AU9638698A - Water treatment process - Google Patents
Water treatment process Download PDFInfo
- Publication number
- AU9638698A AU9638698A AU96386/98A AU9638698A AU9638698A AU 9638698 A AU9638698 A AU 9638698A AU 96386/98 A AU96386/98 A AU 96386/98A AU 9638698 A AU9638698 A AU 9638698A AU 9638698 A AU9638698 A AU 9638698A
- Authority
- AU
- Australia
- Prior art keywords
- membrane
- water
- zeo
- silicic acid
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 82
- 238000000034 method Methods 0.000 title claims description 73
- 239000012528 membrane Substances 0.000 claims description 86
- 239000010457 zeolite Substances 0.000 claims description 44
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 39
- 229910021536 Zeolite Inorganic materials 0.000 claims description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 25
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000356 contaminant Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 230000000977 initiatory effect Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000006193 liquid solution Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000013525 flexibilising agent Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 claims description 3
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- HYUJIYRRLKBBBT-UHFFFAOYSA-N COO[Si](OOC)(OOC)OOC Chemical compound COO[Si](OOC)(OOC)OOC HYUJIYRRLKBBBT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 230000001939 inductive effect Effects 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- 150000003377 silicon compounds Chemical class 0.000 claims 1
- 239000012466 permeate Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 11
- 230000004907 flux Effects 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- 239000001963 growth medium Substances 0.000 description 10
- 238000005373 pervaporation Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 125000005624 silicic acid group Chemical class 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 210000002700 urine Anatomy 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000006194 liquid suspension Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 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
- 241000894007 species Species 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 241000365026 Bathygobius Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005191 phase separation Methods 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
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- 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
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- B01D67/00933—Chemical modification by addition of a layer chemically bonded to the membrane
-
- 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
- B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
WO 99/23034 PCT/GB98/03251 - 1 Water Treatment Process The present invention relates to a method for the preparation of purified water; more particularly, it relates to a method for the preparation of purified water by means of a 5 membrane. Water purification, e.g. preparation of potable water or chemically pure water from water containing dissolved salts or other chemicals, is used in areas where pure water is not available. 10 Two widely used techniques are distillation and reverse osmosis. These methods are used for desalinisation of water and for purification of brackish water and are widely applied. However, these methods are relatively expensive in use as distillation, even using flash distillation and vacuum distillation techniques require large amounts of 15 energy and large scale plant. Reverse osmosis requires the use of high pressures and membranes capable of withstanding these pressures. Other polymeric membranes have been suggested but these have suffered defects in practice due to their lack of robustness, a tendency to foul and difficulty to produce in 20 large sizes. Zeolite membranes are known to be able to remove water from organic fluids and several processes and applications have been disclosed. However, in these previously disclosed applications, relatively small amounts of water are removed from the 25 organic liquid, which is required to be dehydrated. We have found that with previously disclosed zeolite membranes, contact with a liquid mixture which is predominantly water in order to separate water from other compounds is not practicable. This is thought to be due to the defects in the membrane, allowing contaminants to be present in the water and, whereas this is not significant when a 30 dehydrated organic liquid is required, it is not acceptable when pure water is required. Other defects arise from the nature of the zeolite membrane; these include cracking and ion-exchange. When water containing salts come into contact with the zeolite membrane, the membrane will 'crack' and defects appear which affect the utility of 35 the membrane. With salts and other ionic compounds present in the