CN1215351A - 改进的膜 - Google Patents
改进的膜 Download PDFInfo
- Publication number
- CN1215351A CN1215351A CN97193576A CN97193576A CN1215351A CN 1215351 A CN1215351 A CN 1215351A CN 97193576 A CN97193576 A CN 97193576A CN 97193576 A CN97193576 A CN 97193576A CN 1215351 A CN1215351 A CN 1215351A
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- China
- Prior art keywords
- film
- compound
- zeolite
- silicon
- solution
- 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.)
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- 239000012528 membrane Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 61
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010457 zeolite Substances 0.000 claims abstract description 56
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002210 silicon-based material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- -1 pottery Substances 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 229910000765 intermetallic Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229920000592 inorganic polymer Polymers 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920005594 polymer fiber Polymers 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 229910001723 mesolite Inorganic materials 0.000 claims 1
- 150000003755 zirconium compounds Chemical class 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 150000004756 silanes Chemical class 0.000 abstract 1
- 150000004760 silicates Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 108090000723 Insulin-Like Growth Factor I Proteins 0.000 description 11
- 102000013275 Somatomedins Human genes 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 239000006193 liquid solution Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 208000035126 Facies Diseases 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229940001007 aluminium phosphate Drugs 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000006870 function Effects 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- XLVKXZZJSTWDJY-UHFFFAOYSA-N [SiH4].[Si] Chemical class [SiH4].[Si] XLVKXZZJSTWDJY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
