CN114653228A - Preparation method of RHO type molecular sieve membrane - Google Patents
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- CN114653228A CN114653228A CN202210369313.9A CN202210369313A CN114653228A CN 114653228 A CN114653228 A CN 114653228A CN 202210369313 A CN202210369313 A CN 202210369313A CN 114653228 A CN114653228 A CN 114653228A
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- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 66
- 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 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001868 water Inorganic materials 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 110
- 229910052681 coesite Inorganic materials 0.000 claims description 61
- 229910052906 cristobalite Inorganic materials 0.000 claims description 61
- 239000000377 silicon dioxide Substances 0.000 claims description 61
- 229910052682 stishovite Inorganic materials 0.000 claims description 61
- 229910052905 tridymite Inorganic materials 0.000 claims description 61
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000011775 sodium fluoride Substances 0.000 claims description 14
- 235000013024 sodium fluoride Nutrition 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 10
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical group NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 40
- 238000000926 separation method Methods 0.000 description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000000329 molecular dynamics simulation Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940026110 carbon dioxide / nitrogen Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Images
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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparation method of an RHO type molecular sieve membrane, which comprises the following steps: the method comprises the following steps: mixing an alkali source, a silicon source, an aluminum source, a fluorine source and water, aging the sol for 1-48 hours, pouring the sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal synthesis at the temperature of 80-200 ℃ for 1-7 days, and cleaning, centrifuging and drying to obtain an RHO molecular sieve crystal; step two: ultrasonically cleaning and drying the tubular porous support body for later use, dispersing the RHO molecular sieve synthesized in the step one into water or an organic solvent to prepare a seed crystal suspension solution, and coating the seed crystal on the surface of the support body; step three: and (3) mixing an alkali source, a silicon source, an aluminum source, a fluorine source and water, stirring and aging for 6-24 hours, placing the support body coated with the seed crystal layer in the step two in a stainless steel reaction kettle filled with sol, carrying out hydrothermal synthesis for 1-7 days at the temperature of 80-200 ℃, and cleaning and drying after reaction to obtain the RHO type molecular sieve membrane.
Description
Technical Field
The invention belongs to the field of preparation and application of molecular sieve membrane materials, and relates to a preparation method of an RHO type molecular sieve membrane.
Background
Flue gases emitted from thermal power plants and petrochemical industries involve the separation of large amounts of gases such as carbon dioxide and nitrogen, carbon oxides and methane, hydrogen and hydrocarbons, hydrogen and carbon dioxide, and nitrogen and oxygen. Common industrial gas separation methods mainly include a physical chemical solvent absorption method, a solid adsorption method, a low-temperature distillation method, a membrane separation method and the like. The chemical absorption method is used in the industrial field for many years, the process flow is mature, but the traditional chemical absorption devices such as a packed tower and the like are easy to have engineering technical problems of liquid flooding, entrainment and the like during operation. Solid adsorption process for CO separation by reversible adsorption-desorption operation2Simple operation, easy automation, but is not suitable for large-scale CO2The treatment and the energy consumption are very high. The membrane separation technology has the advantages of low energy consumption, continuous separation process, simple operation, easy coupling and the like because the separation process does not involve phase change, and is more and more concerned in the field of gas separation. The flue gas is a main emission source of greenhouse gas, the main components of the flue gas are nitrogen, carbon dioxide and sulfide, the components of the flue gas are complex, and the pollution of the emission of the flue gas to the atmosphere is the composite pollution of various poisons. The key to separate the carbon dioxide gas in the flue gas is. Higher temperatures in the flue gas can damage the structure of some membranes, and the flue gas contains a large amount of water vapor and is due to CO2And N2The molecular dynamics diameter of the membrane is small, and the traditional membrane material is difficult to achieve the purpose of high-efficiency separation.
Inorganic membranes, especially molecular sieve membranes, have been highly thermally, chemically and mechanically stable for over two decadesThe characteristics such as mechanical stability and pressure resistance have been receiving wide attention. Some molecular sieve membranes such as LTA, MFI, CHA, DDR type, etc. have been reported to be applied to pervaporation dehydration or CO2/CH4And (5) separating.