water, ion- WO 99/23034 PCT/GB98/03251 -2 exchange can take place with the zeolite membrane and the membrane loses its effectiveness. Hitherto with known zeolite membranes it has not proved possible to remove 5 contaminants from water when the contaminants are only present in small amounts as the volume of water which has to pass through the water makes it impractical for use. However we have found surprisingly that with our membranes it has proved practical to remove contaminants which are present in a small amount and we have devised a 10 method of purifying water using a treated membrane which reduces these problems. According to the invention there is provided a method for obtaining purified water from water containing contaminants which method comprises passing the contaminated water through a crystalline zeo-type material to separate the 15 contaminants from the water, characterised by the zeolite membrane having been treated by contact with a with a silicic acid and/or polysilicic acid or a mixture of silicic and/or poysilicic acids or with an organic silicate. Zeo-type materials are also known as molecular sieves which are widely known and 20 used. They comprise an extended network of channels formed from silicon/oxygen tetrahedrons joined through the oxygen atoms. Zeolites and alumino-silicates are the most commonly known form of zeo-type materials and the present invention is applicable to any membrane formed from zeo-type materials and particularly applicable to zeolites and alumino-silicates. In the "Atlas of Zeolite Structure Types", 25 Meier and Ofsen, 1987, Polycrystal Book Service, Pittsburg USA, various types of structure are described and, for example, those described as having LTA, MEL, MFI or TON structure can be used. In "New Developments in Zeolite Science and Technology Proceedings of the 7th 30 International Conference, Tokyo, 1986, page 103, another class of zeo-type materials are disclosed as crystalline aluminophosphate, silicoalumina phosphates and other metallo-alumino phosphates. Typical zeolites which can be used in the present invention are Zeolites include but 35 are not limited to, 3A, 4A, 5A, 13X, X, Y, ZSM5, MAPOs, SAPOs, Silicalite, WO 99/23034 PCT/GB98/03251 - 3 0, O,etc. The 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, 5 mineral, carbon or polymer fibres or cellulosic or organic or inorganic polymers. 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. 10 Porous ceramics, glass mineral or carbon materials can be used including porous silicon and other carbides, clays and other silicates and porous silica. If desired, the support can be a zeolite formed by compression or using a binder. The shape of the support is not critical, for example, flat sheet, tubular, wound spiral, etc. can be used. 15 If polymeric 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 material such as a pellitised catalyst. 20 The present invention can be used with porous supports of any suitable size although, for large flux rates through a membrane, large pore sizes are preferred. Preferably pore sizes of 0.01 to 2,000 microns, more preferably of 0.1 to 200 and ideally of 1 to 20 microns are used. Pore sizes up to 300 microns can be determined by bubble point 25 pressure as specified in ISO 4003. Larger pore sizes can be measured by microscopic methods. The larger the relative amount of the surface which is composed of voids in general the more suitable the porous support. 30 The membranes which can be treated to be used in 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 deposition of crystals on conducting substrates e.g. as described in DE 4109037. 35 WO 99/23034 PCT/GB98/03251 - 4 When 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. 5 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- 104800, EP-A-2899 and EP-A-2900. Standard text books by D W Breck ("Zeolites Molecular Sieves, Structure Chemistry and Use") published by John 10 Wiley (1974) and P.A Jacobs and J.A Martens (Studies in Surface Science and Catalysis No. 33, Synthesis of High Silica Alumino silicate Zeolites" published by Elsevier (1987), describe many such synthesis gels. The process which can be used includes conventional syntheses of zeo-type materials, except that the synthesis is carried out in the presence of the porous support. Most commonly, gels are 15 crystallised by the application of heat. The treated membrane which is used in the process of the invention can be prepared by a process which comprises deposition or crystallisation from a growth medium. In one embodiment of the invention the growth medium can be used in two different 20 methods. In 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 25 (1.5 - 3.0)NaO : (1)A1 2 0 3 : (2.0)SiO 2 :(50-200)H 2 0 and the method used can be used in any of the methods disclosed in the references listed above. In the liquid solution method (method 2) the liquid solution used to form the 30 membrane preferably has a molar composition in