Speculum SEM photograph such as Fig. 8 institute
Show.Reference examples 3 are compared to embodiment 1, and generated time is reduced to 24h by 48h, and generated time, which shortens, causes supporting body surface to be given birth to
Into film layer can not be fine and close, separating effect is poor, caused by this is also in that film surface defect is more, and surface Electronic Speculum SEM shines
Piece is as shown in Figure 9.In reference examples 4, using the original crystal seed handled without high-energy ball milling, crystal seed size is about 15 μm, crystal seed mistake
Cause carrier can not obtain the supporter that crystal seed is uniformly present in by the painting crystal type of Best-Effort request greatly, so it is female in synthesis
The good molecular screen membrane of air-tightness can not be prepared in liquid, as shown in Figure 10, it is for CO for surface Electronic Speculum SEM photograph2And CH4Nothing
Select separation property.The SAPO-56 molecular screen membranes of preparation are placed in removing template machine TMHD in Muffle furnace in reference examples 5, at 550 DEG C
Air atmosphere in, there is carbonization phenomenon in film surface, film layer blackening, and without air-tightness, for CO2And CH4Without selection separation
Property, surface Electronic Speculum SEM photograph is as shown in figure 11.
In addition, the CO in table 12The resistance to mass tranfer that the thickness of itself wall of permeability and supporter is brought is relevant, and the present invention is adopted
With high-strength alumina four-way doughnut supporter, support body layer resistance to mass tranfer is reduced.
Claims (10)
1. a kind of SAPO-56 molecular screen membranes, it is characterised in that include selection separating layer and supporter, selection separating layer is overlying on
The surface of supporter；Described selection separating layer is made up of fine and close SAPO-56 molecular sieves；Described supporting layer is by many
Hole ceramics are constituted.
2. SAPO-56 molecular screen membranes according to claim 1, it is characterised in that the configuration of described supporter is selected from piece
Formula, tubular type or hollow fiber form；Number of channels inside the supporter of described hollow fiber form is 1~6, external diametrical extent
It is 2~6mm, inner passage diameter scope is 0.3~1.5mm；The thickness of the supporter of described chip is 1~10mm；It is described
Tubular type supporter external diameter preferably 4~20mm, internal diameter preferably 1~12mm.
3. SAPO-56 molecular screen membranes according to claim 1, it is characterised in that the preferred carborundum of material of porous ceramics,
One or several kinds of mixing in diatomite, mullite, aluminum oxide, zirconium oxide or titanium oxide.
4. the preparation method of the SAPO-56 molecular screen membranes described in claim 1, it is characterised in that comprise the following steps：
1st step, ball-milling treatment is carried out to SAPO-56 molecular sieves using high energy ball mill, stand-by as crystal seed；
2nd step, crystal seed is added water and is configured to suspension, adds thickener, after being well mixed, as crystal seed liquid；Again by drying
Porous ceramic support immersion crystal seed liquid in, carry out Best-Effort request, after taking-up, drying；Again by calcining, obtain being loaded with crystalline substance
The supporter planted；
3rd step, the supporter for being loaded with crystal seed is placed in film Synthesis liquid, carries out Hydrothermal Synthesiss, after taking-up, drying, then smelly
Calcined under oxygen environment, obtain SAPO-56 molecular screen membranes；In the 1st described step, ball milling refers to break in SAPO-56 molecular sieves
The broken fine powder for 50nm~2 μm, more preferably 0.3 μm.
5. the preparation method of SAPO-56 molecular screen membranes according to claim 4, it is characterised in that in the 2nd described step,
Concentration of the crystal seed in suspension is 0.5~1wt%, and concentration of the thickener in crystal seed liquid is 0.02~0.1wt%；Described
In 2 steps, thickener is hydroxypropyl cellulose（HPC）；In the 2nd described step, the preferred carborundum of material of porous ceramic support,
One or several kinds of mixing in diatomite, mullite, aluminum oxide, zirconium oxide or titanium oxide；The structure of described supporter
Type is selected from chip, tubular type or hollow fiber form；The porous ceramic support of described drying is to first pass through to add in distilled water
Ultrasonically treated mistake；In the 2nd described step, the parameter of calcination process is：440~460 DEG C of 6~10h of calcining.
6. the preparation method of SAPO-56 molecular screen membranes according to claim 5, it is characterised in that in the 3rd described step,
In film Synthesis liquid silicon source, phosphorus source, silicon source, template be according to mol ratio be Al2O3：P2O5：SiO2：Template：H2O=0.8：
（0.8~1.2）：（0.5~0.7）：（1.8~2.2）：（45~55）Proportional arrangement；Preferred ratio is 0.8：1.0：
0.6：2：50；Described template is N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine（TMHD）.
7. the preparation method of SAPO-56 molecular screen membranes according to claim 4, it is characterised in that in the 3rd described step,
The parameter of Hydrothermal Synthesiss is：180~220 DEG C are warming up to 0.8~1.2 DEG C/min speed, are incubated 40~50h, then with 0.8~
1.2 DEG C/min speed is cooled to 20~30 DEG C.
8. the preparation method of SAPO-56 molecular screen membranes according to claim 4, it is characterised in that in the 3rd described step,
Calcining refers in ozone environment with 180~220 DEG C of 25~30h of calcining.
9. the SAPO-56 molecular screen membranes described in claim 1 are in CO2/CH4Application in gas separation.
10. application according to claim 9, it is characterised in that refer to improve CO2/CH4CO in gas separation2Permeability and
CO2/CH4Separation selectivity.
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