CN114560474A - Synthesis method of metal modified M-MFI molecular sieve membrane - Google Patents
Synthesis method of metal modified M-MFI molecular sieve membrane Download PDFInfo
- Publication number
- CN114560474A CN114560474A CN202210222066.XA CN202210222066A CN114560474A CN 114560474 A CN114560474 A CN 114560474A CN 202210222066 A CN202210222066 A CN 202210222066A CN 114560474 A CN114560474 A CN 114560474A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mfi molecular
- sieve membrane
- membrane
- mfi
- 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 125
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 102
- 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 102
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000001308 synthesis method Methods 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 44
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000013078 crystal Substances 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 229910052681 coesite Inorganic materials 0.000 claims description 30
- 229910052906 cristobalite Inorganic materials 0.000 claims description 30
- 229910052682 stishovite Inorganic materials 0.000 claims description 30
- 229910052905 tridymite Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 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
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- -1 transition metal salt Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Chemical class 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Chemical class 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 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
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Chemical class 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052718 tin Chemical class 0.000 claims description 2
- 239000010936 titanium Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical class [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 229910052723 transition metal Inorganic materials 0.000 claims 6
- 150000003624 transition metals Chemical class 0.000 claims 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 239000000919 ceramic Substances 0.000 claims 1
- 229910052878 cordierite Inorganic materials 0.000 claims 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 claims 1
- 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 1
- 229910052863 mullite Inorganic materials 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical class [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 29
- 239000011148 porous material Substances 0.000 abstract description 21
- 238000005342 ion exchange Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000007873 sieving Methods 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000005538 encapsulation Methods 0.000 abstract description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 64
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 32
- 239000001282 iso-butane Substances 0.000 description 31
- 235000013847 iso-butane Nutrition 0.000 description 31
- 238000012360 testing method Methods 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 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
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- KHOMMWHGIAOVKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;nickel Chemical compound [Ni].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KHOMMWHGIAOVKF-UHFFFAOYSA-N 0.000 description 1
- 101710184444 Complexin Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Images
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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a synthesis method of a metal modified M-MFI type molecular sieve membrane. The metal complex is used as a metal source, and metal elements are doped into the pore channels of the MFI molecular sieve membrane in situ in the forming process of the MFI molecular sieve membrane, so that the one-step encapsulation of the metal elements in the framework of the MFI molecular sieve membrane is realized. The metal elements exist in the pore channels of the MFI molecular sieve membrane, so that the size of the pore channels of the MFI molecular sieve membrane can be adjusted, and the separation performance of the MFI molecular sieve membrane is improved. Compared with the conventional post-treatment method such as an ion exchange method, the method is simple and easy to implement, has high synthesis repetition rate, and is beneficial to the batch production of the membrane. The M-MFI molecular sieve membrane prepared by the method has better size sieving performance and is suitable for separating alkane isomers.
Description
Technical Field
The invention relates to a method for preparing a metal-doped M-MFI molecular sieve membrane by a metal modification one-step method, belonging to the field of preparation of molecular sieve membrane materials.
Background
The zeolite molecular sieve has a regular pore channel structure, the pore size is adjustable, the zeolite molecular sieve is a novel separation membrane material, fine screening separation of molecular size can be realized, and meanwhile, the molecular sieve membrane has excellent thermal stability and chemical stability, so that the zeolite molecular sieve has wide application prospect in separation of normal/isoparaffin systems with large separation difficulty in industry.