the range of : (6 - 10.0)Na 2 0 : (0.2)A1 2 0 3 : (1.0)SiO 2 : (150-250)H 2 0 The liquid solution preferably contains a maximum amount of the compound capable 35 of crystallising to form a zeo-type material whilst still remaining a liquid solution. By WO 99/23034 PCT/GB98/03251 - 5 maximum amount is meant the maximum amount which can be maintained in solution so that no precipitation occurs before zeolite formation. Methods (1) and (2) can be used under the conditions listed below and method (1) 5 and method (2) can be used either on their own or with method (1) followed by 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 100oC and the pH can be 10 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 of the desired zeolite to be synthesised. The membrane can be washed to pH neutral after membrane formation prior to any post-treatment. 15 The porous support can be contacted with the growth medium by immersion or by pouring the growth medium over the support with the support held substantially horizontal, either face up at the bottom of a container, or face down at the surface of the growth medium, or it can be passed over one or both sides of the support, with the 20 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. The growth medium can be kept static, stirred, tumbled or passed over or around the 25 support, alternatively the growth medium can be passed over both sides of the support with the support held substantially horizontal or at any intermediate position. Pressure may also be applied but it is usually convenient to conduct the crystallisation under autogenous pressure. Preferably the porous support is completely 30 immersed in the growth medium; alternatively, if desired, only one surface of the support may be in contact with the growth medium. 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 outside of the tube need be in contact with the growth medium. 35 It may be useful if it is desired to produce a membrane containing two different WO 99/23034 PCT/GB98/03251 -6 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. 5 If desired, the treatment with the gel or liquid solution can be repeated one or more times to obtain thicker membrane coatings. Preferably the porous support is pre-treated with a zeolite initiating agent. The zeolite initiating agent is preferably a cobalt, molybdenum or nickel oxide or it can be 10 particles of a zeolite, e.g. the zeolite which it is intended to deposit on the porous support, or any combination of these. Another example of an initiating agent is a compound which can deposit a zeo-type pre-cursor material e.g. a silicic acid or polysilicic acid. 15 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. 20 Alternatively 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. If a wet process is used, a liquid suspension of powder of the zeolite initiation agent is formed and the liquid suspension contacted with the porous support to deposit the 25 zeolite initiation agent on the support. 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. 30 When a silicic acid is used as an initiating agent it can be a silicic acid as herein defined. In the present specification by silicic acid is meant monosilicic, low, medium and 35 high molecular weight polysilicic acids and mixtures thereof.
WO 99/23034 PCT/GB98/03251 -7 As well as treatment with silicic acids the zeo-type materials can be treated with alkylorthosilicates such as tetra ethyl ortho silicate (TEOS) and tetra isopropyl ortho silicate (TIPOT) akoxyorthosilicates such as tetramethoxyortho silicate which form a 5 polysilicic acid when applied to the zeo-type material. These alkylorthosilicates and alkoxyorthosilicates form mesoporous silica compounds which consist essentially of a series of polysilicic acid units linked together, each unit comprising a polysilicic acid molecule as described in GB Patent Application 9316350.9 and comprising a plurality of three dimensional species linked together with each species either having 10 silicon atom bridges with an oxygen atom between each silicon atom or hydroxyl groups on the silicon atoms. The treatment of zeo-type materials by silicic acids is described in WO 96/09110. 15 Methods of making silicic acids are described in GB Patent Application 2269377 and a preferred method is by acidification of a sodium silicate solution followed by separation of the silicic acid by phase separation using an organic solvent such as tetrahydrofuran. The organic phase can then be dried and anhydrous silicic acid separated e.g. by addition of n-butanol to obtain a substantially anhydrous solution of 20 silicic acid. The degree of polymerisation of the silicic acid depends on the actual conditions used e.g. the time the sodium silicate solution is in contact with the acid before addition of the organic solvent, temperature etc. The silicic acid used in the present invention preferably has an average molecular 25 weight in the range of 96 to 10,000 and more preferably of 96 to 3220. The silicic acids are known compounds and are usually prepared as a mixture of acids with a range of different molecular weights and this mixture is suitable for use in the present invention. 