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- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 125000005624 silicic acid group Chemical group 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Classifications
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
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- B01J37/024—Multiple impregnation or coating
- B01J37/0246—Coatings comprising a zeolite
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Abstract
一种处理沸石膜以改进其性能和提高其粘结力的方法,此法包括用能同膜反应的硅或金属化合物处理膜,优选的化合物是硅烷和硅酸盐。
Description
本发明涉及一种改进的膜以及生产改进的膜的方法。
众所周知,沸石和相似的结晶沸石材料用于分离和用作催化剂。沸石膜和嵌入沸石的膜也是熟知的并包括许多类型。欧洲专利申请0481660公开和讨论了先有技术沸石型(阳离子交换剂)膜并特别提到US Patents 3244643、3730910和4578372,应用催化剂(AppliedCatalysts)49(1989)1-25,DE-A-3827049,CA1235684,JP-A-63287504,JP-A-63291809,EP-A-180200,EP-A-135069。
在EP 0481 658 A1中公开了表面涂布多孔载体体,在其上通过由合成凝胶中结晶沉积沸石型(阳离子交换剂)材料,并具有呈金属和/或氧化物形式的镍钴或钼的表面涂层。
用于形成这种表面涂层所公开的方法包括由汽相淀积、真空蒸发、Rf喷镀或电镀或由液体沉积盐并氧化此盐。这些方法在不同厚度的多孔载体上生成表面涂层,并提供了主要对载体丝由凝胶中结晶沉积的改进而在单次生长后填补空隙改进不大。EP 0481 659 A1公开了一种类似的预处理多孔载体的方法,除了多孔载体用酸预处理外。
EP 0481660 A1的方法公开了用合成凝胶多次处理多孔载体,并从凝胶中结晶沸石型(zeo型)(阳离子交换剂)材料以得到改进的涂层。但是,此法可能留下凝胶和其它碎片阻塞多孔载体的孔,因此防止完全覆盖,即使在沸石生长间的擦拭也会留下碎片。
但是,这些方法未经多次生长不能得到无缺陷膜,在一次生长后它们不能填补空隙,尽管这些专利申请中公开了用凝胶重复处理以阻塞“针孔”,但这些现有的方法都不是成功的。即使小的缺陷或针孔也能对膜的性能产生非常有害的影响,使其在许多操作中几乎没有价值。这是因为在许多操作中缺陷可为未分离的产品提供通过的渠道。
某些现有的方法宣称,在实验室规模能得到无缺陷的膜,但是,大规模提供基本无缺陷的膜是不成功的。
为了提供具有更好性能的改进的膜,我们设计了这些膜的处理方法。
本发明提供了含结晶沸石型材料薄膜的膜处理方法,此法包括用在之前、之后能同膜进行反应的硅或其它金属化合物处理膜或代替在专利申请PCT/GB/00956用硅酸或聚硅酸处理膜。
沸石型(阳离子交换剂)材料广泛用作分子筛是众所周知的。它们含有经氧原子连接的由硅/氧四面体形成的广泛的通道网。沸石和铝硅酸盐是最广泛知道的沸石型(阳离子交换剂)材料,本发明适用于由沸石型(阳离子交换剂)材料形成的任何膜和特别适用于沸石和铝硅酸盐。在“沸石结构类型图集”(Atlas of Zeolite Structure Types),Meier和Ofsen,1987,Polycrystal Book Service,Pittsburg USA中,讨论了各种结构类型,例如,讨论的LTA、MEL、MFI或TON结构可以使用。
