WO2018037683A1 - Method and system for processing water containing low-molecular-weight organic matter - Google Patents
Method and system for processing water containing low-molecular-weight organic matter Download PDFInfo
- Publication number
- WO2018037683A1 WO2018037683A1 PCT/JP2017/022369 JP2017022369W WO2018037683A1 WO 2018037683 A1 WO2018037683 A1 WO 2018037683A1 JP 2017022369 W JP2017022369 W JP 2017022369W WO 2018037683 A1 WO2018037683 A1 WO 2018037683A1
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- WO
- WIPO (PCT)
- Prior art keywords
- reverse osmosis
- osmosis membrane
- water
- treatment
- low molecular
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000005416 organic matter Substances 0.000 title claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 260
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 234
- 239000000203 mixture Substances 0.000 claims abstract description 85
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 74
- -1 sulfamic acid compound Chemical class 0.000 claims abstract description 73
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 71
- 229920002647 polyamide Polymers 0.000 claims abstract description 55
- 239000007800 oxidant agent Substances 0.000 claims abstract description 34
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 110
- 239000000126 substance Substances 0.000 claims description 79
- 230000001590 oxidative effect Effects 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 14
- 230000001954 sterilising effect Effects 0.000 claims description 14
- 238000004659 sterilization and disinfection Methods 0.000 claims description 14
- 239000012466 permeate Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 4
- 238000011033 desalting Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims 3
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 description 27
- 239000007795 chemical reaction product Substances 0.000 description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 17
- 229910052801 chlorine Inorganic materials 0.000 description 17
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002407 reforming Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 102100035925 DNA methyltransferase 1-associated protein 1 Human genes 0.000 description 2
- 101000930289 Homo sapiens DNA methyltransferase 1-associated protein 1 Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079920 digestives acid preparations Drugs 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- WOHVONCNVLIHKY-UHFFFAOYSA-L [Ba+2].[O-]Cl=O.[O-]Cl=O Chemical compound [Ba+2].[O-]Cl=O.[O-]Cl=O WOHVONCNVLIHKY-UHFFFAOYSA-L 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- FECFIIXKXJBOSU-UHFFFAOYSA-N butylsulfamic acid Chemical group CCCCNS(O)(=O)=O FECFIIXKXJBOSU-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- BAQKWXACUNEBOT-UHFFFAOYSA-N dibutylsulfamic acid Chemical compound CCCCN(S(O)(=O)=O)CCCC BAQKWXACUNEBOT-UHFFFAOYSA-N 0.000 description 1
- YGNOYUCUPMACDT-UHFFFAOYSA-N dimethylsulfamic acid Chemical compound CN(C)S(O)(=O)=O YGNOYUCUPMACDT-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XRVWREPFYXZOPK-UHFFFAOYSA-N dipropylsulfamic acid Chemical compound CCCN(S(O)(=O)=O)CCC XRVWREPFYXZOPK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IOISAJSHULNACL-UHFFFAOYSA-N ethyl(methyl)sulfamic acid Chemical compound CCN(C)S(O)(=O)=O IOISAJSHULNACL-UHFFFAOYSA-N 0.000 description 1
- SIVVHUQWDOGLJN-UHFFFAOYSA-N ethylsulfamic acid Chemical group CCNS(O)(=O)=O SIVVHUQWDOGLJN-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- YZVQGLCYZLGIAM-UHFFFAOYSA-N methyl(propyl)sulfamic acid Chemical compound CCCN(C)S(O)(=O)=O YZVQGLCYZLGIAM-UHFFFAOYSA-N 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical group CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- AMULHDKUJWPBKU-UHFFFAOYSA-L nickel(2+);dichlorite Chemical compound [Ni+2].[O-]Cl=O.[O-]Cl=O AMULHDKUJWPBKU-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- JWQSOOZHYMZRBT-UHFFFAOYSA-N propan-2-ylsulfamic acid Chemical group CC(C)NS(O)(=O)=O JWQSOOZHYMZRBT-UHFFFAOYSA-N 0.000 description 1
- HLIBNTOXKQCYMV-UHFFFAOYSA-N propylsulfamic acid Chemical group CCCNS(O)(=O)=O HLIBNTOXKQCYMV-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- B01D61/08—Apparatus therefor
-
- 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
- B01D61/10—Accessories; Auxiliary operations
-
- 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
- B01D61/14—Ultrafiltration; Microfiltration
-
- 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
- B01D61/58—Multistep processes
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4604—Treatment of water, waste water, or sewage by electrochemical methods for desalination of seawater or brackish water
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
Definitions
- the present invention relates to a treatment method and a treatment system for low molecular organic substance-containing water containing a low molecular organic substance using a reverse osmosis membrane.
- RO membrane reverse osmosis membrane
- Patent Document 1 in a membrane separation apparatus equipped with a reverse osmosis membrane element having a polyamide skin layer, after filling the reverse osmosis membrane element into a pressure vessel in the membrane separation apparatus, bromine is added to the reverse osmosis membrane element.
- a method for treating a reverse osmosis membrane element in which a free chlorine aqueous solution is brought into contact is described.
- Patent Document 1 can temporarily improve the water quality, but if a free chlorine aqueous solution containing bromine is passed for a long time, the reverse osmosis membrane deteriorates and the water quality decreases.
- the reverse osmosis membrane has a low rejection rate for low molecular organic substances
- a treatment method capable of performing a reverse osmosis membrane treatment with a high rejection rate is required. ing.
- An object of the present invention is to provide a treatment method and a treatment system for low-molecular-weight organic substance-containing water, which can treat a water to be treated containing a low-molecular-weight organic substance with a reverse osmosis membrane at a high rejection.