30 The silicic acids are combination of silicon, oxygen and hydrogen, linked together in the case of polysilicic acids through an oxygen bridge, with terminal -OH groups. They have a generic formula of Sin 0p(OH)r where n, p and r can vary from n=1, p=0, 35 r=4 in the case of monosilicic acid through to n=8-12, p=12-20, r-8-12 in the case of WO 99/23034 PCT/GB98/03251 - 8 medium molecular weight silicic acids through to n=20-32, p=36-60 and r=8-20 in the case of a higher molecular weight polymers. The membrane can be treated with anhydrous silicic acid and a preferred method is to 5 contact the membrane with an anhydrous solution of the silicic acid e.g. by dipping, pulling through with vacuum, forming with pressure etc. Preferably the solution containing the silicic acid is removed e.g. by evaporation at room temperature and/or by heating. 10 Alternatively cross-linking can be accomplished by treating with an acid or base or with acidified or basified water e.g. of pH 2 to 12 preferably of 4 to 10. The silicic acids used in the present invention can be used in "narrow" molecular weight distribution as formed or in a combination of different molecular weight ranges. 15 Greater flexibility can be introduced into the final membranes by treating them with a flexibilising agent by adding e.g. a hydroxy terminated polysiloxane into the silicic acid solution before treatment of the membrane. 20 When the membrane is treated by a alkylorthosilicate the membrane is preferably treated as above using the alkylorthosilicate in place of the silicic acids. The membranes treated by this process are improved in terms of their performance and membrane strength compared with untreated membranes. 25 The method of the invention can be used to produce water with very low levels of contaminants e.g. below 10 Oppm from contaminated water.. The degree of purification of the water, i.e. the level of contaminants still present in 30 the purified water will depend on the thickness and nature of the zeolite membrane, the pressure applied to the water, the time of contact of the contaminated water with the zeolite membrane, temperature, etc. At the very low levels of contaminants obtained, particularly when the exact nature of the contaminants is unknown it is convenient to measure the conductivity of the water. De-ionised water typically has a 35 conductivity of about 0.1 to 30gS/cm and distilled water has a conductivity of about WO 99/23034 PCT/GB98/03251 -9 1 to 2 gS/cm. The method of the present invention can produce water with a conductivity of below these values which shows that there is a very low level of contaminants. 5 The water can be purified by being passed through the membrane by applying a reduced pressure or vacuum to one side of the membrane and this reduction in pressure causing the water to pass through the membrane and be separated from the impurities. 10 Owing to the action of the treated membrane, a wide range of contaminated water can be purified, e.g. sea water, brackish water, water contaminated with industrial chemicals such as hydrocarbons, organic chlorine compounds, metals, detergents etc., biological materials such as urines etc. and water contaminated by human or animal use e.g. the so-called "grey" water obtained for example from washing, showers, 15 bathwater etc. If desired, by increasing the severity of the treatment conditions, substantially pure water or de-ionised water can be obtained. Even with sea-water which has a relatively high conductivity levels of conductivity (-30,000 gS/cm) below 30 pS/cm can be achieved indicating a very low level of salt 20 in the water. It is surprising that by treating a zeolite membrane as described above enables the membrane to be used to purify contaminated water in a way not possible with the untreated zeolite membrane and to obtain such very low levels of conductivity. 25 The method can be used in a pervaporation process or as a reverse osmosis process. In general reverse osmosis processes have a higher flux. The invention is described in the following Examples in which Example 1 is an 30 example of the preparation of a membrane using a known method, Example 2 is an example of preparation of a post-treatment solution, Example 3 is an example of the test procedure, Example 4 is an example of the post-treatment procedure and Examples 5 to 11 are examples of production and testing of treated membranes. 