MFI molecular sieve membrane in normal/iso hydrocarbonThe separation shows excellent separation performance, and the research is widely carried out in the separation of systems such as normal/isobutane, ortho/para-xylene and the like. Agrawal et al [ adv. mater. 2015, 27, 3243-]Preparing ultrathin on the surface of a porous quartz fiber carrierb-Axially oriented MFI molecular sieve membrane, 100oUnder C, the permeation rate of the synthesized membrane to the normal/iso-butane mixed system can reach 11.9 multiplied by 10−7 mol (m2 sPa)-1The normal/isobutane selectivity was 20 at 150oAt C, the permeation rate of the membrane to an o/p-xylene system is as high as 5.1 x 10−7 mol (m2 sPa)-1The selectivity was 30. Literature [ Journal of Membrane Science 540 (2017) 50-59]Synthesized on the surface of a tubular alumina carrierh0hSynthesis of oriented MFI molecular sieve membranes, 90oThe permeation rate of the membrane to the normal/iso-butane mixed system is as high as 3.1 multiplied by 10 under C−7 mol (m2 sPa)-1The normal/isobutane separation factor is up to 46. The pore size of the molecular sieve membrane is not continuous, so that in the separation of gas mixture, the precise sieving is difficult to realize for the system with small molecular size difference, such as C4-C6 isomer mixture, and the selectivity of the membrane is not ideal for the mixed system. The separation performance of the membrane material can be improved by using some post-treatment means, such as surface modification means such as Chemical Vapor Deposition (CVD), Molecular Layer Deposition (MLD) and Catalytic Cracking Deposition (CCD), but the method only regulates the surface property and the pore size of the molecular sieve membrane, and the regulation means of the pore size inside the molecular sieve is lacked.
The metal heteroatom is introduced into the inside of the pore channel of the molecular sieve membrane by using an ion exchange method, so that the regulation and control of the size of the pore channel inside the molecular sieve membrane can be realized, the adsorption and mass transfer performance of the molecular sieve membrane can be effectively changed, and the selectivity of the membrane material can be improved. Marturano et al Catalysis Today, 2001, 67 (1-3): 101-]Mixing Fe3+After the ions are introduced into the molecular sieve, the pore volume is from 0.17 cm3The/g is reduced to 0.15 cm3And/g, showing that the introduction of the metal Fe can reduce the pore diameter of the molecular sieve. In the field of molecular sieve membrane research, there are currently many reports on improving the gas separation performance of molecular sieve membranes by introducing metal ions into the pore channels of the molecular sieve membranes.Hong et al [ Microporous and Mesoporous Materials, 2007, 106(1-3): 140-]Introduction of Li into SAPO-34 molecular sieve membrane by ion exchange method+、Na+、K+And NH4 +To make it CO2/CH4The ideal separation selectivity is improved by 60 percent, and the selectivity to H is improved2/CH4The improvement of the system is only 18 percent, which shows that obvious steric hindrance effect exists in the pore channel of the membrane through ion exchange. Sakai et al [ Acs Applied Materials& Interfaces, 2019, 11(4): 4145-4151]An Ag-X molecular sieve membrane is synthesized by a silver ion exchange method and is used for separating propylene/propane and ethylene/ethane, and the selectivity of the membrane to the olefin of the two systems is obviously improved by silver ion exchange.
The method of introducing metal ions into the pore channels inside the molecular sieve membrane by adopting post-treatment means such as an ion exchange method and the like is difficult to ensure the distribution uniformity of the metal ions in the pore channels of the molecular sieve membrane, the ion exchange degree is difficult to control, and the improvement on the membrane separation performance is not high. Meanwhile, the operation process of the method is complicated, and the membrane material needs to be soaked in water or other organic solvents, so that the crystal structure of the membrane is easily damaged, and the separation performance is lost.
