WO1997037752A1 - Improved membrane - Google Patents
Improved membrane Download PDFInfo
- Publication number
- WO1997037752A1 WO1997037752A1 PCT/GB1997/000928 GB9700928W WO9737752A1 WO 1997037752 A1 WO1997037752 A1 WO 1997037752A1 GB 9700928 W GB9700928 W GB 9700928W WO 9737752 A1 WO9737752 A1 WO 9737752A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- compound
- solution
- silicon
- zeolite
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000010457 zeolite Substances 0.000 claims abstract description 32
- 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 25
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000002210 silicon-based material Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- -1 alkoxy compound 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
- 239000000919 ceramic Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims 2
- 229920000592 inorganic polymer Polymers 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 150000003755 zirconium compounds Chemical class 0.000 claims 1
- 150000004760 silicates Chemical class 0.000 abstract description 4
- 150000004756 silanes Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 45
- 229910001868 water Inorganic materials 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000499 gel Substances 0.000 description 20
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000012010 growth Effects 0.000 description 11
- 239000001963 growth medium Substances 0.000 description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 230000000977 initiatory effect Effects 0.000 description 10
- 239000012466 permeate Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000004907 flux Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 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
- 238000000576 coating method Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000006193 liquid solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder 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
- 239000000758 substrate Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000005624 silicic acid group Chemical class 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
- 229910001220 stainless steel Inorganic materials 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
- 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 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 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
- 229910000428 cobalt oxide Inorganic materials 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
- 239000006194 liquid suspension Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000012074 organic phase Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 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
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011268 retreatment Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
-
- 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
- B01D71/0281—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/0272—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
- B01J31/0274—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 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0246—Coatings comprising a zeolite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
Definitions
- the present invention relates to an improved membrane and a process for producing improved membranes.
- Zeolitic membranes and membranes which incorporate zeolites are also well known and can come in a range of different tvpes
- European Patent Application 0481660 discloses and discusses prior art zeo-type membranes and refers in particular to US Patents 3244643, 3730910 and 4578372. Applied Catalysts 49( 1989) 1-25, DE-A-3827049, CA1235684, JP-A-63287504, JP-A-63291809, EP-A-180200, EP-A-135069.
- the methods disclosed for forming this surface coating include vapour deposition, vacuum evaporation, Rf sputtering or electroplating or deposition of a salt from a liquid and oxidising the salt. These methods give a surface coating on the porous support of varying thicknesses and provide for improved crystal deposition from the gel nainly round the wires of the support with little improvement in filling the voids after a single growth.
- EP 0481 659 Al discloses a similar process for pre-treating a porous support, except that the porous support is pre-treated with an acid.
- EP 0481660 Al discloses treating the porous support a plurality of times with the synthesis gel and crystallising a zeo-type material from the gel in order to obtain an improved coating.
- this process can leave gel and other debris blocking the pores of the porous support and ; us prevent complete coverage, even wiping between zeolite growths will leave debris behind.
- a process for treating a membrane comp ⁇ sing a film of a crystalline zeo-type material which process comp ⁇ ses treating the membrane with a silicon or other metal compound capable ot reacting with the membrane either before, after or instead of the ti ument of the membrane with a silicic acid or polysilicic acid as set out in patent application PCT/GB95/00956
- Zeo-t>pe materials are also known as molecular sieves which are widely know n and used They comprise an extended network of channels formed from silicon/oxygen tetrahedrons joined through the oxygen atoms
- Zeolites and jlumino-silicates are the most commonly known form of zeo-type matenals and the present invention is applicable to any membrane formed from z o-type materials and particularly applicable to zeolites and alumino-silicates In th "Atlas of Zeolite Structure Types", Meier and Ofsen, 1987, Polycrystal Book Service.