35 Example 1 Membrane Growth WO 99/23034 PCT/GB98/03251 - 10 The substrate used was a Bekipor (Trade Mark) ST 5BL3 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 5 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 6.5 microns. A 7cm. disc of the metal mesh was placed in a 100ml flat bottomed petri dish which 10 had previously been cleaned by washing with de-ionised water, acetone, toluene and finally acetone before being dried in an oven at 90 degrees C. for 3 hours. (a) Cobalt pre-treatment: 15 The mesh was placed in a beaker to which was added 50ml of 0.1 M cobalt nitrate solution, the beaker was placed in an oven at 90oC to dry, then the mesh was removed from the beaker and fired at 250 0 C for 4 hours. The mesh was removed from the furnace and allowed to cool. This procedure was repeated 2 more times to obtain a good cobalt oxide coating. 20 (b) Zeolite Pre-treatment Zeolite 4A powder was rubbed into the active side of the substrate, which had already been cobalt coated as above, using a gloved finger, until no more zeolite will rub into 25 the surface, any excess zeolite was tapped off. Two solutions A and B were prepared separately in two 500 ml glass bottles as follows: 30 Solution A 24.49g Sodium Aluminate, 3.75g Sodium Hydroxide and 148.60g de-ionised water were mechanically shaken until dissolved. The Sodium Aluminate had an actual composition 62.48% Al 2 0 3 , 35.24% Na 2 0, and 2.28% H20. 35 WO 99/23034 PCT/GB98/03251 - 11 Solution B 50.57g Sodium Silicate of composition 14.21% Na 2 0 , 35.59% SiO 2 and 50.20% H20 was dissolved in 148.60g de-ionised water. 5 Solution A was added slowly to solution B with both stirring and shaking by hand to ensure complete and even mixing (it is important that no lumps of hydrogel are formed). This resulted in a hydrogel having a molar composition 10 2.01 Na 2 0 : A1 2 03:2.0 SiO 2 : 120.0 H 2 0 100 ml of the hydrogel was slowly poured into a growth vessel containing the cobalt oxide treated and zeolite rubbed mesh in a vertical position. The growth vessel was placed in a domestic pressure cooker together with a beaker containing the remaining 15 hydrogel solution. The pressure cooker was placed in an oven preheated to 100 degrees C. for 5 hours. Subsequently it was removed from the oven and allowed to cool for 30 minutes. The growth vessel was removed and the solution poured away. The metal mesh was carefully removed with a long flat rod ensuring that the mesh 20 was not bent or damaged in any way. The mesh was placed in a glass beaker and washed three times with 100ml aliquots of de-ionised water, swirling the solution each time to ensure complete removal of residues. The membrane was allowed to air dry overnight. 25 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 mesh was inverted and the process repeated The mesh was reinverted and the top surface cleaned again. It was then washed with de-ionised water and left to air dry. 30 X-ray Analysis showed this to be a Zeolite 4A Example 2 Preparation of TEOS For Post Treatment of Membrane 35 The post treatment solution was prepared by placing 40ml of (TEOS) into a clean, dry WO 99/23034 PCT/GB98/03251 - 12 beaker, adding 180 ml of deionised water and 180ml of ethanol. The mixture was then stirred at 300r.p.m. for a period of 5 mins. Example 3 Membrane Test Procedure 5 A membrane is loaded into a pervaporated test cell in an apparatus as shown in the accompanying drawing. 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 10 (6) and was sealed into the cell with 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 (11) and relief valve (12). 15 The test cell was filled with an isopropanol/water (IPA/H 2 0) mixture (90/10 wt. % respectively). The membrane was tested at approximately 70 0 C. The pressure on the side of the membrane remote from the liquid was reduced to 4 20 mbar (0.4 kN). Permeate was collected over periods of 8 hours and weighed, and small aliquots were analysed, feed water concentration was monitored throughout. Example 4 Post-treatment Procedure of Membrane 25 After the initial test of the untreated membrane in the apparatus of Example 3 with IPA/Water, the cell was emptied, rinsed with 2 x 50 ml aliquots of ethanol and then another 50ml aliquot of ethanol was placed into the cell which was then placed under vacuum for 30 mins. 30 The ethanol was removed from the cell and the TEOS post-treatment solution prepared as in Example 2 was poured into the cell. The cell was then treated to 70 0 C for a period of 24 hours, with the downstream side under vacuum. After this period, the mix was removed, the heat switched off, vacuum removed and then compressed air was passed over the membrane for a period of one hour.
WO 99/23034 PCT/GB98/03251 - 13 Example 5 A membrane produced by the method of Example 1 was treated under pervaporation 5 conditions described on Example 3 and the results shown in Table 1 below Table 1 Isopropanol/water mixture at 70 0 C 10 Time on Stream Feed Water Permeate Water Permeate Water Flux (J) (hours) % weight % weight kg/m2/day 15 1 11.10 90.11 147.75 1.5 6.00 96.47 88.00 2.0 4.36 94.81 72.87 4.0 2.94 81.14 29.74 5.5 0.47 30.57 4.91 20 The membrane was then post treated as in Example 4, the membrane was re-tested under pervaporation conditions as in Example 3 and the results shown in Table 2.