- the present invention includes a reverse osmosis membrane treatment step of treating water to be treated containing a low molecular organic substance with a reverse osmosis membrane, and the reverse osmosis membrane comprises a stabilized hypobromine containing a bromine-based oxidant and a sulfamic acid compound.
- This is a method for treating low molecular organic substance-containing water, which is a membrane modified by bringing an acid composition into contact with a polyamide-based reverse osmosis membrane.
- the present invention also includes a reverse osmosis membrane treatment step of treating water to be treated containing a low molecular organic substance with a reverse osmosis membrane, wherein the reverse osmosis membrane comprises stabilized hypobromite containing bromine and a sulfamic acid compound.
- This is a method for treating low molecular organic substance-containing water, which is a membrane modified by bringing the composition into contact with a polyamide-based reverse osmosis membrane.
- the stabilized hypobromite composition is obtained by a method comprising a step of adding bromine to a mixed liquid containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere. It is preferable that
- the contact is preferably performed at a pH lower than the pH of the water to be treated.
- the water to be treated in the reverse osmosis membrane treatment step is preferably subjected to at least one of deaeration treatment, ion exchange treatment, and UV sterilization treatment.
- the reverse osmosis membrane treatment step includes a first reverse osmosis membrane treatment step of treating the water to be treated with a first reverse osmosis membrane, and the first reverse osmosis membrane treatment step.
- At least one of the permeated water in the first reverse osmosis membrane treatment step and the permeated water in the second reverse osmosis membrane treatment step is subjected to ion exchange treatment, electric desalting. It is preferable to perform at least one of processing, UV sterilization processing, UV oxidation processing, particulate removal processing, and third reverse osmosis membrane processing.
- the present invention comprises a reverse osmosis membrane treatment apparatus for treating water to be treated containing a low molecular organic substance with a reverse osmosis membrane, and the reverse osmosis membrane comprises a stabilized hypobromine containing a bromine-based oxidizing agent and a sulfamic acid compound.
- This is a low molecular organic substance-containing water treatment system, which is a membrane modified by bringing an acid composition into contact with a polyamide-based reverse osmosis membrane.
- the present invention also includes a reverse osmosis membrane treatment apparatus for treating water to be treated containing a low-molecular organic substance with a reverse osmosis membrane, wherein the reverse osmosis membrane comprises stabilized hypobromite containing bromine and a sulfamic acid compound.
- This is a treatment system for water containing low molecular weight organic matter, which is a membrane modified by bringing the composition into contact with a polyamide-based reverse osmosis membrane.
- the stabilized hypobromite composition is obtained by a method including a step of adding bromine to a mixed liquid containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere. It is preferable that
- the contact is preferably performed at a pH lower than the pH of the water to be treated.
- the low molecular organic substance-containing water treatment system includes at least one of a degassing treatment device, an ion exchange treatment device, and a UV sterilization treatment device that performs treatment on the water to be treated of the reverse osmosis membrane treatment device. Is preferred.
- the reverse osmosis membrane treatment device includes: a first reverse osmosis membrane treatment device for treating the treated water with a first reverse osmosis membrane; and the first reverse osmosis membrane treatment device.
- an ion exchange treatment device for treating at least one of the permeated water of the first reverse osmosis membrane treatment device and the permeated water of the second reverse osmosis membrane treatment device. It is preferable to include at least one of an electric desalination treatment apparatus, a UV sterilization treatment apparatus, a UV oxidation treatment apparatus, a fine particle removal treatment apparatus, and a third reverse osmosis membrane treatment apparatus.
- the water to be treated containing a low-molecular organic substance can be treated with a reverse osmosis membrane with a high rejection.
- FIG. 1 shows an outline of an example of a treatment system for water containing low molecular weight organic matter according to an embodiment of the present invention, and the configuration thereof will be described.
- 1 is a reverse osmosis modified by bringing a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound into contact with a polyamide-based reverse osmosis membrane.
- a reverse osmosis membrane treatment apparatus 10 having a membrane is provided.
- a treated water pipe 12 is connected to the inlet of the reverse osmosis membrane treatment apparatus 10.
- a permeated water pipe 14 is connected to the permeated water outlet of the reverse osmosis membrane treatment apparatus 10, and a concentrated water pipe 16 is connected to the concentrated water outlet.
- the treated water containing the low molecular organic substance is supplied to the reverse osmosis membrane treatment apparatus 10 through the treated water pipe 12, and the reverse osmosis membrane treatment apparatus 10 reverses the treated water using the modified reverse osmosis membrane.
- Osmotic membrane treatment is performed (reverse osmosis membrane treatment step).
- the permeated water obtained by the reverse osmosis membrane treatment is discharged through the permeated water pipe 14, and the concentrated water is discharged through the concentrated water pipe 16.
- FIG. 2 shows an outline of another example of the low molecular organic substance-containing water treatment system according to the embodiment of the present invention.
- the low molecular organic substance-containing water treatment system 3 in FIG. 2 includes a first reverse osmosis membrane treatment device 20 having a first reverse osmosis membrane and a second reverse osmosis membrane treatment device 22 having a second reverse osmosis membrane.
- At least one of the first reverse osmosis membrane and the second reverse osmosis membrane is modified by bringing a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound into contact with the polyamide-based reverse osmosis membrane. Film.
- the water pipe 24 to be treated is connected to the inlet of the first reverse osmosis membrane treatment apparatus 20.
- the first permeate outlet of the first reverse osmosis membrane treatment device 20 and the inlet of the second reverse osmosis membrane treatment device 22 are connected by a first permeate pipe 26.
- a first concentrated water pipe 28 is connected to the first concentrated water outlet of the first reverse osmosis membrane treatment apparatus 20.
- a second permeate outlet 30 of the second reverse osmosis membrane treatment device 22 is connected to a second permeate outlet, and a second concentrate outlet 32 is connected to the second concentrate outlet.