Disclosure of Invention
The invention aims to provide a one-step synthesis method of a metal modified M-MFI molecular sieve membrane (M-MFI for short, the first M represents metal). The metal complex is used as a metal source, and metal elements are doped into the pore channel of the MFI molecular sieve membrane in situ in the synthesis process of the MFI molecular sieve membrane, so that the accurate regulation and control of the pore channel size of the MFI molecular sieve membrane are realized, and the size sieving performance of the membrane material is improved. The method is simple and easy to implement, high in synthesis repetition rate and beneficial to batch production of the membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a synthetic method of a metal modified M-MFI molecular sieve membrane comprises the following steps:
(1) preparing M-MFI molecular sieve seed crystal: mixing and stirring deionized water, metal salt and a complexing agent for 2 hours to form a metal complex MC; sequentially adding deionized water, a structure directing agent SDA, an aluminum source and a silicon source into the metal complexIn the composition, the molar ratio of each component of the formed sol is as follows: SiO-SDA2 = 0.05-0.5,Al2O3: SiO2 = 0-0.5,H2O: SiO2 = 20-200,MC: SiO2 = 0.01-0.5; aging the sol for 12-48 h, and keeping the temperature at 80-150 deg.CoReacting for 12-96 h at the temperature of C, and centrifuging, cleaning, drying and calcining the product to obtain a metal-doped M-MFI molecular sieve crystal;
(2) preparing an M-MFI molecular sieve crystal seed layer: dispersing the M-MFI crystals synthesized in the step (1) in absolute ethyl alcohol to form an M-MFI seed crystal/ethyl alcohol suspension with the mass fraction of 0.05-1%; vertically immersing a porous support body in the suspension, keeping the suspension for 10-60 s, uniformly extracting and drying to obtain an M-MFI molecular sieve seed crystal layer;
(3) preparing an M-MFI molecular sieve membrane: mixing and stirring deionized water, metal salt and a complexing agent for 2 hours to form a metal complex MC; stirring deionized water, a structure directing agent SDA, an aluminum source and a silicon source to form sol; adding the metal complex into the sol, mixing, stirring and aging for 4-24 h, wherein the molar ratio of the components of the formed sol is as follows: SiO-SDA2 = 0.05-0.5,Al2O3: SiO2 = 0-0.5,H2O: SiO2 = 20-1000,MC: SiO2 = 0.01-0.5; pouring the sol into a reaction kettle, and placing the sol into the seeded porous support prepared in the step (2) at the temperature of 100-oC, reacting for 12-48 h; and cleaning, drying and calcining the membrane tube by using a stripper plate agent to prepare the M-MFI molecular sieve membrane.
Preferably, the size of the M-MFI molecular sieve seed crystal prepared in the step (1) is 50-300 nm;
preferably, the mass concentration of the seed crystal suspension in the step (2) is 0.05-1wt%, and more preferably, the mass concentration of the suspension is 0.05-0.5 wt%;
preferably, the metal complex described in steps (1) and (3) is a metal complex formed by copper, silver, titanium, iron, nickel, zinc, cobalt, vanadium, tungsten or tin and complexing agents such as tetraethylenepentamine TEPA, diethylenetriamine DETA, ethylenediamine EDA, beta-diketone (II), ethylenediamine tetraacetic acid EDTA, and more preferably, the metal complex is Cu-TEPA and Fe-TEPA;
preferably, the structure directing agent in steps (1) and (3) is one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium iodide or tetraethylammonium bromide;
preferably, the silicon source in steps (1) and (3) is one or more of silica sol, tetraethyl orthosilicate, tetramethyl orthosilicate, sodium silicate, water glass or silicon powder;
preferably, the aluminum source in the steps (1) and (3) is one or more of aluminate, aluminum hydroxide, n-butyl aluminum alkoxide and aluminum isopropoxide;
preferably, the reaction temperature in step (3) is 100-200-oC, performing hydrothermal reaction for 12-48 h;
preferably, the process of demoulding agent in the step (3) is carried out in an ozone atmosphere, the concentration of ozone is 10-150 mg/L, and the temperature is 150 ℃ and 250 ℃; the calcination time is 24-96 h; the heating rate is 0.2-10 ℃ per min;
the beneficial effects of the invention are:
the invention takes the metal complex as a metal source, and the metal M element is doped into the pore channel of the MFI molecular sieve membrane in situ while the MFI molecular sieve membrane is formed, so that the one-step encapsulation modification of the metal M element in the molecular sieve membrane is realized. Compared with the conventional ion exchange method, the method provided by the invention has the advantages that the metal M element doping and the MFI molecular sieve membrane formation are synchronous, the steps are simple, the complex post-treatment process is not required, and the uniform distribution of the metal M element in the membrane material is ensured. The metal M element is doped into an MFI molecular sieve membrane pore channel, the size of the membrane material pore channel can be precisely regulated and controlled, the metal M element is involved in the transmission process of gas molecules, and the size screening capacity of the membrane material is improved. The selectivity of the metal modified M-MFI molecular sieve membrane synthesized by the method for preparing the n/i-butane mixed system is greatly improved.