The LTA (NaA) type molecular sieve membrane has relatively low hydrothermal stability, is difficult to control intercrystalline defects, and has low separation performance. The pore size of the MFI type molecular sieve membrane is 0.55 nm, and the separation performance of the MFI type molecular sieve membrane is not high for the separation of small molecular gases. DDR-type, CHA-type molecular sieve membranes are widely reported for the separation of carbon dioxide and methane, mainly for natural gas decarbonization and biogas purification. The DDR type molecular sieve has a two-dimensional pore structure, so that the permeation rate of carbon dioxide is low. The CHA-type molecular sieve membrane with a three-dimensional structure has sufficiently high carbon dioxide permeability, but the pore diameter of 0.38nm is slightly larger than the molecular dynamics diameter (0.364 nm) of nitrogen, so the separation performance of carbon dioxide and nitrogen is still insufficient to meet the separation application requirement of industrial flue gas. The method has great scientific significance and application value in the aspects of flue gas carbon capture and energy-saving and efficient recovery of hydrogen in tail gas in the petrochemical industry and development of a novel molecular sieve membrane material with strict molecular sieving capability.
The RHO type molecular sieve membrane has uniform three-dimensional molecular sieve pore channels and high CO2Preferential adsorption selectivity and excellent thermal, chemical and mechanical stability. The pore size of the RHO type molecular sieve crystal is 0.36nm, is larger than hydrogen (0.29 nm) and carbon dioxide (0.33 nm), is smaller than the kinetic diameters of all alkane and olefin gas molecules including nitrogen (0.364 nm) and C1 and above, and has strict molecular sieving capability on hydrogen/hydrocarbon, carbon dioxide/nitrogen, carbon dioxide/methane and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an RHO type molecular sieve membrane, and the RHO type molecular sieve membrane is applied to the field of gas separation. The specific technical scheme of the invention is as follows: a high-quality RHO type molecular sieve membrane is synthesized by adopting a fluorine mineralizer and an alkali mineralizer under the synergistic effect, and the method comprises the following specific steps: a preparation method of an RHO type molecular sieve membrane comprises the following steps: the method comprises the following steps: RHO typePreparing molecular sieve crystal seeds: mixing an alkali source, a silicon source, an aluminum source, a fluorine source and water, wherein the formed sol comprises the following components in molar ratio: SiO 22/Al2O3=5-100， OH-/SiO2=0.1-1.0， H2O/SiO2=10-100， F-/SiO2Aging sol for 1-48 hr, pouring into stainless steel reactor with polytetrafluoroethylene lining, hydrothermal synthesizing at 80-200 deg.C for 1-7 days, cleaning, centrifuging, and drying to obtain RHO molecular sieve crystal; step two: pretreatment of a carrier: ultrasonically cleaning and drying the tubular porous carrier for later use, dispersing the RHO molecular sieve synthesized in the step one into water or an organic solvent to prepare a seed crystal suspension solution, and coating the seed crystal on the surface of the carrier; step three: preparing an RHO type molecular sieve membrane: mixing an alkali source, a silicon source, an aluminum source, a fluorine source and water, stirring and aging for 6-24 hours, wherein the formed sol comprises the following components in molar ratio: SiO 22/Al2O3=5-100，OH-/SiO2=0.1-1.0，H2O/SiO2=10-100，F-/SiO2And 5, putting the carrier coated with the seed crystal layer in the step two into a stainless steel reaction kettle filled with sol, carrying out hydrothermal synthesis at the temperature of 80-200 ℃ for 1-7 days, and cleaning and drying after reaction to obtain the RHO type molecular sieve membrane.
In step one, the OH-/SiO2Is Na2O/SiO2、Cs2O/SiO2、K2O/SiO2、Li2O/SiO2A mixture of one or more of the above, said F-/SiO2Is NaF/SiO2、HF/SiO2、NH4F/SiO2One kind of (1).
The material of the carrier is tubular alumina or mullite or silicon carbide or silicon oxide.
The average pore size of the carrier is 50-2000 nm, the porosity is 30-60%, the inner diameter is 1.5-7.0 mm, the outer diameter is 25-40 mm, and the length of the pipe is 50-1000 mm.
In the second step, the mass concentration of the suspension is 0.01-2 wt%; the solvent is water or ethanol or isopropanol.
In the second step, the method for coating the seed layer on the carrier is a dip coating method or a vacuum suction method or a wiping method or a spin coating method.
In the first step and the third step, the aluminum source is one of aluminum hydroxide, sodium metaaluminate, aluminum boehmite, aluminum isopropoxide, aluminum n-butoxide, aluminum foil, aluminum powder or aluminum oxide.
In the first step and the third step, the silicon source is one of silica sol, tetraethyl orthosilicate, tetramethyl orthosilicate, sodium silicate, water glass or silicon powder.
In the first step and the third step, the alkali source is cesium hydroxide or lithium hydroxide or sodium hydroxide or potassium hydroxide.
In the first step and the third step, the fluorine source is sodium fluoride or hydrogen fluoride or ammonium fluoride or potassium fluoride.