- the treated water containing the low molecular organic substance is supplied to the first reverse osmosis membrane treatment device 20 through the treated water pipe 24, and the first reverse osmosis membrane treatment device 20 uses the first reverse osmosis membrane to treat the treated water.
- the reverse osmosis membrane treatment is performed (first reverse osmosis membrane treatment step).
- the first concentrated water obtained by the first reverse osmosis membrane treatment is discharged through the first concentrated water pipe 28.
- the first permeate obtained by the first reverse osmosis membrane treatment is supplied to the second reverse osmosis membrane treatment device 22 through the first permeate piping 26, and the second reverse osmosis membrane treatment device 22 uses the second reverse osmosis membrane treatment device 22.
- the second permeated water obtained by the second reverse osmosis membrane treatment is discharged through the second permeated water pipe 30, and the second concentrated water is discharged through the second concentrated water pipe 32.
- the modified hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound is contacted with a polyamide-based reverse osmosis membrane and modified reverse.
- a polyamide-based reverse osmosis membrane By using the osmosis membrane, the water to be treated containing the low-molecular organic substance can be subjected to the reverse osmosis membrane treatment with a high rejection rate.
- this reforming method it is possible to improve the reverse osmosis membrane rejection rate and improve the permeated water quality while suppressing the deterioration of the reverse osmosis membrane.
- the stabilized hypobromite composition hardly degrades the polyamide-based reverse osmosis membrane, the water containing the stabilized hypobromite composition is not used for a long time. Even if water is passed through and contacted with the reverse osmosis membrane, the deterioration of the reverse osmosis membrane is suppressed, and the reduction in the rejection rate of the reverse osmosis membrane, that is, the reduction in water quality is suppressed.
- a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound is brought into contact with a polyamide-based reverse osmosis membrane.
- a modified membrane is used.
- the “stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound” is a stabilized hypobromite composition containing a mixture of a “bromine-based oxidant” and a “sulfamic acid compound”.
- it may be a stabilized hypobromite composition containing a “reaction product of a bromine-based oxidant and a sulfamic acid compound”.
- “reformation” of the reverse osmosis membrane in the present specification refers to improvement of permeated water quality, that is, improvement of the rejection rate.
- the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water includes a bromine-based oxidant as a modifier in the feed water, washing water, and the like to the polyamide-based reverse osmosis membrane.
- the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water includes a bromine-based oxidant as a modifier in water supply to the polyamide-based reverse osmosis membrane, washing water, and the like. It is a membrane modified by a method in which a stabilized hypobromite composition which is a “reaction product of a sulfamic acid compound” is present and brought into contact with a polyamide-based reverse osmosis membrane.
- the reverse osmosis membrane in the low molecular organic substance-containing water treatment method and treatment system includes, for example, “bromine”, “bromine chloride” in the water supply to the polyamide-based reverse osmosis membrane.
- “bromine”, “bromine chloride” in the water supply to the polyamide-based reverse osmosis membrane.
- the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water includes, for example, “reaction product of bromine and a sulfamic acid compound in water supply to a polyamide-based reverse osmosis membrane.
- Product "" reaction product of bromine chloride and sulfamic acid compound ",” reaction product of hypobromous acid and sulfamic acid compound ", or” reaction product of sodium bromide and hypochlorous acid, and sulfamine It is a membrane modified by a method in which a stabilized hypobromite composition, which is a reaction product of an acid compound, is present and brought into contact with a polyamide-based reverse osmosis membrane.
- the modification of the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water according to the present embodiment is performed, for example, when the reverse osmosis membrane device including a polyamide-based reverse osmosis membrane is operated. What is necessary is just to inject
- the “bromine-based oxidant” and the “sulfamic acid compound” may be added separately to the water supply or the like, or may be added to the water supply after mixing the stock solutions.
- a polyamide-based reverse osmosis membrane may be immersed and contacted in water to which “bromine-based oxidizing agent” and “sulfamic acid compound” are added for a predetermined time.
- reaction product of bromine-based oxidant and sulfamic acid compound or “reaction product of bromine-based compound and chlorine-based oxidant and sulfamine” You may inject
- reaction product of bromine-based oxidant and sulfamic acid compound or “reaction product of bromine-based compound and chlorine-based oxidant and sulfamic acid compound” is added.
- the polyamide-based reverse osmosis membrane may be immersed and contacted for a predetermined time.
- the modification with the stabilized hypobromite composition is, for example, the above-mentioned stabilized hypobromite in the water supply to the reverse osmosis membrane during the operation of the reverse osmosis membrane device including the polyamide-based reverse osmosis membrane.
- the composition may be added continuously or intermittently, and when the blocking rate of the reverse osmosis membrane is reduced, the stabilized hypobromite composition is continuously added to the water supply to the reverse osmosis membrane. Or you may add intermittently or immerse a reverse osmosis membrane in the water containing a stabilized hypobromite composition.
- the contact of the stabilized hypobromite composition with the reverse osmosis membrane may be performed under normal pressure, pressurized or reduced pressure conditions, but the modification is performed without stopping the reverse osmosis membrane device. It is preferable to carry out the reaction under pressure from the viewpoint that the reverse osmosis membrane can be reliably modified.
- the contact of the stabilized hypobromite composition with the reverse osmosis membrane is preferably performed under a pressurized condition in the range of 0.1 MPa to 8.0 MPa, for example.
- the contact of the stabilized hypobromite composition with the reverse osmosis membrane may be performed under a temperature condition in the range of 5 ° C to 35 ° C, for example.