- Tvpical zeolites which can be used in the present invention are include but are not limited to, A, 4 A, 5A, 13X, X, Y, ZSM5, MPOs, SAPOs, Silica te, ⁇ or theta or theta- 1 , etc
- porous supports on which zeo-type membranes are formed and which can be used in the present invention include those formed of metals, ceramics, glass, mineral, carbon or polvmer fibres or cellulosic or organic or inorganic poh mcrs Suitable metals include titanium, chromium and alloys such as those sold under the Trade Marks "Fecralloy” and “Hastalloy” and stainless steels
- the porous supports may be formed of a mesh or from sintered metal particles or a mixture of both These are commonly sold in the form of filters
- Porous ceramics, glass mineral or carbon matenals can be used including porous silicon and other carbides, clays and other silicates and porous silica
- the support can be a zeolite formed by compression or using a binder, or b the conversion of meta kaolin to a zeolite
- the shape of the support is not critical, tor example, flat sheet, tubular, wound spiral, etc can be used If poi) me ⁇ c materials are used, these can optionally be film coated with metal or metal oxide or a silicic acid as herein defined
- the porous support can be also be a granular solid e g formed of particles of a closely packed mate ⁇ al such as a pelhtised catalyst
- I ! c p r .cr,t invention can be used with porous supports of any suitable size although, lor large flux rates through a membrane, large pore sizes are preieired
- the membranes which can be treated by the method of the present invention can be formed by any method, for example by crystallisation from a gel or solution, by plasma deposition or by any other method such as electro
- the membrane comprising a film of zeo-type material is prepared by crystallisation from a synthesis gel, any of the methods described in the prior art can be used
- the synthesis gel used in the process can be any gel which is capable of producing the desired crystalline zeo-type material.
- Gels for the synthesis of zeo-type materials are well known and are described in the prior art given above or, for example, in EP-A-57049, EP-A-
- the membrane which is treated by the process of the invention can be prepared by a process which comprises deposition or crystallisation from a growth medium.
- the growth medium can be used in two different methods.
- the gel method (method 1 ) for forming the membrane the gel used to form the membrane preferably has a molar composition in the range of
- liquid solution method (method 2) the liquid solution used to form the membrane preferably has a molar composition in the range of -
- the liquid solution preferably contains a maximum amount of the compound capable of crystallising to form a zeo-type material whilst still remaining a liquid solution
- maximum amount is meant the maximum amount which can be maintained tn solution so that no precipitation occurs before zeolite formation
- Methods ( 1 ) and (2) can be used under the conditions listed below and method ( 1 ) and method (2) can be used either on their own or with method (1 ) followed bv method (2) or vice versa
- the conditions which can be used for forming the membrane are with a temperature of the growth solution preferably in the range of 50 to 100°C and the pH can be adjusted e g to pH of 12 5 to 14 by addition of sodium hydroxide or ammonia If desired the sodium ion concentration can be increased without increasing the pH by the addition of a sodium salt such as sodium chloride
- the growth solution can be seeded with zeolite crystals ofthe desired zeolite to be synthesised
- the membrane can be washed to pH neutral after membrane formation prior to any post-treatment
- lie porous support can be contacted with the growth medium by immersion or b ⁇ pouring the growth medium over the support with the support held horizontal, either face up at the bottom of a container, or face nui at the surface of the growth medium, or it can be passed over one or boil, b'de of the support, with the support held substantially horizontal, or it can be passed over one or both sides of the support with the support held substantially vertical or the support can be in any intermediate position or down the inside of a tubular support
- the growth medium can be kept static, stirred, tumbled or passed over or around the support, alternatively the growth medium can be passed over both sides of the support or vertically up and down the inside or outside of a tubular support with the support held substantially horizontal or at any intermediate position
- porous support is completely immersed in the growth medium, alternatively, if desired, only one surface of the support may be in contact with the growth medium
- the treatment with the gel or liquid solution can be repeated one or more times to obtain thicker membrane coatings and/or more coherent coat r.gs
- the porous support is pre-treated with a zeolite initiating agent
- the t ⁇ i.tc initiating agent is preferably a cobalt, molybdenum or nickel oxide or it S... ⁇ ;>e pa r t ⁇ es ot a zeolite, e g the zeolite which it is intended to deposit on i ne porous support, or any combination of these
- Another example of an initiating agent is a compound which can deposit a zeo-type pre-cursor mate ⁇ al e g a silicic acid or polvsihcic acid
- the zeolite initiation agent can be contacted with the porous support by a wet or dry process. If a dry process is used, the particles of the zeolite initiation agent can be rubbed into the surface of the porous material, or the porous material surface can be rubbed in the particles.