在第7次沸石科学和技术新发展国际会议论文集(NewDevelopments in Zeolite Science and Technology Proceedings of 7thInternational Conference,Tokyo,1986,103页)中,公开了另一类沸石型(阳离子交换剂)材料,即结晶铝磷酸盐、硅铝磷酸盐和其它的金属铝磷酸盐。
可用于本发明的典型的沸石包括但不限于3A、4A、5A、13X、X、Y、ZSM5、MPO、SAPO、硅酸盐β或θ或θ-1等。
在其上形成沸石型膜并可用于本发明的多孔载体包括金属、陶瓷、玻璃、矿物、碳或聚合物纤维或纤维素或有机或无机聚合物形成的载体。适宜的金属包括钛、铬或合金如以商标“Fecralloy”和“Hastalloy”出售的合金以及不锈钢。多孔载体可由筛网或烧结的金属粒子或两者的混合物制成。通常以纤维形式出售。
可以使用的多孔陶瓷、玻璃、矿物或碳材料包括多孔硅和其他的碳化物、粘土和其它的硅酸盐和多孔二氧化硅。如果要求,载体可以是通过压缩或用粘合剂制成的沸石,或通过将偏高岭土转化为沸石。载体的形状没有严格要求,例如可以使用平板、管状、卷绕的螺旋状等。如果使用聚合物材料,这些材料可以是任选涂以金属或金属氧化物或所定义的硅酸的薄膜。
多孔载体还可以是颗粒状的固体,例如由密集堆积的材料颗粒制成如丸状催化剂。
尽管本发明可以使用任何适宜大小的多孔载体,但是,优选的是大孔载体,以使大流量通过膜。孔径优选为0.01-2,000微米,更优选为0.01-200,理想的为0.01-5微米。直到300微米的孔径可以用在ISO 4003中规定的始沸点压力测定。一般地说,由空隙组成的表面的相对量越大,则多孔载体越适宜。
可以用本发明方法处理的膜可用任何方法制造,如从凝胶或溶液中结晶,或用等离子沉积或其他的任何方法,如在DE 4109037中讨论的在导电基体上的电沉积或将偏高岭土转化为沸石。
当用从合成凝胶中结晶制造含沸石型(阳离子交换剂)材料薄膜的膜时,可以使用任何在先技术中讨论的方法。
用于本发明的合成凝胶可以是能产生所要求的结晶沸石型(阳离子交换剂)材料的任何凝胶。沸石型材料的合成所用的凝胶是熟知的,并在上述的先有技术中讨论过,例如在EP-A-57049、EP-A-104800、EP-A-2899和EP-A-2900中。由John Wiley(1974)出版的D.W.Breck所著的标准教科书“沸石分子筛、结构化学和应用”(“Zeolites MoleculesSieves,Structure Chemistry and Use”)和Elsevier(1987)出版的由P.A.Jacobs and J.A.Martens所著的表面科学和催化剂的研究,第33期,高二氧化硅铝硅酸盐沸石的合成(Studies in Surface Science andCatalysis No.33,Synthesis of High Silica Alumino silicate Zeolites”)中讨论了许多这些合成凝胶。可以使用的方法包括沸石型材料的传统合成,不包括在多孔载体存在下进行合成的。最通用的是用加热使凝胶结晶。
用本发明方法处理的膜的制备方法包括由生长介质中沉积或结晶。在本发明的一个具体实施方案中生长介质可以两种不同的方法使用。
在形成膜的凝胶法(方法1)中,用于形成膜的凝胶优选具有下列范围的摩尔组成:
(1.5-3.0)Na2O∶(1)Al2O3∶(2.0)SiO2∶(50-200)H2O
所用的方法可以用在上述参考文献中公开的任何方法。在液体溶液法(方法2)中,用以形成膜的液体溶液优选具有下列范围的摩尔组成:
(6-10.0)Na2O∶(0.2)Al2O3∶(1.0)SiO2∶(150-250)H2O
液体溶液优选含最大量的能结晶形成沸石型材料的化合物同时仍保持液体溶液。最大量是指能保持在溶液中最大的量,使得在沸石生成前不出现沉淀。
方法(1)和方法(2)可以在下面列举的条件下使用,方法(1)和方法(2)可以单独使用,或用方法(1)然后用方法(2)或以反顺序使用。
可以用于形成膜的条件是生长溶液的温度优选为50-100℃,以及用加入氢氧化钠或氨将pH调节至如12.5-14。如果要求,可以加入钠盐如氯化钠增加钠离子浓度而不增加pH值。生长溶液可以用所要合成的沸石的沸石晶体作晶种。在膜形成后和进行任何后处理之前可将膜洗至中性。