- the ratio of the equivalent of the “sulfamic acid compound” to the equivalent of the “bromine-based oxidant” is preferably 1 or more, and more preferably in the range of 1 or more and 2 or less. If the ratio of the equivalent amount of the “sulfamic acid compound” to the equivalent amount of the “bromine-based oxidizing agent” is less than 1, the reverse osmosis membrane may be deteriorated, and if it exceeds 2, the production cost may increase.
- the total chlorine concentration in contact with the reverse osmosis membrane is preferably 0.01 to 100 mg / L in terms of effective chlorine concentration. If it is less than 0.01 mg / L, a sufficient reforming effect may not be obtained. If it exceeds 100 mg / L, reverse osmosis membrane deterioration and piping corrosion may occur.
- the method and system for treating low molecular organic substance-containing water according to the present embodiment Can be applied more suitably.
- the low molecular organic substance refers to an organic substance having a molecular weight of 200 or less, for example, an alcohol compound such as methanol, ethanol or isopropyl alcohol, an amine compound such as monoethanolamine or urea, a tetramethylammonium hydroxide having a molecular weight of 200 or less. And tetraalkylammonium salts such as acetic acid, and carboxylic acids such as acetic acid.
- bromine-based oxidizing agents examples include bromine (liquid bromine), bromine chloride, bromic acid, bromate, and hypobromite.
- Hypobromous acid may be produced by reacting a bromide such as sodium bromide with a chlorine-based oxidizing agent such as hypochlorous acid.
- the preparation of “bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound)” or “reaction product of bromine and sulfamic acid compound” using bromine is composed of “hypochlorous acid and bromine compound and Compared to sulfamic acid preparations and bromine chloride and sulfamic acid preparations, etc., there is less chloride ion, which does not degrade polyamide reverse osmosis membranes more and may cause corrosion of metal materials such as piping. Since it is low, it is more preferable.
- the reverse osmosis membrane in the low molecular organic substance-containing water treatment method and treatment system brings bromine and a sulfamic acid compound into contact with a polyamide-based reverse osmosis membrane (a mixture of bromine and a sulfamic acid compound). It is preferable that the film be modified by a method in which the reaction product of bromine and a sulfamic acid compound is contacted.
- bromine compounds include sodium bromide, potassium bromide, lithium bromide, ammonium bromide and hydrobromic acid. Of these, sodium bromide is preferable from the viewpoint of formulation cost and the like.
- Examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, chlorinated isocyanuric acid or a salt thereof.
- examples of the salt include alkali metal hypochlorites such as sodium hypochlorite and potassium hypochlorite, alkaline earth hypochlorite such as calcium hypochlorite and barium hypochlorite.
- alkali metal chlorites such as sodium chlorite and potassium chlorite
- alkaline earth metal chlorites such as barium chlorite
- other metal chlorites such as nickel chlorite
- Alkali metal chlorates such as ammonium chlorate, sodium chlorate and potassium chlorate
- alkaline earth metal chlorates such as calcium chlorate and barium chlorate.
- chlorine-based oxidants may be used alone or in combination of two or more.
- sodium hypochlorite is preferably used from the viewpoint of handleability.
- the sulfamic acid compound is a compound represented by the following general formula (1).
- R 2 NSO 3 H (1) (In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
- sulfamic acid compound examples include sulfamic acid (amidosulfuric acid) in which both two R groups are hydrogen atoms, N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N- A sulfamic acid compound in which one of two R groups such as isopropylsulfamic acid and N-butylsulfamic acid is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, N, N-dimethylsulfamic acid, N, Two R groups such as N-diethylsulfamic acid, N, N-dipropylsulfamic acid, N, N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid, etc.
- sulfamic acid amidosulfuric
- One of two R groups such as a sulfamic acid compound, N-phenylsulfamic acid and the like, both of which are alkyl groups having 1 to 8 carbon atoms Is a hydrogen atom and the other sulfamic acid compound or a salt thereof, such as an aryl group having 6 to 10 carbon atoms.
- the sulfamate include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, strontium salt and barium salt, manganese salt, copper salt, zinc salt, iron salt, cobalt salt, Other metal salts such as nickel salts, ammonium salts, guanidine salts and the like can be mentioned.
- the sulfamic acid compounds and salts thereof may be used alone or in combination of two or more.
- sulfamic acid compound sulfamic acid (amidosulfuric acid) is preferably used from the viewpoint of environmental load.
- an alkali may be further present.
- the alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. From the viewpoint of product stability at low temperatures, sodium hydroxide and potassium hydroxide may be used in combination. Further, the alkali is not solid and may be used as an aqueous solution.
- the treatment method for low molecular organic substance-containing water and the modification method for the reverse osmosis membrane in the treatment system according to the present embodiment can be applied to polyamide polymer membranes that are currently mainstream as reverse osmosis membranes.
- Polyamide polymer membranes have a relatively low resistance to oxidizing agents, and when free chlorine or the like is continuously brought into contact with the polyamide polymer membrane, the membrane performance is significantly reduced.
- the method for reforming a reverse osmosis membrane using a stabilized hypobromite composition such a remarkable decrease in membrane performance hardly occurs even in a polyamide polymer membrane.
- the contact of the stabilized hypobromite composition with the polyamide-based reverse osmosis membrane is treated water. It is preferable to be carried out at a pH lower than pH.
- the pH of the treated water is higher than the pH during the modification. If the pH during the reforming is lower than the pH of the water to be treated, the reforming effect is maintained and fluctuations in the permeate flow rate of the water to be treated can be suppressed.
- the pH of the treated water is lower than the pH at the time of the modification. If the pH during the reforming is higher than the pH of the water to be treated, the reforming effect and the flow rate of the water to be treated may fluctuate.
- the contact of the stabilized hypobromite composition with the polyamide-based reverse osmosis membrane is performed, for example, in the range of more than pH 3, less than 8, or in the range of pH 4 to 6.5. The lower the pH at the time of contact with the stabilized hypobromite composition, the higher the membrane reforming effect, the higher the rejection, and the permeated water quality.