- the particles of the zeolite initiation agent can be caused to flow over and/or through the porous support, or pulled into the support by means of a vacuum.
- a liquid suspension of powder of the zeolite initiation agent is formed and the liquid suspension contacted with the porous support to deposit the zeolite initiation agent on the support.
- the surface Before contacting the surface of the porous support with the zeolite initiation agent the surface is preferably wetted with wetting agent such as an alcohol, water or a mixture of these.
- wetting agent such as an alcohol, water or a mixture of these.
- silicic acid When a silicic acid is used as an initiating agent it can be a silicic acid as herein defined.
- silicic acid is meant monosilicic, low, medium and high molecular weight polysilicic acids and mixtures thereof.
- Preferred compounds used to treat the membrane according to the present invention include silicon, titanium, zirconium or any metal compound which can form a solution or gel and which can condense to form a polymeric type structure.
- silicon containing compounds can include silanes, silicates and organic silicone polymers.
- the preferred silanes are chloro, alkoxy, or any silane with a reactive group functionality which can undergo a condensation reaction.
- the preferred silicates are those which have easily removable cations, e.g. ino ⁇ - and di- valent cations.
- the treatment with the silicon containing compound depends on the state of the silicon containing compound. If it is gaseous then the membrane can be contacted with the silicon containing compound is in the gaseous state, preferably at an elevated temperature e g. of above 0 °C and more preferably above 20°C
- the silicon containing compound is a solid then it can be dissolved in a suitable solvent such as tetrahydofuran, ethanol, butanol or any protonated solvent and the membrane contacted with the solution.
- a suitable solvent such as tetrahydofuran, ethanol, butanol or any protonated solvent
- the membrane can be contacted with the liquid or a mixture of the liquid with a suitable solvent.
- the other metal compounds other than silicon compounds useful in the present invention can be used in the form of a solution or gel of a metal oxide, alkoxide or hydroxide.
- Suitable metals include titanium, zirconium or any metal which can form a solution or gel and which can condense to form a polymeric type structure e.g. a suitable oxide, hydroxide, or alkoxide.
- the membranes treated by this process are improved in terms of their performance and membrane strength compared with untreated membranes.
- the membranes formed using the present invention can be used in a range of separation and catalytic processes, e g. dehydration of LPG, air, alcohols and natural gas, removing linear alkanes, olefins and substituted hydrocarbons from mixtures with branched chain compounds, e.g. in reforming, dewaxing, etc., hydrogenation and dehydrogenation of linear hydrocarbon in admixture with branched chain compounds.
- Example 1 is the preparation of a membrane using a known method
- Example 2 illustrates the test piocedure used to test the membranes and the testing of a known membrane
- Example 3 is an Example of production and testing of membrane according to the invention
- Example 1 Membrane Growth
- the substrate used was a Bekipor (Trade Mark) ST XLS361 S3 filter This consists of very fine 316 stainless steel fibres brought together in a 3 -dimensional labyrinthic structure The fibres are arranged randomly in a homogeneous web This web is further compacted and sintered to give a very strong metallic bond at each fibre crossing The average pore size is approximately 5 3 microns and the diameter of the wire on the surface is 2 0 microns A 7cm disc of the metal mesh was degreased using toluene (3 x 50 ml aliquots) followed by and air dried prior to use.