多孔载体可通过浸入或将生长介质倾于载体上使与生长介质接触,同时将载体基本上保持水平,或在容器底面朝上,或在生长介质表面面朝下,或在载体的一侧或两侧通过并保持载体基本上水平,或在载体的一侧或两侧通过并保持载体基本上垂直,或载体可在任何中间位置或进至管状载体的内部。
生长介质可保持静止、搅拌、翻滚或在载体上或载体周围通过,或生长介质可在载体的两侧通过或垂直向上或垂直向下通过管状载体的内部或外部,同时保持基本上水平或在任何位置。
可以施加压力,但是,一般是在自发压力下进行结晶。优选是将多孔载体完全浸入生长介质,或如果要求,仅载体的一面同生长介质接触。
如果要求生成的膜呈管状,可能是有效的。这时,管的仅内侧或外侧需要同生长介质接触或生长介质可同垂直管状载体的内侧或外侧接触。
如果要求生成的膜含两种不同的沸石,载体的每侧各是一种沸石,这可能效果更好。使用这种双官能膜等同于使用两种分离的膜,每膜载有不同的沸石。
如果要求,可以用凝胶或液体溶液处理一或多次,以得到较厚的膜涂层和/或更有粘合力的涂层。
多孔载体优选用沸石起始剂(initiating agent)预处理。沸石起始剂优选法是钴、钼或镍的氧化物或可是沸石颗粒,例如,打算沉积于多孔载体的沸石,或上述这些的任何的混合物。沸石起始剂的另一实倒是能沉积沸石型前体材料的化合物,例如硅酸或聚硅酸。
沸石起始剂可用湿法或干法同多孔载体接触。如果用干法,沸石起始剂颗粒可以擦入多孔材料的表面,或多孔材料表面可以由擦入颗粒中。
或者,沸石起始剂的颗粒可以流过和/或经过多孔载体,或通过真空拉进载体。
如果使用湿法,制成沸石起始剂粉的悬浮液,使液体悬浮液同多孔载体接触将沸石起始剂沉积于载体上。
在多孔载体表面同沸石起始剂接触前,优选将表面用润湿剂润湿,如用醇、水或它们的混合物。
当使用硅酸作引发剂时,可为此处定义的硅酸。
在本说明书中,硅酸是指单硅酸、低、中和高分子量的聚硅酸和它们的混合物。
用于处理本发明膜的优选的化合物包括硅、钛、锆或能形成溶液或凝胶以及能缩合聚合结构的任何金属化合物。例如含硅的化合物能包括硅烷、硅酸盐和有机硅氧烷聚合物。
优选的硅烷是氯、烷氧基或任何具有能进行缩合反应的活性官能团的硅烷。
优选的硅酸盐是具有易于除去的阳离子,如一和二价阳离子的硅烷。
用含硅化合物处理取决于含硅化合物的状态。如果是气态,膜可同含硅化合物在气态接触,优选是在高温下如0℃以上,更优选是高于20℃。
如果含硅化合物是固体,可将其溶于适当的溶剂,如四氢呋喃、乙醇、丁醇或任何的质子化溶剂,然后膜同溶液接触。
如果含硅化合物是液体,则膜同该液体或同该液体同适宜的溶剂的混合物接触。
除了硅化合物外的适用于本发明的其它金属化合物可以是金属氧化物、金属烷氧化物、金属氢氧化物的凝胶或溶液。适宜的金属包括钛、锆或任何能形成溶液或凝胶并能缩合形成聚合型结构,如适宜的氧化物、氢氧化物或烷氧化物的任何金属。
用本法处理过的膜与未经处理过的膜相比,其性能和膜的强度得到改进。
用本发明制造的膜可用在分离和催化过程,例如液化石油气、空气、醇类和天然气的脱水、由支链化合物中除去直链烷烃、烯烃和取代的烃,例如重整和脱蜡等,以及同支链化合物的混合物中的直链烃加氢和脱氢。
在下列实施例中讨论本发明。其中实施例1是用己知方法制备膜,实施例2说明用来评试膜的试验方法和已知膜的评试,实施例3是本发明膜的制备和评试的实施例。
实施例1膜生长
所用的基体是Bekipor(商标)ST XLS361S3滤器。它由很细的316支不锈钢纤维在一起组成,呈三维迷宫结构。在均匀网中纤维无规地排列。将网经进一步压实和烧结,在每一纤维交叉处得到强的金属结合。平均孔径约为5.3微米,表面的丝的直径是2.0微米。在使用前将7厘米的金属筛网盘用甲苯(3×50毫升等分)脱气然后空气干燥。
然后用0.1摩尔/升的硝酸钴溶液处理盘,放入90℃的炉中干燥,稍后在125-300℃下煅烧4小时。然后将盘从炉中取出使其冷却。如此重复三次得到良好的氧化钴涂层。
用带手套的手指将沸石A粉擦进基体的活性一侧,直到不再能擦进表面为止。将任何多余的粉除去。
将盘放入100毫升的平底陪替氏培养皿盘中,此陪替氏培养皿盘已经用去离子水、丙酮、甲苯最后用丙酮洗过,然后在100℃炉中干燥3小时。
所有的仪器和设备,包括基体和生长容器预热到100℃的温度。
A和B两种溶液制备如下:
溶液A