WO 99/23034 PCT/GB98/03251 - 14 Table 2 Isopropanol/water mixture at 70 0 C 5 Time on Stream Feed Water Permeate Water Permeate Water Flux (J) (hours) % weight % weight kg/m 2 /day 10 0.5 7.36 98.62 102.82 0.8 5.27 100.00 99.40 1.3 4.01 99.69 63.05 1.8 2.60 98.28 30.96 3.2 0.75 89.06 10.51 15 3.5 0.63 85.00 1.13 Example 6 A membrane produced by the method as described in Example 1 was treated under 20 pervaporation conditions described in example 3 and the results shown in Table 3 Table 3 Isopropanol/water mixture at 70 0 C 25 Time on Stream Feed Water Permeate Water Permeate Water Flux (J) (hours) % weight % weight kg/m 2 /day 30 1.0 9.42 87.46 156.34 1.5 3.33 86.31 65.84 2.0 2.10 76.84 45.81 4.0 1.15 46.30 12.65 5.5 0.37 18.88 1.36 35 WO 99/23034 PCT/GB98/03251 - 15 The membrane was then post treated as in Example 4, the membrane was re-tested under pervaporation conditions as in example 3 and the results shown in Table 4. 5 Table 4 Isopropanol/water mixture at 70 0 C Time on Stream Feed Water Permeate Water Permeate 10 Water Flux (J) (hours) % weight % weight kg/m2/day 0.5 10.16 98.83 103.04 0.83 6.86 100.00 99.40 15 1.33 4.91 99.53 62.95 1.83 3.39 97.43 30.69 3.17 0.40 88.48 10.44 3.5 0.28 85.00 1.13 20 Examples 7-11 Various different water samples were purified using the membrane of the invention. Example 7 25 The membrane used was prepared as in Example 6 and after post treatment was re tested under pervaporation conditions as in Example 3 and the results shown in Table 5.
WO 99/23034 PCT/GB98/03251 - 16 Table 5 Tap Water at 70 0 C 5 Time on Stream Permeate Water Flux (J) (hours) kg/m 2 /day 1 269.6 2 270.2 10 3 274.1 4 274.7 5 279.2 6 280.2 15 Conductivity Tap Water 660 gS/cm Tap Water Permeate 2.2 gS/cm 20 Example 8 The membrane used was prepared as in Example 6 and after post treatment was re 25 tested under pervaporation conditions as in Example 3 and the results shown in Table 6.
WO 99/23034 PCT/GB98/03251 - 17 Table 6 De-ionised Water at 70 0 C 5 Time on Stream Permeate Water Flux (J) (hours) kg/m 2 /day 1 394.9 2 368.1 10 3 346.3 4 339.4 Conductivity 15 De-ionised Water 1.8 pS/cm De-ionised Water Permeate 0.8 tS/cm Example 9 20 The membrane used was prepared as in Example 5 and after post treatment was re tested under pervaporation conditions as in Example 3 and the results shown in Table 7 Table 7 25 Soapy Water at 700C Time on Stream Permeate Water Flux (J) (hours) kg/m 2 /day 1 129.1 30 2 154.1 3 172.4 4 182.1 5 183.9 6 182.2 35 7 180.7 WO 99/23034 PCT/GB98/03251 - 18 Conductivity Soapy Water 771 gS/cm 5 Soapy Water Permeate 24.8 pS/cm Example 10 The membrane used was prepared as in Example 5 and after post treatment was re 10 tested under pervaporation conditions as in Example 3 and the results shown in Table 8. Table 8 15 Urine at 700C Time on Stream Permeate Water Flux (J) (hours) kg/m 2 /day 1 91.9 20 2 77.1 3 77.2 4 71.9 5 72.3 6 70.1 25 Conductivity Urine 12,600 ps/cm Urine Permeate 25.6 ps/cm 30 Example 11 The membrane used in Example 6 and after post treatment was re-tested under pervaporation conditions as in Example 3 and the results shown in Table 9. 35 WO 99/23034 PCT/GB98/03251 - 19 Table 9 Synthetic Sea Water at 70 0 C 5 Time on Stream Permeate Water Flux (J) (hours) kg/m 2 /day 1 96.1 2 97.0 3 96.0 10 4 103.7 5 104.6 6 91.9 Conductivity 15 Sea Water 31,000 RS/cm Sea Water Permeate 25.2 RS/cm
Claims (20)
1. A method for obtaining purified water from water containing contaminants which method comprises passing the contaminated water through a crystalline zeo-type 5 material to separate the contaminants from the water, characterised in that the zeolite membrane has been treated by contact with a with a silicon compound selected from silicic acid and/or polysilicic acid or a mixture of silicic and/or polysilicic acids and organic silicates. 10
2. A method as claimed in claim 1 characterised in that the membrane is formed by the deposition of a film of zeo-type material on a porous support.