- toluene 3 x 50 ml aliquots
- the disc was then coated with 0 1 M cobalt nitrate solution, placed into an oven at 90°C to dry, then fired at 125-300 °C for 4 hours The disc was then removed from the furnace and allowed to cool This was repeated a further three times to obtain a good cobalt oxide coating
- Zeolite A powder was rubbed into the active side of the substrate, using a gloved finger, until such time as no more could be rubbed into the surface. Any ofthe remaining excess was tapped off
- the disc was then placed in a 100 ml flat bottomed petri dish which had previously been cleaned by washing with de-ionised water, acetone, toluene and finally acetone befoie drying in an oven at 100°C for 3 hours
- the growth vessel was placed in a domestic pressure cooker together with a beaker containing the remaining hydrogel solution
- the pressure cooker was placed in an oven at 100°C for 5 hours
- the metal mesh was carefully removed ensuring that the mesh was not bent or damaged in anv way
- the mesh was placed in a clean dry glass beaker and washed three times with 100ml aliquots of de-ionised water, swirling the solution each time to ensure the removal of residues, and was then allowed to an over ⁇ i-iht
- the surface of the dried coated mesh was subsequently wiped clean with a clean lens tissue in order to remove any loose powdery deposits which may have formed on the surface.
- the membrane is placed in a glass beaker and rinsed with 25 ml aliquots of de-ionised water, until the wash water is at pH7.
- the membrane is placed into a pervaporation test cell in an apparatus as shown in the accompanying drawin
- the apparatus consists of a stainless steel test cell (1 ) fitted with a pressure gauge (2) relief valve (3) magnetic stirrer (4) and thermocouple (5).
- the membrane prepared as in Example 1 was placed on a porous stainless steel disc (6) and was sealed into the cell with a KALREZ (Trade Mark) O ring (7).
- the cell could be simultaneously heated and stirred by a heater /stirrer (8). Vacuum could be applied through line (9). Vapour removed from the test cell was condensed out in cold trap ( 10) Line (9) had a pressure gauge (1 1) and relief valve ( 12).
- Prepolymerised silicic acids in organic solution was prepared from "Soluble Sodium Silicate Powder” (ex Crosfield, Trade Name Pyramid P40) with mean S ⁇ /Na ⁇ weight ratio 2 00. 1 and a molar ratio 2.06.1, mean Na ⁇ 27%, mean SiO 2 53%, mean water 20 00% and total solids 80%.
- Tetrahydrofuran (THF, 1000ml) and sodium chloride (500g) were then added with stirring, followed by a further 60 minutes stirring and 30 minutes standing to produce an organic phase containing silicic acid and an aqueous phase.
- the silicic acid can be analysed by treatment with chlorotrimethyl silane in dimethyl formamide to form trimethylsilyl derivatives followed by gel permeation * I ⁇ n r.ograp. and can form a single peak, found to be a mixture of polysilicic acids ⁇ f n jn moleculai w eight approximately 800 a m u Solution 2
- the rapid post treatment solution was prepared in a clean dry glass beaker using the following amounts ofthe solutions previously described.
- PDMS polydimethylsiloxane ex Huls-Petrach, viscosity 25-35cSt
- the cell was prepared by removing the IPA/H 2 O solution and then rinsing with two 25g aliquots of absolute ethanol 50g of absolute ethanol was then placed in the cell, the was applied for a period of approximately 15 minutes, to replace any water in the membrane pores with absolute ethanol
- the ethanol was then poured out from the cell and the post treatment solution was added to the cold cell. The vacuum was applied and the solution was then heated to 70°C and stirred at 300 r p.m.
- the permeate was weighed but not recycled. The permeate was then weighed every 0 5 of an hour until such time as it was less than 0 05g. When this occurred, the post treatment solution was removed from the cell, which was then rinsed with two 25ml aliquots of absolute ethanol The heating and stirring was then stopped. A stream of air was passed over the membrane, using a compressor, for a period of one hour
- test solution of approximately 200g of an isopropyl alcohol/de-ionised water solution ( ⁇ 5% water) was then placed into the cell, heated to 70°C and stirred at approximately 300 r.p.m.
- the membrane was tested as before.