将3.75克氢氧化钠溶解在148.6克预热过的去离子水中。然后将24.29克铝酸钠小心加入,搅拌混合物直到溶解。将此溶液保持在95-100℃。
铝酸钠的实际组成为:62.48%Al2O3,35.24%Na2O和2.28%H2O。
溶液B
将50.57克硅酸钠(组成为14.21%Na2O,35.59%SiO2和50.20%H2O)溶于148.6克的冷至约50℃的去离子水中。
溶液A在搅拌下缓慢加到溶液B中以确保完全和平稳混合(这是重要的以使不生成水凝胶块)。然后将烧瓶盖住,再加热10-15分钟。得到下列摩尔组成的水溶胶:
2.01Na2O∶Al2O3∶2.0SiO2∶143.10H2O
将100毫升的水溶胶缓慢倒进预热过的聚丙烯生长容器中。此容器含用硝酸钴处理的筛网,筛网垂直悬挂在塑料包封的丝上。
将生长容器和含剩余水溶胶溶液的烧杯一起放进家用压力锅中,将压力锅放在温度100的炉中5小时。
随后从压力锅中取出使之冷却30分钟。将生长容器和水溶胶溶液倒入一容器中供处理。
将金属筛网谨慎取出,确保其不弯曲和受损害。筛网放入干净干的玻璃烧杯中并用100毫升等分的去离子水洗三次,每次旋动溶液以确保除去残余液。然后在空气中干燥过夜。
用干净的擦棱镜纸将干的涂布过的筛网表面擦干净以除去任何可能在表面形成的松散的粉状沉积物。
然后将膜进行试验。
实施例2 膜试验方法
将膜放入玻璃烧杯中用25毫升等分的去离子水漂洗直到水的pH等于7。将膜放在附图所示的设备中的预蒸发试验小室中。
此设备的不锈钢试验小室(1)装有压力计(2)、减压阀(3)、磁搅拌器(4)和热电偶(5)。将在实施例1制备的膜放在多孔不锈钢盘(6)上,用KALREZ(商标)O型环(7)密封进小室。
用加热器/搅拌器(8)将小室同时加热和搅拌。经管线(9)抽真空,由试验小室除去的蒸气在冷阱(10)凝聚出来。管线(9)有压力计(11)和减压阀(12)。
将200.0克的异丙醇/去离子水溶液(约5%重量/重量水)倒入试验小室。然后将溶液加热到70℃并以约300转/分钟的速度搅拌。
用真空管线将膜下侧的压力降低到1毫巴(0.1千牛顿)。以一定的间隔和在时间内收集渗透液,经称重和分析以测定存在水的浓度。进料水的浓度在整个过程加以检测。水流量和渗透水的含量作为进料水的浓度的函数一起示于表1。
表1
流动时间(小时) | 进料水(%重量/重量) | 渗透水(%重量/重量) | 渗透流量(克/小时) | 水流量(千克/米2/天) |
1.25 | 3.72 | 38.52 | 11.67 | 59.55 |
2.00 | 0.83 | 10.15 | 12.31 | 16.55 |
2.75 | 0.54 | 4.49 | 12.25 | 7.29 |
实施例3 快速后处理制剂
由平均重量比2.00∶1和摩尔比2.06∶1,平均含Na2O 27%,平均含SiO2 53%,平均含水20.00%和固体总量80%的SiO2/Na2O“可溶的硅酸钠粉”(前Crosfield,商标名Pryramid P40)制备在有机溶液中的预聚合的硅酸。
将上述的粉200.0克(含106克SiO2))溶于水(835毫升)中,将得到的溶液在45分钟内在搅拌和0℃-10℃下逐滴加到盐酸水溶液(3摩尔/升,100毫升)中,然后再搅拌90分钟。
随后在搅拌下加入四氢呋喃(THF,1000毫升)和氯化钠(500克),然后再搅拌60分钟,静置30分钟后得到含硅酸的有机相和水相。
将有机相分离并用分子筛4A(1/8英寸珠、4-8筛目,200克)干燥。在干燥过的有机相加入正丁醇(1.28升),将溶液蒸馏2小时得到预聚的硅酸在丁醇中的透明溶液(500克,含103克SiO2),此溶液基本是无水的。
用在二甲基甲酰胺中的氯代三甲基硅烷处理有机相得到三甲硅硅烷基衍生物,然后用凝胶透过色谱进行分析,得到-单峰,是平均分子量约为800原子质量单位的硅酸混合物。
溶液2
按照溶液1的方法,但是加入硅酸钠后,将附加的搅拌时间降低的45分钟。最后得到的硅酸分子量低于溶液1的硅酸分子量,平均分子量约为600原子质量单位。溶液3
按照溶液1的方法,但是加入硅酸钠后不再搅拌。最后得到的硅酸比溶液1的硅酸的分子量低,平均分子量为96原子质量单位。
实施例4 快速后处理
用下列量的前述溶液在清洁干燥的玻璃烧杯中制备快速后处理溶液。
名称 活性材料(%) 质量(克)
溶液1 26.64 3.13
溶液2 22.86 3.65
溶液3 21.22 3.93
乙醇 114.29