The preparation method is simple and feasible, has high synthesis repetition rate, and has industrial development prospect.
Drawings
FIG. 1 is an SEM image of Cu-MFI molecular sieve seeds prepared in example 1.
Figure 2 is an XRD pattern of Cu-MFI molecular sieve seeds prepared in example 1.
FIG. 3 is a UV-Vis diagram of Cu-MFI molecular sieve seeds prepared in example 1.
Fig. 4 is an SEM image of the Cu-MFI molecular sieve seed layer prepared in example 1.
Fig. 5 is a surface SEM image of the Cu-MFI molecular sieve membrane prepared in example 1.
FIG. 6 is a sectional SEM photograph of the Cu-MFI molecular sieve membrane prepared in example 1.
Detailed Description
Specific examples for carrying out the invention are given below, but the scope of the invention claimed is not limited to the examples.
Example 1
A synthetic method of a metal modified M-MFI molecular sieve membrane comprises the following steps:
(1) preparing M-MFI molecular sieve seed crystal: deionized water and CuSO4·5H2Mixing and stirring O and a complexing agent tetraethylenepentamine for 2 hours to form a Cu-TEPA complex; deionized water, tetrapropylammonium hydroxide and tetraethyl orthosilicate are added into the Cu-TEPA complex, and the formed sol comprises the following components in molar ratio: SiO-SDA2 = 0.2,H2O: SiO2 = 96,Cu-TEPA: SiO2 = 0.01; after aging the sol for 12 h, 150 foReacting for 48 hours at the temperature of C, and centrifuging, cleaning, drying and calcining the product to obtain Cu-MFI molecular sieve crystals;
(2) preparing an M-MFI molecular sieve crystal seed layer: dispersing the M-MFI crystals synthesized in the step (1) in absolute ethyl alcohol to form a Cu-MFI seed crystal/ethanol suspension with the mass fraction of 0.25%; vertically immersing an alumina porous support in the suspension, keeping for 40 s, uniformly extracting and drying to prepare an M-MFI molecular sieve seed crystal layer, wherein the thickness of the seed crystal layer is about 0.5 mu M;
(3) preparing an M-MFI molecular sieve membrane: deionized water and CuSO4·5H2Mixing and stirring O and TEPA for 2 h to form a Cu-TEPA complex; stirring deionized water, tetrapropylammonium hydroxide and tetraethyl orthosilicate to form sol; adding the Cu-TEPA complex into sol, stirring the sol for agingAnd reacting for 4 h to form the sol, wherein the molar ratio of each component of the sol is as follows: SiO-SDA2 = 0.12,H2O: SiO2 = 60,MC: SiO2 = 0.01; pouring the sol into a reaction kettle, placing the sol into the seeded alumina porous support prepared in the step (2), and placing the support at 140 DEGoC, reacting for 24 hours; the membrane tube is cleaned, dried and treated with ozone in an atmosphere of 200 deg.CoAnd C, calcining for 48 hours to remove the template agent. And preparing the Cu-MFI molecular sieve membrane.
FIG. 1 is an SEM image of the Cu-MFI molecular sieve prepared in step (1), and shows that the dispersibility of the seed crystal is good, the particle size of the seed crystal is about 200 nm, and the seed crystal is in a short cylindrical shape;
FIG. 2 is an XRD (X-ray diffraction) diagram of the Cu-MFI molecular sieve prepared in the step (1), and the synthesized Cu-MFI molecular sieve has a typical MFI structural characteristic peak and is a pure MFI molecular sieve crystal;
FIG. 3 is a diagram of the Cu-MFI molecular sieve UV-Vis prepared in the step (1), and the synthesized Cu-MFI molecular sieve has a sharp peak at 222 nm and is isolated Cu2+And Cu+. Meanwhile, a broad absorption peak appears at 500-600 nm, which is CuO;
FIG. 4 is a surface SEM image of the molecular sieve crystal layer prepared in step (2), showing that the surface of the support is completely covered with Cu-MFI seeds;
FIG. 5 is a surface SEM image of the Cu-MFI molecular sieve membrane prepared in the step (3), which shows that the Cu-MFI molecular sieve crystals grow well in a cross-linking manner on the surface of the support body to form a compact Cu-MFI molecular sieve membrane;
FIG. 6 is a SEM (scanning Electron microscope) view of the section of the Cu-MFI molecular sieve membrane prepared in the step (3), and the thickness of the Cu-MFI molecular sieve membrane is about 2.5 μm.