The invention adopts fluorine mineralizer and alkali mineralizer to cooperatively regulate the microstructure of the RHO crystal layer, and synthesizes the RHO molecular sieve membrane with no defect and high separation performance on the outer wall of the porous carrier. The molecular sieve membrane with higher compactness and separation efficiency is synthesized under the synergistic action of the fluorine mineralizer and the alkali mineralizer, the synthesis time is obviously shortened, and CO is separated2/N2Has high classification selectivity in the system.
Drawings
FIG. 1 is an XRD pattern of the RHO-type molecular sieve and molecular sieve membrane prepared in example 1.
FIG. 2 is an SEM image of seeds of the RHO type molecular sieve prepared in example 1.
FIG. 3 is a surface SEM image of the RHO type molecular sieve membrane prepared in example 1.
FIG. 4 is a SEM image of a cross-section of a RHO type molecular sieve membrane prepared in example 1.
FIG. 5 is a graph of the permeation performance of a single component of the RHO type molecular sieve membrane prepared in example 1.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
The preparation method of the RHO type molecular sieve membrane is specifically as follows: the method comprises the following steps: : RHO type moleculesPreparing the sieve seed crystal, namely mixing cesium hydroxide, sodium hydroxide, silica sol, aluminum hydroxide, sodium fluoride and deionized water according to a certain proportion, wherein the formed sol comprises the following components in molar ratio: SiO 22/Al2O3=10，Na2O/SiO2=0.3，Cs2O/SiO2=0.04， H2O/SiO2=11，NaF/SiO2Aging sol for 24 hours, pouring the sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal synthesis at the temperature of 100 ℃ for 2 days, and cleaning, centrifuging and drying to obtain an RHO molecular sieve crystal; step two: pretreatment of a carrier: and (2) ultrasonically cleaning and drying the tubular porous alumina carrier for later use, dispersing the RHO molecular sieve seed crystals synthesized in the step one into an ethanol solvent to prepare a 0.01wt% seed crystal suspension solution, and coating the seed crystals on the surface of the carrier by using a dipping and pulling method. Step three: preparing an RHO type molecular sieve membrane: mixing cesium hydroxide, sodium hydroxide, silica sol, aluminum hydroxide, sodium fluoride and deionized water according to a certain proportion, aging for 6-24 hours, wherein the molar ratio of the components of the formed sol is as follows: SiO 22/Al2O3=10，Na2O/SiO2=0.3，Cs2O/SiO2=0.04，H2O/SiO2=22，NaF/SiO2And 5, putting the alumina carrier coated with the seed crystal layer in the step two in a stainless steel reaction kettle filled with the sol, carrying out hydrothermal synthesis at 120 ℃ for 2 days, and cleaning and drying after reaction to obtain the RHO type molecular sieve membrane. The resultant membrane was designated as M1.
In the first step and the third step, the silicon source is one of silica sol, tetraethyl orthosilicate, tetramethyl orthosilicate, sodium silicate, water glass or silicon powder. The alkali source is cesium hydroxide or lithium hydroxide or sodium hydroxide or potassium hydroxide. The fluorine source is sodium fluoride or hydrogen fluoride or ammonium fluoride or potassium fluoride.
As shown in figure 1, XRD diffraction patterns of the RHO type molecular sieve seed crystal and the molecular sieve membrane M1 have XRD peaks completely matched with simulated RHO phases, which indicates that the synthesized ROH type molecular sieve seed crystal and the molecular sieve membrane are pure RHO phases.
As shown in fig. 2, the SEM image of the RHO molecular sieve seeds has a morphology of a typical octahedral shape with a particle size of about 1 m.
As shown in FIGS. 3 and 4, which are SEM images of the surface and cross-section of the membrane M1, it can be seen that the surface of the resultant membrane is continuous and dense, and the membrane thickness is about 3M.
The separation performance of membrane M1 in the CO2/N2 system is shown in fig. 5 and table 1. Under the test conditions of 0.2MPa and 150 ℃, the separation selectivity of the membrane M1 to CO2/N2 is 15, and the corresponding permeation rate of CO2 is 2.5 multiplied by 10 < -7 > mol/(M2 s Pa).
Example 2
The procedure was as in example 1, except that the sol synthesized in step one and step three had the following molar composition: SiO 22/Al2O3=10，Na2O/SiO2=0.3，Cs2O/SiO2=0.05，H2O/SiO2=44，NaF/SiO2=0.1 the procedure was otherwise the same as in example 1, and the film produced was designated as M2.
