JP6801839B2 - 酸化剤および還元剤を用いてtfc膜の流水量を向上させる方法 - Google Patents
酸化剤および還元剤を用いてtfc膜の流水量を向上させる方法 Download PDFInfo
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- JP6801839B2 JP6801839B2 JP2018517429A JP2018517429A JP6801839B2 JP 6801839 B2 JP6801839 B2 JP 6801839B2 JP 2018517429 A JP2018517429 A JP 2018517429A JP 2018517429 A JP2018517429 A JP 2018517429A JP 6801839 B2 JP6801839 B2 JP 6801839B2
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- QFYJRROWSOMHGM-UHFFFAOYSA-L [Zn+2].[O-]S(=O)(=O)S([O-])(=O)=O Chemical compound [Zn+2].[O-]S(=O)(=O)S([O-])(=O)=O QFYJRROWSOMHGM-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SEBXDYXHAAUQIT-UHFFFAOYSA-N aluminum lithium propan-2-olate Chemical compound [Li+].[Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] SEBXDYXHAAUQIT-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
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- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 150000004678 hydrides Chemical class 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
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- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UIXTUDLFNOIGRA-UHFFFAOYSA-N n-carbamoyl-2-chloroacetamide Chemical compound NC(=O)NC(=O)CCl UIXTUDLFNOIGRA-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- BEZDDPMMPIDMGJ-UHFFFAOYSA-N pentamethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1C BEZDDPMMPIDMGJ-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- VIMFRQPQNUFOEQ-UHFFFAOYSA-M sodium;hydrogen sulfate;propan-2-one Chemical compound [Na+].CC(C)=O.OS([O-])(=O)=O VIMFRQPQNUFOEQ-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- XIUROWKZWPIAIB-UHFFFAOYSA-N sulfotep Chemical compound CCOP(=S)(OCC)OP(=S)(OCC)OCC XIUROWKZWPIAIB-UHFFFAOYSA-N 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 150000005201 tetramethylbenzenes Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/10—Spiral-wound membrane modules
- B01D63/107—Specific properties of the central tube or the permeate channel
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- 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
- B01D67/0095—Drying
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- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D69/122—Separate manufacturing of ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Description