The prepared membrane (M1) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 2
The procedure used is as in example 1. Except that in the step (1), the SDA is SiO2 = 0.05,H2O: SiO2 = 20,Cu-TEPA: SiO2 = 0.5, reaction at 80oAnd (4) carrying out the reaction for 96 h under the condition of C. Step (2) Cu-MFI molecular sieve seed crystal suspensionThe concentration of the supernatant was 1 wt%. The molar ratio of each component of the synthetic sol in the step (3) is as follows: SiO-SDA2 = 0.05,H2O: SiO2 = 20,Cu-TEPA: SiO2 = 0.01。
The prepared membrane (M2) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 3
The procedure was as in example 1, except that in step (1), SDA: SiO2 = 0.5,H2O: SiO2 = 200,Cu-TEPA: SiO2 Aging for 48 h, and reacting at 150 deg.C oCThe process was carried out for 12 h. The concentration of the Cu-MFI molecular sieve seed crystal suspension in the step (2) is 0.05 wt%. And (3) aging for 48 hours, wherein the molar ratio of each component of the synthetic sol is as follows: SiO-SDA2 = 0.5,H2O: SiO2 = 1000,Cu-TEPA: SiO2 = 0.5。
The prepared membrane (M3) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 4
The procedure used is as in example 1, except that the complexing agent used in steps (1) and (3) is Diethylenetriamine (DETA), the structure directing agent is tetrapropylammonium bromide, the silicon source is silica sol, and the membrane synthesis temperature is 100oAnd C, the synthesis time is 48 h.
The prepared membrane (M4) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 5
The procedure was as in example 1, except that the synthesis temperature of the membrane was 200oAnd C, the synthesis time is 12 h.
The prepared membrane (M5) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCPermeation rate of the membrane and normal butane/isobutaneThe selectivity data are shown in table 1.
Example 6
The procedure used was as in example 1, except that in step (3) the molar composition of the synthesis sol of the Cu-MFI molecular sieve membrane was: SiO-SDA2 = 0.2,H2O: SiO2 = 200,Cu-TEPA: SiO2 = 0.05。
The prepared membrane (M6) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 7
The procedure was as in example 1, except that the doped metal was nickel and the metal complex used was Ni-EDTA. The synthesized membrane is a Ni-MFI molecular sieve membrane.
The prepared membrane (M7) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 8
The procedure was as in example 1, except that the doped metal was silver, the metal complex used was Ag-EDTA, and the membrane synthesized was an Ag-MFI molecular sieve membrane.
The prepared membrane (M8) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 9
The procedure was as in example 1, except that the doped metals were iron and zinc in a molar ratio of 1: 1, the synthesized membrane is Fe, Zn-MFI molecular sieve membrane.
The prepared membrane (M9) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 10
The procedure used is as in example 1, except that in both steps (1) and (3) alumina hydroxide is added as aluminium source, Al2O3: SiO2 = 0.5。
The prepared membrane (M10) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Example 11
The procedure was as in example 1, except that alumina hydroxide was added as the aluminum source and Al was added to the sol in both steps (1) and (3)2O3: SiO2 = 0.0025。
The prepared membrane (M11) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
Comparative example 1
The preparation procedure used was the same as in example 1, except that the sol did not contain Cu and the coordination compound in steps (1) and (3).
Then carrying out Cu ion exchange by adopting an ion exchange method: adding the membrane to a solution containing copper sulfate-sulfuric acid-H2In a solution of O (pH 2 and Cu ion content 0.2 mol/l) at 90oIon exchange 2d under C. And taking out the membrane, cleaning and drying.