- TEOS tetraethylorthosilicate
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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Transplantation (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97915578A EP0956149A1 (en) | 1996-04-03 | 1997-04-02 | Improved membrane |
US09/155,316 US6383563B1 (en) | 1996-04-03 | 1997-04-02 | Membrane |
AU23006/97A AU728692B2 (en) | 1996-04-03 | 1997-04-02 | Improved membrane |
JP9535953A JP2000508231A (en) | 1996-04-03 | 1997-04-02 | Improved membrane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB9607090.9 | 1996-04-03 | ||
GBGB9607090.9A GB9607090D0 (en) | 1996-04-03 | 1996-04-03 | Improved membrane |
Publications (1)
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WO1997037752A1 true WO1997037752A1 (en) | 1997-10-16 |
Family
ID=10791588
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1997/000928 WO1997037752A1 (en) | 1996-04-03 | 1997-04-02 | Improved membrane |
Country Status (9)
Country | Link |
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US (1) | US6383563B1 (en) |
EP (1) | EP0956149A1 (en) |
JP (1) | JP2000508231A (en) |
KR (1) | KR20000005219A (en) |
CN (1) | CN1215351A (en) |
AU (1) | AU728692B2 (en) |
CA (1) | CA2249003A1 (en) |
GB (1) | GB9607090D0 (en) |
WO (1) | WO1997037752A1 (en) |
Cited By (6)
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WO1999023034A1 (en) * | 1997-11-04 | 1999-05-14 | Smart (Isle Of Man) Limited | Water treatment process |
US6248682B1 (en) | 1998-11-23 | 2001-06-19 | Worcester Polytechnic Institute | Incorporation of zeolites into hybrid polymer matrices |
WO2006017557A3 (en) * | 2004-08-03 | 2007-01-11 | Univ Colorado | Membranes for highly selective separations |
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 |
US8409326B2 (en) | 2006-05-15 | 2013-04-02 | The Regents Of The University Of Colorado | High flux and selectivity SAPO-34 membranes for CO2/CH4separations |
US8679227B2 (en) | 2010-04-29 | 2014-03-25 | The Regents Of The University Of Colorado | High flux SAPO-34 membranes for CO2/CH4 separation and template removal method |
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GB9822056D0 (en) * | 1998-10-10 | 1998-12-02 | Bratton Graham J | Membrane pre-treatment process |
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 |
KR100763893B1 (en) * | 2006-02-01 | 2007-10-05 | 삼성에스디아이 주식회사 | Preparation of electron emission device having grooved carbon nanotube layer |
US7923060B2 (en) * | 2006-10-18 | 2011-04-12 | Ngk Insulators, Ltd. | Method of manufacturing ceramic filter |
JP2014533201A (en) * | 2011-11-10 | 2014-12-11 | ブリスフィールド マニュファクチャリング カンパニー | Method and apparatus for increasing gas concentration in a liquid |
WO2014156579A1 (en) * | 2013-03-28 | 2014-10-02 | 日本碍子株式会社 | Ceramic separation membrane structure and method for producing same |
JP6217242B2 (en) * | 2013-08-28 | 2017-10-25 | 三菱ケミカル株式会社 | Method for producing porous support-zeolite membrane composite |
NO2697473T3 (en) * | 2014-01-13 | 2018-07-07 |
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- 1997-04-02 CN CN97193576A patent/CN1215351A/en active Pending
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WO1999023034A1 (en) * | 1997-11-04 | 1999-05-14 | Smart (Isle Of Man) Limited | Water treatment process |
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US8409326B2 (en) | 2006-05-15 | 2013-04-02 | The Regents Of The University Of Colorado | High flux and selectivity SAPO-34 membranes for CO2/CH4separations |
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 |
US8679227B2 (en) | 2010-04-29 | 2014-03-25 | The Regents Of The University Of Colorado | High flux SAPO-34 membranes for CO2/CH4 separation and template removal method |
Also Published As
Publication number | Publication date |
---|---|
US6383563B1 (en) | 2002-05-07 |
EP0956149A1 (en) | 1999-11-17 |
AU728692B2 (en) | 2001-01-18 |
GB9607090D0 (en) | 1996-06-05 |
JP2000508231A (en) | 2000-07-04 |
KR20000005219A (en) | 2000-01-25 |
CN1215351A (en) | 1999-04-28 |
CA2249003A1 (en) | 1997-10-16 |
AU2300697A (en) | 1997-10-29 |
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