WO1993019840A1 - Deposition process - Google Patents
Deposition process Download PDFInfo
- Publication number
- WO1993019840A1 WO1993019840A1 PCT/GB1993/000627 GB9300627W WO9319840A1 WO 1993019840 A1 WO1993019840 A1 WO 1993019840A1 GB 9300627 W GB9300627 W GB 9300627W WO 9319840 A1 WO9319840 A1 WO 9319840A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- support
- zeo
- type material
- solution
- suspension
- Prior art date
Links
- 238000005137 deposition process Methods 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007654 immersion Methods 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000001939 inductive effect Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 abstract description 56
- 239000010457 zeolite Substances 0.000 abstract description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 24
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000499 gel Substances 0.000 description 33
- 239000013078 crystal Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 30
- 239000011148 porous material Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000017 hydrogel Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000005373 porous glass Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- -1 Fecralloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000856 hastalloy Inorganic materials 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
- 229910001026 inconel Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010042618 Surgical procedure repeated Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 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 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
- B01D71/0281—Zeolites
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0048—Inorganic membrane manufacture by sol-gel transition
-
- 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
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
Definitions
- the present invention relates to a deposition process' useful in membrane preparation. ⁇
- Zeolites and related crystalline-' materials are well known for their ability to accomplish separations and to act as catalysts.
- Membranes are well known in separations applications, and merabranss incorporating zeolites are known. These membranes are of a number of distinct types.
- CA 1235684 claims a filter for substance separation, comprisiiag a substrate made of a porous glass and a zeolite-based film formed directly on the porous glass, the zeolite-based film having a thickness of 1 micron to 500 microns.
- the filter is prepared by suspending, for example, a borosilicate glass in an aqueous solution of sodium hydroxide and tetrapropylammonium bromide, and heating im an autoclave.
- JP-A-63291809 describes a membrane comprising a film of zeolite on a porous alumina carrier.
- EP-A-180200 describes a membrane comprising a porous support impregnated with fine particles of a zeolite.
- the membrane is prepared by permeating, for example, an ultrafiltration membrane, or a porous glass, with an alkaline solution of ultrafine (e.g. less than 75 angstrom diameter) zeolite particles. These particles become lodged in the pores of the support.
- EP-A-180200 describes a process for preparing a zeolite membrane in which a zeolite synthesis gel is passed through a microfilter and deposited in a thin film on the surface of a support.
- DE-A-3827049 describes a zeolite membrane consisting of a layer of zeolitic crystals on a porous support. During preparation of the membrane, the support is provided with a nucleo-active surface by immersing the porous support for a short time in an alumina-containing solution, and then evaporating the solvent.
- a novel membrane which comprises crystals of a zeo-type material carried by a porous support characterised in that the crystal growth of the zeo-type material is essentially continuous over the pores of the support and that the zeo-type material is crystallised directly from and bonds directly to the support.
- the present invention provides a process for the deposition of a zeo-type material on a porous support, which comprises the following steps: i) contacting at least one surface ⁇ f the porous support with a solution or suspension containing a source of silicic acid, under conditions such that oligomers of silicic acid become bonded directly to said surface of the support; ii) separating the support with said oligomers bonded thereto and said solution or suspension containing a source of silicic acid; and iii) subsequently contacting said surface of the support with a synthesis gel which is capable of crystallising to produce a crystalline zeo-type material, and inducing crystallisation of said gel so that zeo-type material crystallises on said surface.
- Suitable solutions or suspensions containing a source of silicic acid include basic mixtures of silica or a silicate with a solvent or suspending medium; such mixtures may contain a silicate, e.g. sodium silicate already containing silicic acid oligomers or these may form slowly.
- a synthesis gel which is capable of producing a crystalline zeo-type material.
- Such gels contain a source of silicic acid as well as other components.
- this gel may be of the same composition as the gel used in step iii) of the process, or it may be of a different composition. Preferably it is of the same composition.