- a dispersant may be used in combination with the stabilized hypobromite composition for scale suppression.
- the dispersant include polyacrylic acid, polymaleic acid, and phosphonic acid.
- the amount of the dispersant added to the feed water is, for example, in the range of 0.1 to 1,000 mg / L as the concentration in the RO concentrated water.
- Examples of the use of the reverse osmosis membrane device include pure water production, seawater desalination, and wastewater collection.
- the reverse osmosis membrane treatment apparatus 10 (reverse osmosis membrane treatment step) water to be treated may be subjected to at least one of degassing treatment, ion exchange treatment, and UV sterilization treatment. .
- a deaeration treatment device, an ion exchange treatment device, and a UV sterilization treatment device that perform treatment on the treated water of the first reverse osmosis membrane treatment device 20 Of the first reverse osmosis membrane treatment apparatus 20 (first reverse osmosis membrane treatment step), and the water to be treated is at least one of degassing treatment, ion exchange treatment, and UV sterilization treatment. Processing may be performed.
- At least one of the permeated water of the first reverse osmosis membrane treatment device 20 and the permeated water of the second reverse osmosis membrane treatment device 22 is used.
- the apparatus comprises at least one of an ion exchange treatment device, an electrical desalination treatment device, a UV sterilization treatment device, a UV oxidation treatment device, a fine particle removal treatment device, and a third reverse osmosis membrane treatment device, Ion exchange is performed on at least one of the permeated water of the first reverse osmosis membrane treatment device 20 (first reverse osmosis membrane treatment step) and the permeated water of the second reverse osmosis membrane treatment device 22 (second reverse osmosis membrane treatment step). At least one of processing, electrical desalting, UV sterilization, UV oxidation, particulate removal, and third reverse osmosis membrane may be performed.
- the polyamide-based reverse osmosis membrane modifier composition according to the present embodiment contains a stabilized hypobromite composition containing a mixture of a “bromine-based oxidant” and a “sulfamic acid compound”, Furthermore, you may contain an alkali.
- the polyamide reverse osmosis membrane modifier composition according to the present embodiment contains a stabilized hypobromite composition containing a “reaction product of a bromine-based oxidant and a sulfamic acid compound”. Yes, it may further contain an alkali.
- the bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent, and sulfamic acid compound are as described above.
- a compound containing a mixture of bromine, sulfamic acid compound, alkali and water, or a reaction product of bromine and sulfamic acid compound
- Preferred are, for example, a mixture of a reaction product of bromine and a sulfamic acid compound, an alkali and water.
- the polyamide-based reverse osmosis membrane modifier composition according to the present embodiment has an effect of modifying a polyamide-based reverse osmosis membrane as compared with a modifier such as hypochlorous acid or free chlorine containing bromine. However, it hardly causes significant film deterioration such as hypochlorous acid and free chlorine containing bromine. At normal use concentrations, the effect on film degradation can be substantially ignored. Therefore, it is optimal as a modifier for polyamide-based reverse osmosis membranes.
- the polyamide-based reverse osmosis membrane modifier composition according to the present embodiment unlike hypochlorous acid, free chlorine containing bromine and the like, hardly permeates the reverse osmosis membrane, and therefore has an effect on the quality of treated water. rare. Further, since the concentration can be measured on site in the same manner as hypochlorous acid or the like, more accurate concentration management is possible.
- the pH of the modifier composition is, for example, more than 13.0, and more preferably more than 13.2.
- the pH of the modifier composition is 13.0 or less, the effective halogen in the modifier composition may become unstable.
- the bromic acid concentration in the polyamide reverse osmosis membrane modifier composition is preferably less than 5 mg / kg.
- concentration of bromate ions in the RO permeate may increase.
- the modifier composition for a polyamide-based reverse osmosis membrane according to this embodiment is obtained by mixing a bromine-based oxidant and a sulfamic acid compound, and may further be mixed with an alkali.
- bromine is not added to a mixed liquid containing water, an alkali and a sulfamic acid compound. It is preferable to include a step of adding and reacting under an active gas atmosphere or a step of adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound under an inert gas atmosphere.
- a step of adding and reacting under an active gas atmosphere or a step of adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound under an inert gas atmosphere By adding and reacting under an inert gas atmosphere or adding under an inert gas atmosphere, the bromate ion concentration in the modifier composition is lowered, and the bromate ion concentration in the RO permeated water is lowered. Become.
- the inert gas to be used is not limited, at least one of nitrogen and argon is preferable from the viewpoint of manufacturing and the like, and nitrogen is particularly preferable from the viewpoint of manufacturing cost and the like.
- the oxygen concentration in the reactor during the addition of bromine is preferably 6% or less, more preferably 4% or less, further preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reactor during the bromine reaction exceeds 6%, the amount of bromic acid produced in the reaction system may increase.
- the addition ratio of bromine is preferably 25% by weight or less, more preferably 1% by weight or more and 20% by weight or less, based on the total amount of the modifier composition. If the bromine addition rate exceeds 25% by weight based on the total amount of the modifier composition, the amount of bromic acid produced in the reaction system may increase. If it is less than 1% by weight, the reforming effect may be inferior.
- the reaction temperature at the time of bromine addition is preferably controlled in the range of 0 ° C. to 25 ° C., but more preferably in the range of 0 ° C. to 15 ° C. from the viewpoint of production cost.
- the reaction temperature at the time of bromine addition exceeds 25 degreeC, the production amount of the bromic acid in a reaction system may increase, and when it is less than 0 degreeC, it may freeze.
- the pH of the resulting solution was 14 as measured by the glass electrode method.