即以1∶1比的2.50克活性硅酸单元。
将2.50克PDMS(聚二甲基硅氧烷,Huls-Petrech产,粘度25-35厘沲)加入到此混合物中,得到硅酸与PDMS比为1∶1。
将IPA/H2O溶液除去然后用两份25克等分无水乙醇漂洗以准备小室。然后将50克的无水乙醇放入小室,抽真空约15分钟。用无水乙醇代替膜孔中的任何水。然后将乙醇从小室中倾出并将后处理溶液加到冷的小室中。抽真空,然后将溶液加热到70并以300转/分钟的速度搅拌。
经第一个1.5小时后,将渗透液称重但不循环。然后将渗透液每0.5小室称重一次,直到少于0.05克。这时,从小室中除去后处理液,用两份的25毫升等分的无水乙醇漂洗。然后停止加热和搅拌。使用压缩机使气流通过膜一小时。
此后,将约200克的异丙醇/去离子水溶液(~5%水)放进小室,加热到70℃并以约300转/分钟的速度搅拌。
如上述进行膜的试验。
结果示于表2。
表2
流动时间(小时) | 进料水(%重量/重量) | 渗透水(%重量/重量) | 渗透液流量(克/小时) | 水流量(千克/米2/天) |
0.25 | 3.76 | 98.85 | 2.46 | 32.22 |
0.75 | 3.15 | 99.37 | 5.38 | 70.83 |
1.25 | 1.29 | 98.37 | 3.15 | 41.05 |
1.75 | 1.00 | 96.93 | 1.84 | 21.63 |
实施例5 TEOS处理
将含有
4.0克四乙基原硅酸酯(TEOS)
18.0克去离子水
18.0克乙醇的TEOS处理液放在清洁干燥的100毫升的烧杯中。然后用漏斗经小室顶部的孔将混合物倾在试验小室的膜上。膜的下侧置于真空(1毫巴)下,从而经膜孔拉溶液。将小室内的溶液加热到70℃,并在约300转/分钟的速度下搅拌19小时。
此后除去小室中的内容物,用四份的50毫升等分的去离子水漂洗小室。将膜经过小室通过压缩空气流使膜风干1小时。然后将约200克的异丙醇/去离子水溶液(~5%重量/重量水)放入小室,加热到70℃,并在约300转/分钟的速度下搅拌。然后如上面一样进行试验膜,结果列于表3。
表3
流动时间(小时) | 进料水(%重量/重量) | 渗透水(%重量/重量) | 渗透流量(克/小时) | 水流量(千克/米2/天) |
0.50 | 3.75 | 99.01 | 6.83 | 89.59 |
1.75 | 1.89 | 100.00 | 2.22 | 29.42 |
2.50 | 0.48 | 81.12 | 0.79 | 8.49 |
3.50 | 0.19 | 73.62 | 0.12 | 1.17 |
Claims (20)
1.含结晶沸石型材料薄膜的膜处理方法,此法包括用能够同膜反应的除硅酸或聚硅酸外的硅或金属化合物处理此膜。
2.权利要求1的方法,其中沸石型材料是沸石膜。
3.权利要求2的方法,其中沸石是选自沸石3A、4A、5A、13X、X、Y、ZSM5、MPO、SAPO、硅酸盐β、θ、θ-1。
4.权利要求1、2或3的方法,其中其上有沸石型(阳离子交换剂)膜形成的多孔载体是由金属、陶瓷、玻璃、矿物、碳或聚合物纤维或纤维素或有机或无机聚合物形成。
5.权利要求5的方法,其中多孔载体由筛网形或由烧结的金属粒子或两者的混合物制成。
6.权利要求1-5的任一方法,其中多孔载体的孔径为0.01-2,000微米。
7.权利要求6的方法,其中多孔载体的孔径为0.01-5微米。
8.上述权利要求中的任一方法,其中膜由凝胶或溶液结晶制成。
9.权利要求8的方法,其中膜呈板或管的形式。
10.上述权利要求中的任一方法,其中用于处理膜的化合物是硅、钛、锆化合物,此化合物能形成溶液或凝胶并能缩合形成聚合型结构。
11.权利要求10的方法,其中化合物是硅烷、硅酸盐、或有机硅氧烷聚合物。
12.权利要求11的方法,其中化合物是氯或烷氧基化合物或任何具有能进行缩合反应的活性官能团的硅烷化合物。
13.权利要求10的方法,其中化合物是具有一或二价阳离子的硅酸盐。
14.权利要求10-13的任一方法,其中含硅化合物是气态的,膜同含硅化合物的接触是在气态。
15.权利要求14的方法,其中膜同含硅化合物接触的温度是在20℃以上。
16.权利要求10-13的任一方法,其中含硅化合物是固体并溶于溶剂中,膜同该溶液接触。
17.权利要求10-13的任一方法,其中含硅化合物是液体,膜同液体或液体同溶剂的混合物接触。