- Any of the synthesis gels described below as being suitable for use in step iii) of the process of the invention may be used in step i) of the process of the invention.
- the contact of surface of the support in step (i) with the solution or suspension preferably involves immersion of the surface of the support therein, but other methods may be used, such as application of a layer thereof, e.g. by painting on the surface, and maintenance of that layer of solution or suspension in contact with. the surface until the silicic 'acid oligomers have bonded to it; the contact is maintained with the liquid, so that the humidity level above the surface is kept high enough, e.g. by operation under autogenous pressure, to avoid the solution or suspension drying on the surface.
- step (ii) the surface having the oligomers bonded thereto and the solid/suspension are separated, e.g.
- step (iii) the contact of surface and the synthesis gel may be by immersion, but other methods may be used such as painting in the manner as in step (iii) as described above but with contact until the zeo-type material has crystallized on the surface.
- step iii) reimmersed in a fresh synthesis gel according to step iii) until zeo-type crystals have grown on the surface.
- this two-stage contact e.g. immersion process leads to cover of the zeo-type material on the surface of the porous support which is much greater than when a single immersion leading to crystal deposition is used.
- the support is treated between steps ii) and iii) of the process of the invention, for example by washing with water such as distilled and/or deionized water, to remove any adherent residual solution or suspension from step (i) and/or to remove loose material prior to contact, e.g. Immersion in synthesis gel in step iii).
- a water jet may be used.
- the treatment should be vigorous enough to remove loose material but should of course not remove the deposit of oligomers of silicic acid bonded to the surface of the support.
- the support carrying the oligomer deposit is preferably dried before step (iii), e.g. at 50-120°C such as 80-105°C, for 1-100 minutes such as 5-50 minutes.
- the porous support is completely immersed in the solution or suspension containing a source of silicic acid, and subsequently in a synthesis gel.
- a synthesis gel e.g., a styrene gel
- only one surface of the support may be in contact with the solution or suspension and then the gel.
- This may be useful, for example, if it is desired to produce a membrane in the form of a tube where only the inside or the outside of the tube needs to carry zeo-type material. It may also be useful if it is desired to produce a membrane containing two different zeolites, one on each side of the support. Use of such a bi-functional membrane would be equivalent to using two separate membranes each carrying a different zeolite. It is also of course possible to immerse the support completely in the solutisn or suspension containing a source of silicic acid, but subsequently to contact only one side of the support with the synthesis gel according to step iii).
- the contact e.g. immersion of the surface of the porous support in a solution or suspension containing a source of silicic acid may be carried out more than once if desired.
- the surface is preferably treated to remove loose material after removal from one solution or suspension prior to contact, e.g. immersion in a fresh solution or suspension.
- the surface of the porous support must be contacted, e.g. immersed in the solution or suspension containing a source of silicic acid for a period of time such that oligomers of silicic acid become bonded to the surface.
- the optimum time taken for this contact will of course depend on the nature of the solution or suspension used, and also on the temperature.
- the temperature of the contact may vary widely, for example from 20 to 200"C; room temperature may be convenient, but this may necessitate a rather long contact time, whereas contact at a higher temperature will reduce the optimum time.
- contact e.g. immersion times of 3 minutes to 48 hours such as from 5 minutes to 24 hours, typically from half an hour to 3 hours, are suitable.
- the combination of contact e.g. immersion time and temperature is equivalent to less than 8 hours, e.g. less than 6 hours at 90°C, such as 3 minutes to 5 hours at 90°C, e.g. 3 minutes to 30 minutes, suitably when the source of silicic acid is a synthesis gel and/or with pretreated supports as described below.
- the contact time is sufficient at the contact temperature to bond the oligomers of silicic acid, but insufficient to deposit said crystalline zeo-type material as an adherent coating.
- the oligomers of silicic acid are bonded to the surface as an amorphous layer. Their presence on the surface may be seen by transmission or scanning electron microscopy, X-ray analysis or EDAX, either on the support itself or after treatment of the support to dissolve the support and leave the oligomers.