- the bromine content of the resulting solution was 16.9% as measured by a redox titration method using sodium thiosulfate after bromine was converted to iodine with potassium iodide, and the theoretical content (16.9% ) Of 100.0%.
- the oxygen concentration in the reaction vessel during the bromine reaction was measured using “Oxygen Monitor JKO-02 LJDII” manufactured by Zico Corporation.
- the bromic acid concentration was less than 5 mg / kg.
- Electrode type Glass electrode type pH meter: IOL-30, manufactured by Toa DKK Corporation
- Electrode calibration Neutral phosphate pH (6.86) standard solution (type 2) manufactured by Kanto Chemical Co., boric acid manufactured by the same company Salt temperature (9.18) Standard solution (type 2) was measured by two-point calibration
- Measurement value Immerse the electrode in the measurement solution and use the value after stabilization as the measurement value.
- Example 1 The stabilized hypobromite composition (Example 1), hypochlorous acid (Comparative Example 1), and hypobromite (a mixture of sodium bromide and hypochlorous acid) (Comparative Example 2) prepared above.
- SWC4 + polyamide polymer reverse osmosis membrane
- the reverse osmosis membrane can be prevented from deteriorating and the urea rejection rate of the reverse osmosis membrane is improved. did. It was possible to perform reverse osmosis membrane treatment of low molecular organic substance-containing water containing low molecular organic substances with a high rejection.
- the reverse osmosis membrane apparatus provided with the reverse osmosis membrane was supplied with 10 ppm of the above modifier at an operating pressure of 1.0 MPa for 1 hour at 25 ⁇ 1 ° C. to supply water to the reverse osmosis membrane. The effect of pH was investigated.
Abstract
Provided are a method and system for processing water containing low-molecular-weight organic matter, with which the water containing low-molecular-weight organic matter can be processed with a reverse-osmosis membrane at a high blocking rate. The method for processing water containing low-molecular-weight organic matter includes a reverse-osmosis-membrane processing step for processing water to be processed, which contains low-molecular-weight organic matter having a molecular weight of 200 or less, using a reverse-osmosis membrane, the reverse-osmosis membrane being reformed by bringing a stabilized hypobromous acid composition that contains a bromine-based oxidizer and a sulfamic acid compound into contact with a polyamide-based reverse-osmosis membrane.
Description
本発明は、逆浸透膜を用いる、低分子有機物を含有する低分子有機物含有水の処理方法および処理システムに関する。
The present invention relates to a treatment method and a treatment system for low molecular organic substance-containing water containing a low molecular organic substance using a reverse osmosis membrane.
逆浸透膜（ＲＯ膜）の透過水質改善等のための改質方法は数多く存在する。その中でも、逆浸透膜に臭素を含む遊離塩素を所定の時間接触させて性能を改善する方法がある。
There are many reforming methods for improving the quality of the permeated water of the reverse osmosis membrane (RO membrane). Among them, there is a method for improving performance by bringing a free chlorinated bromine into contact with a reverse osmosis membrane for a predetermined time.
例えば、特許文献１には、ポリアミドスキン層を有する逆浸透膜エレメントを搭載した膜分離装置において、逆浸透膜エレメントを膜分離装置内の圧力容器に充填した後、前記逆浸透膜エレメントに臭素を含む遊離塩素水溶液を接触させる逆浸透膜エレメントの処理方法が記載されている。
For example, in Patent Document 1, in a membrane separation apparatus equipped with a reverse osmosis membrane element having a polyamide skin layer, after filling the reverse osmosis membrane element into a pressure vessel in the membrane separation apparatus, bromine is added to the reverse osmosis membrane element. A method for treating a reverse osmosis membrane element in which a free chlorine aqueous solution is brought into contact is described.
しかし、特許文献１の方法では、一時的な水質改善はできるが、臭素を含む遊離塩素水溶液を長期的に通水すると、逆浸透膜が劣化し、水質が低下する。
However, the method of Patent Document 1 can temporarily improve the water quality, but if a free chlorine aqueous solution containing bromine is passed for a long time, the reverse osmosis membrane deteriorates and the water quality decreases.
特に被処理水が低分子（例えば、分子量２００以下）有機物を含む場合、逆浸透膜は低分子有機物の阻止率が低いため、高い阻止率で逆浸透膜処理することができる処理方法が求められている。
In particular, when the water to be treated contains a low molecular weight organic substance (for example, a molecular weight of 200 or less), since the reverse osmosis membrane has a low rejection rate for low molecular organic substances, a treatment method capable of performing a reverse osmosis membrane treatment with a high rejection rate is required. ing.
本発明の目的は、低分子有機物を含有する被処理水を、高い阻止率で逆浸透膜処理することができる、低分子有機物含有水の処理方法および処理システムを提供することにある。
An object of the present invention is to provide a treatment method and a treatment system for low-molecular-weight organic substance-containing water, which can treat a water to be treated containing a low-molecular-weight organic substance with a reverse osmosis membrane at a high rejection.
本発明は、低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理工程を含み、前記逆浸透膜は、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜である、低分子有機物含有水の処理方法である。
The present invention includes a reverse osmosis membrane treatment step of treating water to be treated containing a low molecular organic substance with a reverse osmosis membrane, and the reverse osmosis membrane comprises a stabilized hypobromine containing a bromine-based oxidant and a sulfamic acid compound. This is a method for treating low molecular organic substance-containing water, which is a membrane modified by bringing an acid composition into contact with a polyamide-based reverse osmosis membrane.
また、本発明は、低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理工程を含み、前記逆浸透膜は、臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜である、低分子有機物含有水の処理方法である。
The present invention also includes a reverse osmosis membrane treatment step of treating water to be treated containing a low molecular organic substance with a reverse osmosis membrane, wherein the reverse osmosis membrane comprises stabilized hypobromite containing bromine and a sulfamic acid compound. This is a method for treating low molecular organic substance-containing water, which is a membrane modified by bringing the composition into contact with a polyamide-based reverse osmosis membrane.