The prepared membrane (M12) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1. The membrane selectivity is low, which indicates that the M-MFI molecular sieve membrane prepared by the Cu ion exchange method has more defects and more complicated steps.
Comparative example 2
The procedure used is as in example 1, except that CuSO is used directly4·5H2And O is used as a Cu source to synthesize M-MFI seed crystals and M-MFI molecular sieve membranes.
The prepared membrane (M13) is used for the separation of an equimolar n-butane/isobutane mixed system, and the testing temperature is 30 oCThe permeation rate and n-butane/isobutane selectivity data for the membranes are shown in table 1.
TABLE 1M-MFI molecular sieve membranes at 30 oCSeparation performance data for equimolar n-butane/isobutane mixed system
Claims (8)
1. A method for synthesizing a metal modified M-MFI molecular sieve membrane is characterized in that a metal complex is used as a metal source, and a layer of metal element doped M-MFI molecular sieve membrane is synthesized in situ on the surface of a porous ceramic support body, and comprises the following steps:
(1) preparing M-MFI molecular sieve seed crystal: mixing and stirring deionized water, transition metal salt and a complexing agent for 2 hours to form a transition metal complex MC; deionized water, a structure directing agent SDA, an aluminum source and a silicon source are sequentially added into the metal complex, and the molar ratio of each component of the formed sol is as follows: SiO-SDA2 = 0.05-0.5,Al2O3: SiO2 = 0-0.5,H2O: SiO2 = 20-200,MC: SiO2 = 0.01-0.5; aging the sol for 12-48 h, and keeping the temperature at 80-150 deg.CoReacting for 12-96 h at the temperature of C, and centrifuging, cleaning, drying and calcining the product to obtain a metal-doped M-MFI molecular sieve crystal;
(2) preparing an M-MFI molecular sieve crystal seed layer: dispersing the M-MFI crystals synthesized in the step (1) in absolute ethyl alcohol to form an M-MFI seed crystal/ethyl alcohol suspension with the mass fraction of 0.05-1%; vertically immersing a porous support body in the suspension, keeping the suspension for 10-60 s, uniformly extracting and drying to obtain an M-MFI molecular sieve seed crystal layer;
(3) preparing an M-MFI molecular sieve membrane: mixing and stirring deionized water, transition metal salt and a complexing agent for 2 hours to form a transition metal complex MC; stirring deionized water, a structure directing agent SDA, an aluminum source and a silicon source to form sol; adding the transition metal complex into the sol, mixing, stirring and aging for 4-24 h, wherein the molar ratio of the components of the formed sol is as follows: SiO-SDA2 = 0.05-0.5,Al2O3: SiO2 = 0-0.5,H2O: SiO2 = 20-1000,MC: SiO2 = 0.01-0.5; pouring the sol into a reaction kettle, and placing the sol into the seeded porous support prepared in the step (2) at the temperature of 100-oC, reacting for 12-48 h; and cleaning, drying and calcining the membrane tube by using a stripper plate agent to prepare the M-MFI molecular sieve membrane.
2. The method for synthesizing a metal modified M-MFI molecular sieve membrane as claimed in claim 1, wherein the mass concentration of the seed suspension in the step (2) is 0.05 to 1 wt%.
3. The method for synthesizing a metal modified M-MFI molecular sieve membrane of claim 1, wherein the transition metal salt in steps (1) and (3) is one or more mixed salts of copper, silver, titanium, iron, nickel, zinc, cobalt, vanadium, tungsten or tin, and the complexing agent is tetraethylenepentamine TEPA, diethylenetriamine DETA, ethylenediamine EDA, beta-diketone (II) or ethylenediamine tetraacetic acid EDTA.
4. The method for synthesizing a metal modified M-MFI molecular sieve membrane as claimed in claim 1, wherein the structure directing agent SDA in steps (1) and (3) is one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium iodide or tetraethylammonium bromide.
5. The method for synthesizing a metal modified M-MFI molecular sieve membrane as claimed in claim 1, wherein the silicon source in steps (1) and (3) is one or more of silica sol, tetraethyl orthosilicate, tetramethyl orthosilicate, sodium silicate, water glass, or silicon powder.