- Zeo-type materials are well known, and are often referred to as molecular sieves. They are characterised by having a crystal structure made up of tetrahedra joined together through oxygen atoms to produce an extended network with channels of molecular dimensions. Any zeo-type material may be used in the present invention, depending on the desired use of the finished membrane. Zeolites, or aluminosilicates, are the best known example of zeo-type materials.
- Any zeolite may be used in the present invention, for example those having LTA, FAU, SOD, MEL, MFI or TON structure types as defined in "Atlas of Zeolite Structure Types", Meier and Olsen, 1987, Polycrystal Book Service, PIttsburg USA.
- Zeolite ZSM-5 and zeolite A, X and Y may be used.
- Other zeo-type materials which may be used include metallosilicates in which some or all of the aluminium is replaced by another metal, such as gallium, boron, zinc, Iron or titanium, and crystalline silicates having zeolite-type structure, such as sillcalites as described in US 4061724 or Nature, 28J , 664-665 (1979).
- a further class of zeo-type materials are the crystalline aluminophosphates ("ALPO's”), silicoaluminophosphates ("SAPO's") and other metalloaluminophosphates .
- APO's crystalline aluminophosphates
- SAPO's silicoaluminophosphates
- ALPO-8, ALPO-54 and MCM-9 may be prepared for example as referred to in Zeolites £ September 1989, page 436.
- a membrane is a continuous structure whose length and width are very much greater than its thickness. It is selectively permeable to liquids or gases.
- any suitable porous support having the desired physical shape may be used in the process of the present invention; suitable forms include for example flat sheet, tubular or spiral wound forms; suitable materials are, for example, a porous metal, ceramic, cermet, glass, mineral, carbon or polymer.
- suitable metals include stainless steels, Inconel, Hastalloy, Fecralloy, chromium and titanium.
- the metal may be in the form of a fibrous mesh (e.g. Bekipor filters), a combination of fibrous metal with sintered metal particles (e.g. Pall PMM metal filter and Supramesh filter), or sintered metal filters (e.g. Pall PSS filter media). Woven metal filter media may also be used.
- Inconel, Hastalloy, Fecralloy, Bekipor, Pall and Supramesh are Trade Marks.
- Typical polymeric substances include any type of filtration media including woven and non-woven media. These may optionally be coated with metal or metal oxide films.
- Porous ceramic, glass, carbon or mineral media may be used including porous carbons, silicon carbide, porous clays or other silicate minerals, e.g. kaolin, vermiculite, montmorillonite and pillared clays, aerogels or supported aerogels and supported porous silica.
- the support may itself be a zeolite, formed into a suitable shape using a binder. By choice of a suitable support, very robust membranes may be produced. The use of metal supports is especially preferred. The pore size of the support is an important parameter. Many prior art membranes have used supports with very small pore sizes. A major advantage of the present invention compared with published prior art Is that it enables a support with a large pore size to be used.
- the pore diameter can be larger than the average crystal size of the zeo-type material.
- Large pores are advantageous because they permit the preparation of high surface area membranes, and thus maximise flux.
- the average pore diameter of a support used in the present invention is in the range of from 0.1 to 2000 microns, preferably 1 to 2000 microns, especially 5 to 200 microns.
- the pore size may be determined by the technique of bubble point pressure as defined by ISO4003, and the pore size distribution may be measured by a Coulter porometer (Trade Mark).
- Coulter porometer Trade Mark
- optical microscopy methods may be used.
- the surface of the support which is immersed in a solution or suspension containing a source of silicic acid and subsequently in a synthesis gel which is capable of crystallising to produce a crystalline zeo-type material, incorporates a surface coating of nickel, cobalt or molybdenum in the form of the metal and/or the oxide.
- This surface coating incorporated in the support will normally be predominantly in the form of the oxide, as nickel, cobalt or molybdenum tend to oxidise in air.