前記低分子有機物含有水の処理方法において、前記安定化次亜臭素酸組成物は、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加する工程を含む方法により得られたものであることが好ましい。
In the method for treating low-molecular-weight organic substance-containing water, the stabilized hypobromite composition is obtained by a method comprising a step of adding bromine to a mixed liquid containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere. It is preferable that
前記低分子有機物含有水の処理方法において、前記接触が、前記被処理水のｐＨより低いｐＨで行われることが好ましい。
In the method for treating low molecular organic substance-containing water, the contact is preferably performed at a pH lower than the pH of the water to be treated.
前記低分子有機物含有水の処理方法において、前記逆浸透膜処理工程の被処理水について、脱気処理、イオン交換処理、ＵＶ殺菌処理のうちの少なくとも１つの処理を行うことが好ましい。
In the method for treating low molecular organic substance-containing water, the water to be treated in the reverse osmosis membrane treatment step is preferably subjected to at least one of deaeration treatment, ion exchange treatment, and UV sterilization treatment.
前記低分子有機物含有水の処理方法において、前記逆浸透膜処理工程が、前記被処理水を第１逆浸透膜で処理する第１逆浸透膜処理工程と、前記第１逆浸透膜処理工程の透過水を第２逆浸透膜で処理する第２逆浸透膜処理工程とを含み、前記第１逆浸透膜および前記第２逆浸透膜のうちの少なくとも１つが、前記安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることが好ましい。
In the method for treating low molecular organic substance-containing water, the reverse osmosis membrane treatment step includes a first reverse osmosis membrane treatment step of treating the water to be treated with a first reverse osmosis membrane, and the first reverse osmosis membrane treatment step. A second reverse osmosis membrane treatment step of treating permeated water with a second reverse osmosis membrane, wherein at least one of the first reverse osmosis membrane and the second reverse osmosis membrane comprises the stabilized hypobromite composition It is preferably a membrane modified by bringing the product into contact with a polyamide-based reverse osmosis membrane.
前記低分子有機物含有水の処理方法において、前記第１逆浸透膜処理工程の透過水および前記第２逆浸透膜処理工程の透過水のうちの少なくとも１つについて、イオン交換処理、電気式脱塩処理、ＵＶ殺菌処理、ＵＶ酸化処理、微粒子除去処理、第３逆浸透膜処理のうちの少なくとも１つの処理を行うことが好ましい。
In the method for treating water containing low molecular weight organic substances, at least one of the permeated water in the first reverse osmosis membrane treatment step and the permeated water in the second reverse osmosis membrane treatment step is subjected to ion exchange treatment, electric desalting. It is preferable to perform at least one of processing, UV sterilization processing, UV oxidation processing, particulate removal processing, and third reverse osmosis membrane processing.
本発明は、低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理装置を備え、前記逆浸透膜は、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜である、低分子有機物含有水の処理システムである。
The present invention comprises a reverse osmosis membrane treatment apparatus for treating water to be treated containing a low molecular organic substance with a reverse osmosis membrane, and the reverse osmosis membrane comprises a stabilized hypobromine containing a bromine-based oxidizing agent and a sulfamic acid compound. This is a low molecular organic substance-containing water treatment system, which is a membrane modified by bringing an acid composition into contact with a polyamide-based reverse osmosis membrane.
また、本発明は、低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理装置を備え、前記逆浸透膜は、臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜である、低分子有機物含有水の処理システムである。
The present invention also includes a reverse osmosis membrane treatment apparatus for treating water to be treated containing a low-molecular organic substance with a reverse osmosis membrane, wherein the reverse osmosis membrane comprises stabilized hypobromite containing bromine and a sulfamic acid compound. This is a treatment system for water containing low molecular weight organic matter, which is a membrane modified by bringing the composition into contact with a polyamide-based reverse osmosis membrane.
前記低分子有機物含有水の処理システムにおいて、前記安定化次亜臭素酸組成物は、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加する工程を含む方法により得られたものであることが好ましい。
In the low-molecular-weight organic substance-containing water treatment system, the stabilized hypobromite composition is obtained by a method including a step of adding bromine to a mixed liquid containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere. It is preferable that
前記低分子有機物含有水の処理システムにおいて、前記接触が、前記被処理水のｐＨより低いｐＨで行われることが好ましい。
In the low molecular organic substance-containing water treatment system, the contact is preferably performed at a pH lower than the pH of the water to be treated.
前記低分子有機物含有水の処理システムにおいて、前記逆浸透膜処理装置の被処理水について処理を行う、脱気処理装置、イオン交換処理装置、ＵＶ殺菌処理装置のうちの少なくとも１つの装置を備えることが好ましい。
The low molecular organic substance-containing water treatment system includes at least one of a degassing treatment device, an ion exchange treatment device, and a UV sterilization treatment device that performs treatment on the water to be treated of the reverse osmosis membrane treatment device. Is preferred.
前記低分子有機物含有水の処理システムにおいて、前記逆浸透膜処理装置が、前記被処理水を第１逆浸透膜で処理する第１逆浸透膜処理装置と、前記第１逆浸透膜処理装置の透過水を第２逆浸透膜で処理する第２逆浸透膜処理装置とを含み、前記第１逆浸透膜および前記第２逆浸透膜のうちの少なくとも１つが、前記安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることが好ましい。
In the low molecular organic substance-containing water treatment system, the reverse osmosis membrane treatment device includes: a first reverse osmosis membrane treatment device for treating the treated water with a first reverse osmosis membrane; and the first reverse osmosis membrane treatment device. A second reverse osmosis membrane treatment device for treating permeated water with a second reverse osmosis membrane, wherein at least one of the first reverse osmosis membrane and the second reverse osmosis membrane comprises the stabilized hypobromite composition It is preferably a membrane modified by bringing the product into contact with a polyamide-based reverse osmosis membrane.