本出願は、2016年3月3日付で米国特許庁に出願された米国特許出願第15/059,711号の優先権および利益を主張し、その内容のすべては本明細書に参考として組み込まれる。
本発明は、例えば、水道水、汽水および海水を含む水を精製するために、ナノ濾過、逆浸透または正浸透に用いられる膜を含む薄膜複合(TFC)膜に関し、より詳細には、識別層(discrimination layer)の形成後にTFC膜内で流水量を増加させる方法であって、酸化剤を含有する溶液に膜の識別層を露出させた後に、処理された膜を還元剤に露出させる段階を含むことで、膜の脱塩率特性に否定的な影響を最小限に有したり、膜の脱塩率特性を維持または改善させながら流水量が改善される方法に関する。
[項目1]
ポリアミド識別層を含む薄膜複合(TFC)膜の流水量を改善する方法であって、
a)前記TFC膜を約7ppm〜約35ppmの量の酸化剤を含有する酸化溶液で約10.4以下のpHで少なくとも5分の期間に処理し、前記ポリアミド識別層と反応して処理された膜を形成する段階;および
b)前記処理された膜を還元剤を含有する還元溶液で約4〜約8のpHで少なくとも1分の期間に接触する段階を含み、
段階a)および段階b)の間に近い時間的連結がある
方法。
[項目2]
前記膜を前記酸化溶液で処理する段階の時間の終結と前記酸化した膜を前記還元剤と接触する段階の間の時間の量は、約60分以下である、
項目1に記載の方法。
[項目3]
前記酸化溶液での処理の期間は、約5分〜約90分である、
項目1または2に記載の方法。
[項目4]
前記還元溶液での処理の期間は、約1分〜約60分である、
項目1から3のいずれか1項に記載の方法。
[項目5]
前記還元溶液は、分子塩素、次亜塩素酸またはハイポ亜塩素酸塩イオン、またはこれらの組み合わせを含む、
項目1から4のいずれか1項に記載の方法。
[項目6]
前記還元溶液は、アルカリ−金属メタ−重亜硫酸塩を含む、
項目1から5のいずれか1項に記載の方法。
[項目7]
段階a)および段階b)の間に、洗浄段階をさらに含む、
項目1から6のいずれか1項に記載の方法。
[項目8]
前記酸化溶液は、約7ppm〜約35ppmの量で遊離塩素を含み;
前記還元溶液は、約0.1重量%〜約5重量%の量で塩素除去剤を含むものである、
項目1から7のいずれか1項に記載の方法。
[項目9]
前記塩素除去剤は、アルカリ−金属重亜硫酸塩、アルカリ−土−金属重亜硫酸塩、アルカリ−金属メタ−重亜硫酸塩、アルカリ−金属チオ硫酸塩、アルカリ−土−金属チオ硫酸塩、および過酸化水素、およびこれらの組み合わせからなる群より選択される、
項目8に記載の方法。
[項目10]
前記酸化溶液は、約7ppm〜約35ppmの量で遊離塩素を含み;
前記還元溶液は、約0.1重量%〜約5重量%の量でアルカリ−金属メタ−重亜硫酸塩を含む、
項目1から7のいずれか1項に記載の方法。
[項目11]
前記TFC膜は、2,000ppm以下のNaClを含有する汽水の精製方法に用いられる、
項目1から10のいずれか1項に記載の方法。
[項目12]
前記TFC膜は、海水の精製方法に用いられる、
項目1から10のいずれか1項に記載の方法。
Claims (10)
- ポリアミド識別層を含む薄膜複合膜(TFC膜)の流水量を改善する方法であって、
a)前記TFC膜を7ppm〜35ppmの量の酸化剤を含有する酸化溶液で、8以上11以下のpHで5分から90分の期間に処理し、前記ポリアミド識別層と反応して処理された膜を形成する段階;および
b)前記処理された膜を還元剤を含有する還元溶液で4〜8のpHで少なくとも1分の期間に接触する段階を含み、
前記膜を前記酸化溶液で処理する段階の時間の終結と酸化した前記膜を前記還元剤と接触する段階の間の時間の量は、60分以下であり、
前記酸化剤は、塩素源であり、
前記還元剤は、塩素除去剤である、
方法。 - 前記還元溶液での処理の期間は、1分〜60分である、
請求項1に記載の方法。 - 前記酸化溶液は、分子塩素、次亜塩素酸またはハイポ亜塩素酸塩イオン、またはこれらの組み合わせを含む、
請求項1または2に記載の方法。 - 前記還元溶液は、アルカリ−金属重亜硫酸塩、アルカリ−土−金属重亜硫酸塩、アルカリ−金属メタ−重亜硫酸塩、アルカリ−金属チオ硫酸塩、アルカリ−土−金属チオ硫酸塩、および過酸化水素、およびこれらの組み合わせからなる群より選択される還元剤を含む、
請求項1から3のいずれか1項に記載の方法。 - 前記還元溶液は、アルカリ−金属メタ−重亜硫酸塩を含む、
請求項1から4のいずれか1項に記載の方法。 - 段階a)および段階b)の間に、洗浄段階をさらに含む、
請求項1から5のいずれか1項に記載の方法。 - 前記酸化溶液は、7ppm〜35ppmの量で遊離塩素を含み;
前記還元溶液は、0.1重量%〜5重量%の量で還元剤を含むものである、
請求項1から6のいずれか1項に記載の方法。 - 前記酸化溶液は、7ppm〜35ppmの量で遊離塩素を含み;
前記還元溶液は、0.1重量%〜5重量%の量でアルカリ−金属メタ−重亜硫酸塩を含む、
請求項1から7のいずれか1項に記載の方法。 - 前記TFC膜は、2,000ppm以下のNaClを含有する汽水の精製方法に用いられる、
請求項1から8のいずれか1項に記載の方法。 - 前記TFC膜は、海水の精製方法に用いられる、
請求項1から8のいずれか1項に記載の方法。
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