- the use of molybdenum or, especially, cobalt is preferred.
- the surface coating may be deposited by any suitable method, for example by vacuum evaporation, vapour deposition, Rf sputtering or electroplating.
- this initial deposit may if desired be converted to give a thick layer of the oxide by heating in a stream of oxidising gas, conveniently air.
- the synthesis gel used in step iii) of the process of the present invention may 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-104800, EP-A-2899 and EP-A-2900. .Standard text books by D W Breck ("Zeolite Molecular Sieves, Structure Chemistry and Use", published by John Wiley, 1974) and P A Jacobs and J A Martens (Studies in Surface Science and Catalysis, No.
- the time may be in the range 3-200 hr, in particular 4-150 hr with higher temperatures needing lower times; crystallization times of at least 8 hr, especially at 80-100°C, e.g. 8 hr to 5 days, in particular 10-80, especially 10-30 hr are preferred.
- the process of immersion and crystallisation may be repeated as required, preferably until a complete and continuous coverage of the support surface is obtained.
- a much greater coverage of crystals is obtained after carrying out a single Immersion and crystallisation step iii) following the steps i) and II) than is obtained without steps i) and ii).
- a finished membrane with a single immersion and crystallisation step ill it may sometimes be possible to obtain a finished membrane with a single immersion and crystallisation step ill).
- the invention also provides a process for * the preparation of a membrane which comprises a process according to the Invention, characterised in that, after crystallisation of the initial gel according to step iii), the support is removed from the mix, and the contact, e.g. immersion and crystallisation of step iii) are repeated one or more times to obtain the required membrane.
- the number of contacts e.g.
- immersions and crystallisations according to step Iii) required will of course depend on the nature of and the pore size of the support, the nature of the zeo-type material and the synthesis conditions; for example, up to 10, especially up to 4, immersions may be desirable.
- the use of the process of the present invention increases the initial coverage of zeo-type material and hence reduces the total number of contacts required to make a finished membrane. •
- the process according to the invention leads to a finished membrane which is in general thinner than the membranes prepared by other methods. This in turn improves the flux through the membrane.
- loose material is removed, for example by thorough washing, before carrying out any subsequent contact and crystallisation steps III) .
- the support may also be dried between each immersion. Drying for at least 12 hours at ambient temperature, at a temperature of 30-50°C for at least 2 hours, or at a temperature of 80-100°C for 15 to 30 minutes, are suitable regimes.
- the finished membranes claimed in our European application No. 91309239 and which can be produced by the process of the present invention have two distinct characteristics.
- the zeo-type material is in direct contact with the surface of the support and directly bonds thereto.
- the nature of the bonding is not fully understood; it may be primarily chemical bonding and/or physical bonding, but in either event the crystals form directly from the support surface without any intermediate "glue” or binder.
- This is distinct from prior art membranes, for example those described in EP-A-180200, where pre-formed crystals of zeolite are brought together with the pores of a support and, in effect, glued or cemented in position.
- crystal growth begins at the support surface, and continues outwards continuously, until it cross-links with the crystals growing from the opposite sides of the pores of the support and forms an essentially continuous film of zeo-type material.
- the zeo-type material presents an essentially continuous crystal growth, each individual crystal growing out from the surface of the support or from the surface of adjacent crystals. This is, again, distinct from prior art membranes where pre-formed crystals are brought into intimate contact and "glued" together,._or where coverage of the surface of a support is incomplete. There is no intermediate layer of amorphous material between the support and the crystal growth.
- the growth of zeo-type material is essentially continuous over the pores of the support.
- it is essentially continuous over the whole surface of the support.
- the layer of zeo-type material may for example be 100 microns thick or even thicker; it may for example be from 1 to 100 microns, especially from 1 to 70 microns, thick.
- the growth of * zeo-type material may if desired extend through the pores, into the body of the support.
- the crystal growth. in a membrane produced by the process of the invention is completely free from pin-holes.