Membrane M2 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 3
The procedure was as in example 1, except that the sol synthesized in step one and step three had the following molar composition: SiO 22/Al2O3=10， K2O/SiO2=0.1，Cs2O/SiO2=0.1，H2O/SiO2=10，HF/SiO2=0.1 and the rest of the procedure is the same as example 1 and the film produced is denoted as M3.
Membrane M3 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 4
The procedure was as in example 1, except that the sol synthesized in step one and step three had the following molar composition: SiO 22/Al2O3=22，Li2O/SiO2=0.4，Cs2O/SiO2=0.04，H2O/SiO2=44，NaF/SiO2=0.05, the rest steps are as in the examples1 and the film obtained is designated M4.
Membrane M4 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 5
The procedure was as in example 1, except that the sol synthesized in step one and step three had the following molar composition: SiO 22/Al2O3=100，Na2O/SiO2=0.8，Cs2O/SiO2=0.1，H2O/SiO2=88，NH4F/SiO2=0.5, the remaining steps are the same as example 1, and the prepared film is denoted as M5.
Membrane M5 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 6
The procedure was as in example 1, except that the sol synthesized in step one and step three had the following molar composition: SiO 22/Al2O3=5，Na2O/SiO2=0.03，Cs2O/SiO2=0.01，H2O/SiO2=10，NH4F/SiO2=0.05 and the rest of the procedure is the same as example 1 and the film produced is denoted as M6.
Membrane M5 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 7
The procedure is as in example 1 except that in steps one and two aluminum sources are sodium metaaluminate, silicon sources are silica fume, the seed suspension used in step two has a concentration of 2 wt%, the remaining steps are the same as in example 1, and the film obtained is designated as M7.
Membrane M6 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 8
The procedure used is as in example 1, except that in step one) and in step two) the NaF/SiO in the seed and film synthesis sol is2=0.5、H2O/SiO2=100, the carrier used in step two is mullite carrier, RHO molecular sieve seeds in step two are dispersed in 0.01wt% isopropanol solvent, the rest steps are the same as example 1, and the obtained film is marked as M8.
Membrane M7 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 9
The procedure used was as in example 1, except that in step two, the seed coating was carried out by vacuum suction, the seed suspension concentration was 0.01% by weight and the solvent was water. The procedure is otherwise as in example 1, and the film obtained is designated M9.
Membrane M8 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 10
The procedure is as in example 1 except that the RHO molecular sieve membrane in step three is reacted at a temperature of 200 ℃ for 1 day, and the rest of the procedure is the same as in example 1, and the membrane obtained is designated as M10.
Membrane M9 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions are as follows: 0.2MPa, 150 ℃.
Example 11
The procedure is as in example 1 except that the RHO molecular sieve membrane in step three is reacted at 80 ℃ for 7 days, the rest of the procedure is the same as in example 1, and the membrane obtained is designated M11.
Membrane M10 in CO2/N2The separation performance of the system is shown in fig. 5 and table 1. And (3) testing conditions: 0.2MPa, 150 ℃.
Comparative example 1
The CHA-type molecular sieve Membrane is prepared by the following methods in Journal of Membrane Science, 2019, 573, 333-:
the method comprises the following steps: the CHA type molecular sieve seed crystal is prepared by mixing silicon powder, N-N-N-trimethyl-1-adamantyl ammonium hydroxide and deionized water according to a certain proportion, and fully stirring at room temperature until the mixture is completely stirredDissolving, adding all-silicon CHA molecular sieve, heating the mixture at 60 deg.C, stirring thoroughly to evaporate water to obtain dry powder, and adding hydrofluoric acid until the sol is neutral. Heating to evaporate water to reach required water content, and the synthesized sol comprises the following components in mol percentage: 1.0 SiO2:0.8 TMAdaF:5.7 H2And (O). Putting the sol into a stainless steel reaction kettle at 150 DEG C。Hydrothermal synthesis is carried out for 96 h at the temperature of C, the product obtained after the reaction is finished is taken out, and the product obtained after the reaction is centrifuged, washed to be neutral, dried and calcined to obtain the all-silicon CHA molecular sieve seed crystal, wherein the size of the seed crystal is about 200 nm. Step two: pretreatment of a carrier: and (2) ultrasonically cleaning and drying the tubular porous carrier for later use, dispersing the CHA molecular sieve synthesized in the step (1) into an ethanol solvent to prepare a seed crystal suspension solution, and coating the seed crystal on the surface of the carrier by means of dipping, pulling and the like. Step three: preparation of CHA-type molecular sieve membrane: mixing sodium hydroxide, aluminum hydroxide, sodium fluoride and water, stirring and aging at room temperature for 24 hours to form sol, wherein the sol comprises the following components in molar ratio: 1.0 SiO2: 0.09 Al2O3: 0.3 Na2O: 0.04 Cs2O: 0.3 NaF: 60H2And O, placing the carrier coated with the seed crystal layer in the step (2) in a stainless steel reaction kettle filled with sol, carrying out hydrothermal synthesis for 3 days at the temperature of 140 ℃, cleaning and drying after reaction to obtain the CHA type molecular sieve membrane, and marking the synthesized membrane as M12.