3. A method as claimed in claim 1 or 2 characterised in that the membrane is formed by crystallisation of a film of a zeo-type material from a synthesis gel by 15 immersing a porous support in a synthesis gel comprising a gel of a zeo-type material and the zeo-type material deposited onto the porous support by the application of pressure and/or heat.
4. A method as claimed in any one of the preceding claims characterised in that the 20 zeo-type material is zeolite 3A, 4A, 5A, 13X, X, Y, ZSM5, MPOs, SAPOs, Silicalite, P, or 0.
5. A method as claimed in any one of claims 1 to 4 characterised in that the porous support is pre-treated with a zeolite initiating agent selected from cobalt oxide, nickel 25 oxide or molybdenum oxide, a zeolite or a silicic acid.
6. A method as claimed in any one of claims 1 to 5 characterised in that the crystalline zeo-type membrane is produced by a process which comprises immersing at least one surface of a porous support in a synthesis gel or solution which is capable 30 of crystallising to produce a crystalline zeo-type material, inducing crystallisation of said gel so that zeo-type material crystallises on the support, removing the support from the mix and then contacting the porous support with a liquid solution containing a dissolved compound capable of crystallising from the solution to produce a crystallisation from the said solution so that a second coating of a zeo-type material 35 crystallises on the support. VV"J Y7IZ.3.31#r% YL I/t..jD 3 jI - 21
7. A method as claimed in any one of the preceding cliaims in which the silicic acid has an average molecular weight in the range of 96 to 10,000 and in that the silicic acid is cross-linked in the pores of the membrane. 5
8. A method as claimed in claim 7 characterised in that the silicic acid has an average molecular weight in the range of 96 to 3220.
9. A method as claimed in any one of claims 1 to 8 characterised in that the silicic 10 acid has a generic formula of SinOp(OH)r where n, p and r can vary from n=1, p=0, r-4 through to n=8-12, p=12-20, r-8-12.
10. A method as claimed in any one of claims 1 to 9 characterised in that the silicic acid has a generic formula of SinOp(OH)r where n, p and r are from n=20-32, p= 3 6 15 60 and r-8-20.
11. A method as claimed in any one of claims 1 to 10 characterised in that the membrane is treated with anhydrous silicic acid. 20
12. A method as claimed in claim 11 characterised in that the silicic acid is cross linked by treating with an acid or base.
13. A method as claimed in any one of claims 1 to 6 characterised in that the organic silicate is an alkylorthosilicate or an alkoxyorthosilicates. 25
14. A method as claimed in claim 13 characterised in that the organic silicate is tetra ethyl ortho silicate, or tetra isopropyl ortho silicate or tetramethoxyortho silicate.
15. A process as claimed in any one of claims 1 to 14 characterised in that a 30 flexibilising agent is added to the silicic acid or organic silicate solution before treatment of the membrane.
16. A process as claimed in claim 15 characterised in that the flexibilising agent is a hydroxy terminated polysiloxane. 35 VVU WJYhUJ1 rL, IIIYDIUJADI - 22
17. A process as claimed in any one of the preceding claims characterised in that the porous support is formed from a metal mesh and/or sintered metal particles.
18. A method as claimed in any one of claims 1 to 17 characterised in that the water 5 containing the contaminants is passed through the membrane so that at least some of the contaminants do not pass through the membrane.
19. A method as claimed in claim 18 characterised in that reduced pressure is applied on the side of the membrane remote from the water containing contaminants. 10
20. A method as claimed in any one of claims 18 or 19 characterised in that the decontaminated water has a conductivity of less than 30.0 gs/cm.