- the term "essentially continuous" is intended to include membranes having a small number of pin-holes in the crystal growth.
- pin-holes are fissures formed when the faces of growing crystals do not match up exactly-
- Such-pin holes may be present immediately after preparation of the membrane, but are also likely to occur after dehydration or ion-exchange of the membrane, or during the working life of the membrane.
- the membranes are clearly distinct from prior art membranes where the crystal growth has major discontinuities, the growth resulting in macro-pores.
- Minor quantities of pin-holes in the membrane can be blocked using a suitable post-treatment, for example using an organic material, for example a polymer or an organo silicon material, or an inorganic material, for example an Inorganic silicon material, capable of cross-linking with silicon and oxygen atoms.
- a suitable post-treatment for example using an organic material, for example a polymer or an organo silicon material, or an inorganic material, for example an Inorganic silicon material, capable of cross-linking with silicon and oxygen atoms.
- the essentially continuous crystal growth in the finished membranes, supplemented If necessary by a post-treatment, is such that there is no access from one side of the membrane to the other except through the intra-crystalline pores of the zeo-type material.
- the finished membranes made by a process incorporating the present invention have a wide range of applications. They may for example be used for dehydration, for example to remove water from materials such as LPG, natural gas or alcohols.
- Such membranes are very much more effective than the traditionally used organic polymer membranes, for example the commercially available caesium polyacrylate membranes described in WO 86/00819, in dehydrating mixtures of water with other liquids; they have the additional advantage of being useful at relatively high temperatures.
- the membranes may be used in catalysis to shift thermodynamic equilibria towards the desired product, for example by removal of hydrogen from a dehydrogenation reaction or removal of water from an esterification reaction or an alcohol dehydrogenation.
- the chemicals used in the Examples are:-
- the substrate used was a 3 x 3 x 1 cm block of a multi-channel membrane available undeyr the Trade Mark "Membralox" SCT Type Z.
- This substrate is composed of alpha-alumina and zirconia, has a pore size of 50 nm, and has 19 channels of 4 mm Internal diameter.
- the block was degreased by soaking it in a beaker containing approximately 200 ml of toluene for 1 hour (liquor being replaced 3 times). The toluene was then replaced by acetone and the washing procedure repeated. The block was subsequently air dried by carefully placing it in a clean petri dish, loosely covering with aluminium foil and placing in a fume cupboard overnight.
- the clean, dry block was placed in a QVF (Trade Mark) glass tube (80 cm diameter).
- the QVF tube was equipped with PTFE end plates which were held in place by stainless steel flanges held in place by metal nuts and bolts.
- the vessel had previously been cleaned by washing it with distilled water, acetone, toluene and finally acetone before being dried in a stream of clean, dry air.
- Solution A 34.4 g sodium aluminate (BDH Technical Grade) and 155.0 g distilled, deionised water. The aluminate was analysed with results as follows: 27.44% Na 2 0, 43.36% A1 2 0 3 and 29.20% H 2 0.
- the hydrogel was slowly poured into the QVF tube containing the block.
- the tube was sealed with the second PTFE disc and metal end flanges and placed In an oven pre-heated to 90° for 2 hours.
- Example 3 The procedure of Example 2 was repeated exactly except that the initial immersion step (2 hours at ' 90°C) and subsequent washing was omitted. Examination of the resulting block by SEM showed a much inferior coverage of zeolite.
- Example 1 The procedure of Example 1 was repeated exactly except that, before the initial immersion step, the block was provided with a surface coating containing cobalt.
- the support was immersed in 500 mis of 0.1 M Co(N0 3 )-*• .6H 0 for 2 hrs at room temperature: The support was then removed and put in a glass petri dish and a layer of fresh 0.1 M Co(N0 3 ) .6H 2 0 solution was pipetted onto the surface. The support was dried for 30 minutes at 90°C and a second aliquot was applied. The support was dried at 90°C for 90 minutes, and then heated in air at 550°C for 6 hours.