6. The method for synthesizing a metal modified M-MFI molecular sieve membrane as claimed in claim 1, wherein the aluminum source in steps (1) and (3) is one or more of aluminate, aluminum hydroxide, aluminum n-butoxide and aluminum isopropoxide.
7. The synthesis method of the metal modified M-MFI molecular sieve membrane of claim 1, wherein in the step (3), the support body used for preparing the M-MFI molecular sieve membrane is a tubular or hollow fibrous support, and the material is alumina, stainless steel, mullite, cordierite, zirconia or silica.
8. The method for synthesizing a metal modified M-MFI molecular sieve membrane as claimed in claim 1, wherein the atmosphere for calcining the release sheet agent in step (3) is air, oxygen, ozone/air or ozone/oxygen.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210222066.XA CN114560474A (en) | 2022-03-09 | 2022-03-09 | Synthesis method of metal modified M-MFI molecular sieve membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210222066.XA CN114560474A (en) | 2022-03-09 | 2022-03-09 | Synthesis method of metal modified M-MFI molecular sieve membrane |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114560474A true CN114560474A (en) | 2022-05-31 |
Family
ID=81718235
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210222066.XA Pending CN114560474A (en) | 2022-03-09 | 2022-03-09 | Synthesis method of metal modified M-MFI molecular sieve membrane |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114560474A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116808847A (en) * | 2023-07-27 | 2023-09-29 | 大连理工大学 | Preparation method of ultrathin oriented W-MFI zeolite membrane for efficiently separating butane isomers |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1332114A (en) * | 2001-06-28 | 2002-01-23 | 复旦大学 | Optimized and oriented growth process of MFT-type zeolite crystal |
JP2011121854A (en) * | 2009-11-11 | 2011-06-23 | Mitsubishi Chemicals Corp | Method for producing porous support-zeolite membrane complex |
CN102350229A (en) * | 2011-08-24 | 2012-02-15 | 北京中电加美环境工程技术有限责任公司 | Metal element modified ZSM-5 molecular sieve composite membrane as well as preparation method and application thereof |
CN103260757A (en) * | 2010-12-11 | 2013-08-21 | 尤米科尔股份公司及两合公司 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides |
CN107176613A (en) * | 2017-07-12 | 2017-09-19 | 天津工业大学 | A kind of multi-stage porous zeolite crystal embeds the preparation method of Fe nanoparticle catalysts |
CN108097293A (en) * | 2017-12-12 | 2018-06-01 | 南开大学 | The synthetic method of the MFI structure zeolite molecular sieve of tin dope and application |
CN108636128A (en) * | 2018-05-14 | 2018-10-12 | 南京工业大学 | A kind of method that microwave heating method quickly prepares h0h orientation MFI-type molecular screen membranes |
JP2020131184A (en) * | 2019-02-26 | 2020-08-31 | 東ソー株式会社 | Porous support with zeolite membrane, production method of the same and nitrogen separation method using the same |
CN112744828A (en) * | 2019-10-31 | 2021-05-04 | 上海工程技术大学 | Ultrathin molecular sieve membrane and preparation method thereof |
CN112973782A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Bimetal modified catalyst and preparation method and application thereof |
-
2022
- 2022-03-09 CN CN202210222066.XA patent/CN114560474A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1332114A (en) * | 2001-06-28 | 2002-01-23 | 复旦大学 | Optimized and oriented growth process of MFT-type zeolite crystal |
JP2011121854A (en) * | 2009-11-11 | 2011-06-23 | Mitsubishi Chemicals Corp | Method for producing porous support-zeolite membrane complex |
CN103260757A (en) * | 2010-12-11 | 2013-08-21 | 尤米科尔股份公司及两合公司 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides |
CN102350229A (en) * | 2011-08-24 | 2012-02-15 | 北京中电加美环境工程技术有限责任公司 | Metal element modified ZSM-5 molecular sieve composite membrane as well as preparation method and application thereof |
CN107176613A (en) * | 2017-07-12 | 2017-09-19 | 天津工业大学 | A kind of multi-stage porous zeolite crystal embeds the preparation method of Fe nanoparticle catalysts |