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GB9723253 | 1997-11-04 | ||
GBGB9723253.2A GB9723253D0 (en) | 1997-11-04 | 1997-11-04 | Water treatment process |
PCT/GB1998/003251 WO1999023034A1 (en) | 1997-11-04 | 1998-11-02 | Water treatment process |
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JP (1) | JP2001521823A (en) |
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AU (1) | AU9638698A (en) |
CA (1) | CA2306847A1 (en) |
GB (1) | GB9723253D0 (en) |
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US6857945B1 (en) * | 2000-07-25 | 2005-02-22 | Applied Materials, Inc. | Multi-chamber carrier head with a flexible membrane |
GB0704797D0 (en) * | 2007-03-13 | 2007-04-18 | Phoenix Ipr Ltd | Membrane structures and their production and use |
CA2687105A1 (en) * | 2007-05-08 | 2008-11-13 | The University Of Queensland | Desalination method and apparatus |
GB0710265D0 (en) * | 2007-05-30 | 2007-07-11 | Phoenix Ipr Ltd | Membrane structures and their production and use |
US8147735B2 (en) | 2008-07-09 | 2012-04-03 | Eltron Research & Development, Inc. | Semipermeable polymers and method for producing same |
EP2192090A1 (en) * | 2008-12-01 | 2010-06-02 | Technische Universiteit Delft | Process for the production of ultra pure water using a membrane |
JP5153809B2 (en) * | 2010-03-15 | 2013-02-27 | 三井造船株式会社 | Zeolite membrane production method |
KR101445154B1 (en) * | 2011-08-01 | 2014-10-01 | 한국에너지기술연구원 | PERVAPORATIVE SEAWATER DESALINATION APPARATUS AND METHOD USING NaA ZEOLITE MEMBRANE |
US20160030893A1 (en) * | 2013-03-14 | 2016-02-04 | Mary Laura Lind | Nanocomposite Membranes |
CN107328773B (en) * | 2017-02-28 | 2020-03-13 | 上海大学 | High-throughput experimental platform for water/salt migration/dissolution/crystallization characterization |
CN109179727A (en) * | 2018-10-31 | 2019-01-11 | 黄山学院 | A kind of drinkable water heavy metal purification device based on zeolite molecular sieve film |
BR102021020147B1 (en) * | 2021-10-07 | 2022-10-04 | João Carlos Gomes De Oliveira | IMPLEMENTATION PROCESS OF ARTIFICIAL RUNNING WATER BEACH FOR RECREATION |
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US5019263A (en) * | 1990-06-05 | 1991-05-28 | Mobil Oil Corp. | Membrane composed of a pure molecular sieve |
GB9022836D0 (en) * | 1990-10-19 | 1990-12-05 | British Petroleum Co Plc | Membranes |
EP0782473B1 (en) * | 1994-09-20 | 2002-11-27 | Smart (Isle Of Man) Limited | Improved membrane |
GB9523854D0 (en) * | 1995-11-22 | 1996-01-24 | Bratton Graham J | Water removal device |
GB9607090D0 (en) * | 1996-04-03 | 1996-06-05 | Bratton Graham J | Improved membrane |
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1997
- 1997-11-04 GB GBGB9723253.2A patent/GB9723253D0/en not_active Ceased
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1998
- 1998-11-02 WO PCT/GB1998/003251 patent/WO1999023034A1/en not_active Application Discontinuation
- 1998-11-02 KR KR1020007004850A patent/KR20010031784A/en not_active Application Discontinuation
- 1998-11-02 AU AU96386/98A patent/AU9638698A/en not_active Abandoned
- 1998-11-02 CA CA002306847A patent/CA2306847A1/en not_active Abandoned
- 1998-11-02 JP JP2000518914A patent/JP2001521823A/en not_active Withdrawn
- 1998-11-02 CN CN98810856.9A patent/CN1278235A/en active Pending
- 1998-11-02 EP EP98950233A patent/EP1073612A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
KR20010031784A (en) | 2001-04-16 |
JP2001521823A (en) | 2001-11-13 |
CA2306847A1 (en) | 1999-05-14 |
GB9723253D0 (en) | 1998-01-07 |
WO1999023034A1 (en) | 1999-05-14 |
CN1278235A (en) | 2000-12-27 |
EP1073612A1 (en) | 2001-02-07 |
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Legal Events
Date | Code | Title | Description |
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MK5 | Application lapsed section 142(2)(e) - patent request and compl. specification not accepted |