- Example 4 The resulting block was subjected to the procedure of Example 1 and then examined by SEM. It had a continuous surface coating of zeolite crystals: an SEM, magnification x 500, is shown in Figure 1.
- Example 4 An SEM, magnification x 500, is shown in Figure 1.
- the substrate used was a Bekipor (Trade Mark) ST5BL3 filter. This consists of very fine 316 stainless steel fibres brought together in a 3-dimensional labyrinthic structure. The fibres are arranged randomly into 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 measured by Coulter porometer is 5.3 microns and the diameter of the wires on the top surface is 6.5 microns. A 7 cm disc of this mesh was degreased as described in Example 1. It was then immersed in a solution of 53.4 g sodium silicate in 155 g water at 90"C for 4 hours. After removal, the mesh was washed thoroughly with water, and then immersed in a hydrogel prepared from solutions A and B as described in Example 1. Subsequent treatment was as in Example 1.
- Example 1 The general procedure of Example 1 was repeated using the substrate defined in Example 4; immersion in the initial hydrogel was for 5 minutes at 90°C. After removal from the initial hydrogel - and washing, the mesh was analysed using transmission electron microscopy and X-ray analysis.'
- a transmission electron micrograph magnification x 100,000 is shown in Figure 2. Hemispherical globules are shown bonded directly to the surface. The X-ray analysis showed these globules to contain predominantly silicon and oxygen. These globules are silicic acid oligomers.
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Glass Compositions (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP93907930A EP0632743A1 (en) | 1992-03-27 | 1993-03-26 | Deposition process |
CA002132969A CA2132969A1 (en) | 1992-03-27 | 1993-03-26 | Deposition process |
JP5517203A JPH07505331A (en) | 1992-03-27 | 1993-03-26 | Deposition method |
AU38944/93A AU663181B2 (en) | 1992-03-27 | 1993-03-26 | Deposition process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB929206783A GB9206783D0 (en) | 1992-03-27 | 1992-03-27 | Deposition process |
GB9206783.4 | 1992-03-27 |
Publications (1)
Publication Number | Publication Date |
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WO1993019840A1 true WO1993019840A1 (en) | 1993-10-14 |
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ID=10713011
Family Applications (1)
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PCT/GB1993/000627 WO1993019840A1 (en) | 1992-03-27 | 1993-03-26 | Deposition process |
Country Status (6)
Country | Link |
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EP (1) | EP0632743A1 (en) |
JP (1) | JPH07505331A (en) |
AU (1) | AU663181B2 (en) |
CA (1) | CA2132969A1 (en) |
GB (1) | GB9206783D0 (en) |
WO (1) | WO1993019840A1 (en) |
Cited By (16)
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---|---|---|---|---|
FR2719238A1 (en) * | 1994-04-29 | 1995-11-03 | Centre Nat Rech Scient | Porous composite inorganic material, especially in the form of a membrane, and a process for obtaining such a material. |
WO1996001686A1 (en) * | 1994-07-08 | 1996-01-25 | Exxon Research And Engineering Company | A zeolite containing composition with a selectivity enhancing coating |
WO1996001683A1 (en) * | 1994-07-08 | 1996-01-25 | Exxon Chemical Patents Inc. | Molecular sieves and processes for their manufacture |
WO1996001685A1 (en) * | 1994-07-08 | 1996-01-25 | Exxon Research And Engineering Company | An in-situ crystallized zeolite containing composition (lai-isc) |