TABLE 1 example and comparative example to CO2/N2Separation performance of mixed gas
It can be seen from the examples and table 1 that the RHO type molecular sieve membrane with high quality is prepared for the first time by the crystal growth promotion effect of the mineralizer fluorine and the secondary growth method. The RHO type molecular sieve membrane synthesized under the synergistic condition of the fluorine mineralizer and the alkali mineralizer has higher compactness and separation efficiency, and obviously shortens the synthesis time. The RHO type molecular sieve membrane synthesized by the invention can be applied to carbon capture of flue gas and CO2/N2Separation ofThe factor is greater than 15.
Claims (10)
1. A preparation method of an RHO type molecular sieve membrane comprises the following steps: the method comprises the following steps: preparing RHO type molecular sieve seed crystal: mixing an alkali source, a silicon source, an aluminum source, a fluorine source and water, wherein the formed sol comprises the following components in molar ratio: SiO 22/Al2O3=5-100， OH-/SiO2=0.1-1.0， H2O/SiO2=10-100， F-/SiO2Aging sol for 1-48 hr, pouring into stainless steel reactor with polytetrafluoroethylene lining, hydrothermal synthesizing at 80-200 deg.C for 1-7 days, cleaning, centrifuging, and drying to obtain RHO molecular sieve crystal; step two: pretreatment of a carrier: ultrasonically cleaning and drying the tubular porous carrier for later use, dispersing the RHO molecular sieve synthesized in the step one into water or an organic solvent to prepare a seed crystal suspension solution, and coating the seed crystal on the surface of the carrier; step three: preparing an RHO type molecular sieve membrane: mixing an alkali source, a silicon source, an aluminum source, a fluorine source and water, stirring and aging for 6-24 hours, wherein the formed sol comprises the following components in molar ratio: SiO 22/Al2O3=5-100，OH-/SiO2=0.1-1.0，H2O/SiO2=10-100，F-/SiO2And 5, putting the carrier coated with the seed crystal layer in the step two into a stainless steel reaction kettle filled with sol, carrying out hydrothermal synthesis at the temperature of 80-200 ℃ for 1-7 days, and cleaning and drying after reaction to obtain the RHO type molecular sieve membrane.
2. The method of claim 1, wherein: in step one, the OH-/SiO2Is Na2O/SiO2、Cs2O/SiO2、K2O/SiO2、Li2O/SiO2A mixture of one or more of the above, said F-/SiO2Is NaF/SiO2、HF/SiO2、NH4F/SiO2One kind of (1).
3. The method of claim 1, wherein: the material of the carrier is tubular alumina or mullite or silicon carbide or silicon oxide.
4. The method of claim 1, wherein: the average pore size of the carrier is 50-2000 nm, the porosity is 30-60%, the inner diameter is 1.5-7.0 mm, the outer diameter is 25-40 mm, and the length of the pipe is 50-1000 mm.
5. The method of any one of claims 1 to 4, wherein: in the second step, the mass concentration of the suspension is 0.01-2 wt%; the solvent is water or ethanol or isopropanol.
6. The method of any one of claims 1 to 4, wherein: in the second step, the method for coating the seed layer on the carrier is a dip coating method or a vacuum suction method or a wiping method or a spin coating method.
7. The method of any one of claims 1 to 4, wherein: in the first step and the third step, the aluminum source is one of aluminum hydroxide, sodium metaaluminate, aluminum boehmite, aluminum isopropoxide, aluminum n-butoxide, aluminum foil, aluminum powder or aluminum oxide.
8. The method of any one of claims 1 to 4, wherein: in the first step and the third step, the silicon source is one of silica sol, tetraethyl orthosilicate, tetramethyl orthosilicate, sodium silicate, water glass or silicon powder.
9. The method of any one of claims 1 to 4, wherein: in the first step and the third step, the alkali source is cesium hydroxide or lithium hydroxide or sodium hydroxide or potassium hydroxide.
10. The method of any one of claims 1 to 4, wherein: in the first step and the third step, the fluorine source is sodium fluoride or hydrogen fluoride or ammonium fluoride or potassium fluoride.
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