CN108097293A (en) * | 2017-12-12 | 2018-06-01 | 南开大学 | The synthetic method of the MFI structure zeolite molecular sieve of tin dope and application |
CN108636128A (en) * | 2018-05-14 | 2018-10-12 | 南京工业大学 | A kind of method that microwave heating method quickly prepares h0h orientation MFI-type molecular screen membranes |
JP2020131184A (en) * | 2019-02-26 | 2020-08-31 | 東ソー株式会社 | Porous support with zeolite membrane, production method of the same and nitrogen separation method using the same |
CN112744828A (en) * | 2019-10-31 | 2021-05-04 | 上海工程技术大学 | Ultrathin molecular sieve membrane and preparation method thereof |
CN112973782A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Bimetal modified catalyst and preparation method and application thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116808847A (en) * | 2023-07-27 | 2023-09-29 | 大连理工大学 | Preparation method of ultrathin oriented W-MFI zeolite membrane for efficiently separating butane isomers |
CN116808847B (en) * | 2023-07-27 | 2024-04-12 | 大连理工大学 | Preparation method of ultrathin oriented W-MFI zeolite membrane for efficiently separating butane isomers |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Valtchev et al. | Preparation and characterization of hollow fibers of silicalite-1 | |
KR101614544B1 (en) | Method of Preparation Using Crystalline Nano-sized Seed | |
JP6834003B2 (en) | Methods for Synthesizing Mordenite (MOR) Molecular Sieves, Their Products and Uses | |
CN108126533B (en) | Method for preparing porous ceramic support body by adding molecular sieve and in-situ hydro-thermal synthesis of molecular sieve membrane | |
Zhou et al. | Synthesis of oriented zeolite T membranes from clear solutions and their pervaporation properties | |
US9981852B2 (en) | Selective sonication-assisted deposition method of inorganic particles and CHA zeolite membranes grown from seeded layers on substrates using the method and plate-like Si-CHA zeolite particles used for seed layer formation and manufacturing method of the same | |
CN112794338B (en) | ZSM-5 molecular sieve and preparation method and application thereof | |
CN105797597A (en) | Preparation method for chabasite molecular sieve membrane | |
JP2010131600A (en) | Method of manufacturing zsm-5 type zeolite membrane | |
JP2003159518A (en) | Method for manufacturing ddr type zeolite membrane | |
CN114560474A (en) | Synthesis method of metal modified M-MFI molecular sieve membrane | |
CN113184877B (en) | Hollow octahedral NaP molecular sieve and preparation method thereof | |
CN112645344B (en) | Method for preparing SSZ-13 molecular sieve membrane by steam-assisted conversion | |
US11434140B2 (en) | Hierarchical zeolites and preparation method therefor | |
Wang et al. | Preparation of MFI zeolite membranes on coarse macropore stainless steel hollow fibers for the recovery of bioalcohols | |
CN109867293B (en) | Synthesis method of morphology-adjustable NaP type molecular sieve | |
CN113880110B (en) | Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof | |
CN106395856A (en) | Method for preparing ZSM-5 hollow molecular sieve through hydrothermal recrystallization | |
CN112694100A (en) | Fe-ZSM-5 molecular sieve, preparation method and application thereof | |
CN109694086B (en) | Preparation method of nano ZSM-5 zeolite molecular sieve aggregate | |
KR101693599B1 (en) | Method for manufacturing zeolite membrane | |
CN112624141B (en) | Preparation method of MFI molecular sieve membrane | |
KR102220082B1 (en) | Aluminosilicates structure with novel structure and wool-like type morphology, manufacturing method thereof and HPLC column packed with the same as stationary phase | |
Zhou et al. | Inexpensive synthesis of silicalite-1 membranes with high pervaporation performance | |
CN111097293A (en) | Preparation method of MFI molecular sieve membrane material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220531 |
|
RJ01 | Rejection of invention patent application after publication |