WO1996001687A1 (en) * | 1994-07-08 | 1996-01-25 | Exxon Research & Engineering Company | Zeolite layers with controlled crystal width and preferred orientation grown on a growth enhancing layer |
WO1996009110A1 (en) * | 1994-09-20 | 1996-03-28 | Graham John Bratton | Improved membrane |
EP0778076A1 (en) * | 1995-12-08 | 1997-06-11 | Institut Francais Du Petrole | Process for the preparation of supported zeolite membranes and membranes obtained by such process |
EP0778075A1 (en) * | 1995-12-08 | 1997-06-11 | Institut Francais Du Petrole | Process for the preparation of porous glass supported zeolite membranes and zeolite membranes obtained thereby |
US5672388A (en) * | 1994-07-08 | 1997-09-30 | Exxon Research & Engineering Company | Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition |
US5824617A (en) * | 1994-07-08 | 1998-10-20 | Exxon Research & Engineering Company | Low alkaline inverted in-situ crystallized zeolite membrane |
US5866654A (en) * | 1996-05-04 | 1999-02-02 | Clariant Gmbh | Process for preparing poly ( vinyl acetals ) and poly (vinyl ketals) |
US5871650A (en) * | 1994-07-08 | 1999-02-16 | Exxon Research And Engineering Company | Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer |
FR2771418A1 (en) * | 1997-11-25 | 1999-05-28 | Inst Francais Du Petrole | Separation of C5 - C8 fraction or an intermediate fraction in three effluents rich in linear, mono-branched and multi-branched paraffins |
WO2000020105A1 (en) * | 1998-10-07 | 2000-04-13 | Smart (Isle Of Man) Limited | Membrane structure |
WO2000021648A1 (en) * | 1998-10-10 | 2000-04-20 | Smart (Isle Of Man) Limited | Membrane pre-treatment process |
WO2000053298A1 (en) * | 1999-03-11 | 2000-09-14 | Exxonmobil Chemical Patents Inc. | Processes for the manufacture of supported materials |
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1992
- 1992-03-27 GB GB929206783A patent/GB9206783D0/en active Pending
-
1993
- 1993-03-26 AU AU38944/93A patent/AU663181B2/en not_active Ceased
- 1993-03-26 CA CA002132969A patent/CA2132969A1/en not_active Abandoned
- 1993-03-26 WO PCT/GB1993/000627 patent/WO1993019840A1/en not_active Application Discontinuation
- 1993-03-26 EP EP93907930A patent/EP0632743A1/en not_active Withdrawn
- 1993-03-26 JP JP5517203A patent/JPH07505331A/en active Pending
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Cited By (30)
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FR2719238A1 (en) * | 1994-04-29 | 1995-11-03 | Centre Nat Rech Scient | Porous composite inorganic material, especially in the form of a membrane, and a process for obtaining such a material. |
WO1995029751A1 (en) * | 1994-04-29 | 1995-11-09 | Centre National De La Recherche Scientifique (Cnrs) | Porous composite inorganic material, particularly in membrane form, and method for making same |
AU711013B2 (en) * | 1994-07-08 | 1999-10-07 | Exxon Research And Engineering Company | A zeolite containing composition with a selectivity enhancing coating |
WO1996001686A1 (en) * | 1994-07-08 | 1996-01-25 | Exxon Research And Engineering Company | A zeolite containing composition with a selectivity enhancing coating |
WO1996001685A1 (en) * | 1994-07-08 | 1996-01-25 | Exxon Research And Engineering Company | An in-situ crystallized zeolite containing composition (lai-isc) |
WO1996001687A1 (en) * | 1994-07-08 | 1996-01-25 | Exxon Research & Engineering Company | Zeolite layers with controlled crystal width and preferred orientation grown on a growth enhancing layer |
US5849980A (en) * | 1994-07-08 | 1998-12-15 | Exxon Research And Engineering Company | Low alkaline inverted in-situ crystallized zeolite membrane |