18.权利要求10-13的任一方法,其中金属化合物是金属氧化物、烷氧化物或氢氧化物的溶液或凝胶。
19.上述权利要求的任一方法,其中在用化合物处理前,用硅酸或聚硅酸处理膜。
20.上述权利要求的任一方法,其中用化合物处理后,处理过的膜用硅酸或聚硅酸再处理。
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CN (1) | CN1215351A (zh) |
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CN103987450A (zh) * | 2011-11-10 | 2014-08-13 | 布里斯菲尔德制造公司 | 用于富集气体的液体的方法和装置 |
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DE19853971B4 (de) | 1998-11-23 | 2011-06-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Anorganisch/organische Polysiloxanhybridpolymere und ihre Verwendung |
US20020114958A1 (en) * | 2000-11-27 | 2002-08-22 | Toray Industries, Inc. | Method of coating zeolite crystals, substrate containing zeolite crystals, method of manufacturing zeolite membrane, method of processing zeolite membrane, zeolite membrane, aluminum electrolytic capacitor, degassing membrane and separation method |
US20050067344A1 (en) * | 2003-09-30 | 2005-03-31 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Zeolite membrane support and zeolite composite membrane |
AU2005271542A1 (en) | 2004-08-03 | 2006-02-16 | The Regents Of The University Of Colorado | Membranes for highly selective separations |
KR100763893B1 (ko) * | 2006-02-01 | 2007-10-05 | 삼성에스디아이 주식회사 | 굴곡진 cnt층을 갖는 전자방출소자의 제조 방법 |
CN101443298A (zh) | 2006-05-15 | 2009-05-27 | 科罗拉多州立大学董事会 | 用于co2/ch4分离的高通量和高选择性的sapo-34膜 |
US7923060B2 (en) * | 2006-10-18 | 2011-04-12 | Ngk Insulators, Ltd. | Method of manufacturing ceramic filter |
US8302782B2 (en) | 2007-03-09 | 2012-11-06 | The Regents of the University of Colorado, a body corporated | Synthesis of zeolites and zeolite membranes using multiple structure directing agents |
AU2011245307B2 (en) | 2010-04-29 | 2014-10-09 | The Regents Of The University Of Colorado, A Body Corporate | High flux SAPO-34 membranes for CO2/CH4 separation and template removal method |
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