AU700321B2 (en) * | 1994-07-08 | 1998-12-24 | Exxon Chemical Patents Inc. | Molecular sieves and processes for their manufacture |
WO1996001683A1 (en) * | 1994-07-08 | 1996-01-25 | Exxon Chemical Patents Inc. | Molecular sieves and processes for their manufacture |
US5871650A (en) * | 1994-07-08 | 1999-02-16 | Exxon Research And Engineering Company | Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer |
CN1087182C (en) * | 1994-07-08 | 2002-07-10 | 埃克森美孚化学专利公司 | Molecular sieves and processes for their manufacture |
US5672388A (en) * | 1994-07-08 | 1997-09-30 | Exxon Research & Engineering Company | Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition |
US5824617A (en) * | 1994-07-08 | 1998-10-20 | Exxon Research & Engineering Company | Low alkaline inverted in-situ crystallized zeolite membrane |
US5935440A (en) * | 1994-09-20 | 1999-08-10 | Bratton; Graham John | Membrane |
AU697188B2 (en) * | 1994-09-20 | 1998-10-01 | Smart (Isle Of Man) Limited | Improved membrane |
WO1996009110A1 (en) * | 1994-09-20 | 1996-03-28 | Graham John Bratton | Improved membrane |
US6140263A (en) * | 1995-12-08 | 2000-10-31 | Institute Francais Du Petrole | Process for the production of supported zeolite membranes, and zeolite membranes so produced |
EP0778075A1 (en) * | 1995-12-08 | 1997-06-11 | Institut Francais Du Petrole | Process for the preparation of porous glass supported zeolite membranes and zeolite membranes obtained thereby |
FR2742070A1 (en) * | 1995-12-08 | 1997-06-13 | Inst Francais Du Petrole | PROCESS FOR THE CONTROLLED PRODUCTION OF SUPPORTED ZEOLITE MEMBRANES |
FR2742071A1 (en) * | 1995-12-08 | 1997-06-13 | Inst Francais Du Petrole | PROCESS FOR PREPARING ZEOLITH MEMBRANES SUPPORTED BY POROUS GLASS |
EP0778076A1 (en) * | 1995-12-08 | 1997-06-11 | Institut Francais Du Petrole | Process for the preparation of supported zeolite membranes and membranes obtained by such process |
US5866654A (en) * | 1996-05-04 | 1999-02-02 | Clariant Gmbh | Process for preparing poly ( vinyl acetals ) and poly (vinyl ketals) |
FR2771418A1 (en) * | 1997-11-25 | 1999-05-28 | Inst Francais Du Petrole | Separation of C5 - C8 fraction or an intermediate fraction in three effluents rich in linear, mono-branched and multi-branched paraffins |
EP0922748A1 (en) * | 1997-11-25 | 1999-06-16 | Institut Français du Pétrole | Process for the separation of a C5-C8 feed in three fractions rich in normal , mono-branched and multi-branched paraffins |
US6156950A (en) * | 1997-11-25 | 2000-12-05 | Institut Francais Du Petrole | Process for separating a C5-C8 feed or an intermediate feed into three effluents, respectively rich in straight chain, non-branched and multi-branched paraffins |
WO2000020105A1 (en) * | 1998-10-07 | 2000-04-13 | Smart (Isle Of Man) Limited | Membrane structure |
WO2000021648A1 (en) * | 1998-10-10 | 2000-04-20 | Smart (Isle Of Man) Limited | Membrane pre-treatment process |
US6635594B1 (en) | 1998-10-10 | 2003-10-21 | Smart (Isle Of Man) Limited | Membrane pre-treatment process |
WO2000053298A1 (en) * | 1999-03-11 | 2000-09-14 | Exxonmobil Chemical Patents Inc. | Processes for the manufacture of supported materials |
US7033968B1 (en) | 1999-03-11 | 2006-04-25 | Exxonmobil Research And Engineering Company | Processes for the manufacture of supported materials |
Also Published As
Publication number | Publication date |
---|---|
JPH07505331A (en) | 1995-06-15 |
EP0632743A1 (en) | 1995-01-11 |
AU3894493A (en) | 1993-11-08 |
CA2132969A1 (en) | 1993-10-14 |
GB9206783D0 (en) | 1992-05-13 |
AU663181B2 (en) | 1995-09-28 |
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