前記低分子有機物含有水の処理システムにおいて、前記第１逆浸透膜処理装置の透過水および前記第２逆浸透膜処理装置の透過水のうちの少なくとも１つについて処理を行う、イオン交換処理装置、電気式脱塩処理装置、ＵＶ殺菌処理装置、ＵＶ酸化処理装置、微粒子除去処理装置、第３逆浸透膜処理装置のうちの少なくとも１つの装置を備えるが好ましい。
In the treatment system for low molecular organic substance-containing water, an ion exchange treatment device for treating at least one of the permeated water of the first reverse osmosis membrane treatment device and the permeated water of the second reverse osmosis membrane treatment device, It is preferable to include at least one of an electric desalination treatment apparatus, a UV sterilization treatment apparatus, a UV oxidation treatment apparatus, a fine particle removal treatment apparatus, and a third reverse osmosis membrane treatment apparatus.
本発明では、低分子有機物を含有する被処理水を、高い阻止率で逆浸透膜処理することができる。
In the present invention, the water to be treated containing a low-molecular organic substance can be treated with a reverse osmosis membrane with a high rejection.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。
Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.
本発明の実施形態に係る低分子有機物含有水の処理システムの一例の概略を図１に示し、その構成について説明する。図１の低分子有機物含有水の処理システム１は、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された逆浸透膜を有する逆浸透膜処理装置１０を備える。
FIG. 1 shows an outline of an example of a treatment system for water containing low molecular weight organic matter according to an embodiment of the present invention, and the configuration thereof will be described. 1 is a reverse osmosis modified by bringing a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound into contact with a polyamide-based reverse osmosis membrane. A reverse osmosis membrane treatment apparatus 10 having a membrane is provided.
図１の処理システム１において、被処理水配管１２が逆浸透膜処理装置１０の入口に接続されている。逆浸透膜処理装置１０の透過水出口には透過水配管１４が接続され、濃縮水出口には濃縮水配管１６が接続されている。
In the treatment system 1 of FIG. 1, a treated water pipe 12 is connected to the inlet of the reverse osmosis membrane treatment apparatus 10. A permeated water pipe 14 is connected to the permeated water outlet of the reverse osmosis membrane treatment apparatus 10, and a concentrated water pipe 16 is connected to the concentrated water outlet.
本実施形態に係る低分子有機物含有水の処理方法および低分子有機物含有水の処理システム１の動作について説明する。
The operation of the low molecular organic substance-containing water treatment method and the low molecular organic substance-containing water treatment system 1 according to the present embodiment will be described.
低分子有機物を含有する被処理水は、被処理水配管１２を通して逆浸透膜処理装置１０に供給され、逆浸透膜処理装置１０において、改質された逆浸透膜を用いて被処理水の逆浸透膜処理が行われる（逆浸透膜処理工程）。逆浸透膜処理で得られた透過水は、透過水配管１４を通して排出され、濃縮水は、濃縮水配管１６を通して排出される。
The treated water containing the low molecular organic substance is supplied to the reverse osmosis membrane treatment apparatus 10 through the treated water pipe 12, and the reverse osmosis membrane treatment apparatus 10 reverses the treated water using the modified reverse osmosis membrane. Osmotic membrane treatment is performed (reverse osmosis membrane treatment step). The permeated water obtained by the reverse osmosis membrane treatment is discharged through the permeated water pipe 14, and the concentrated water is discharged through the concentrated water pipe 16.
本発明の実施形態に係る低分子有機物含有水の処理システムの他の例の概略を図２に示す。図２の低分子有機物含有水の処理システム３は、第１逆浸透膜を有する第１逆浸透膜処理装置２０と、第２逆浸透膜を有する第２逆浸透膜処理装置２２とを備える。第１逆浸透膜および第２逆浸透膜のうちの少なくとも１つが、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜である。
FIG. 2 shows an outline of another example of the low molecular organic substance-containing water treatment system according to the embodiment of the present invention. The low molecular organic substance-containing water treatment system 3 in FIG. 2 includes a first reverse osmosis membrane treatment device 20 having a first reverse osmosis membrane and a second reverse osmosis membrane treatment device 22 having a second reverse osmosis membrane. At least one of the first reverse osmosis membrane and the second reverse osmosis membrane is modified by bringing a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound into contact with the polyamide-based reverse osmosis membrane. Film.
図２の処理システム３において、被処理水配管２４が第１逆浸透膜処理装置２０の入口に接続されている。第１逆浸透膜処理装置２０の第１透過水出口と、第２逆浸透膜処理装置２２の入口とは、第１透過水配管２６により接続されている。第１逆浸透膜処理装置２０の第１濃縮水出口には第１濃縮水配管２８が接続されている。第２逆浸透膜処理装置２２の第２透過水出口には第２透過水配管３０が接続され、第２濃縮水出口には第２濃縮水配管３２が接続されている。
In the treatment system 3 of FIG. 2, the water pipe 24 to be treated is connected to the inlet of the first reverse osmosis membrane treatment apparatus 20. The first permeate outlet of the first reverse osmosis membrane treatment device 20 and the inlet of the second reverse osmosis membrane treatment device 22 are connected by a first permeate pipe 26. A first concentrated water pipe 28 is connected to the first concentrated water outlet of the first reverse osmosis membrane treatment apparatus 20. A second permeate outlet 30 of the second reverse osmosis membrane treatment device 22 is connected to a second permeate outlet, and a second concentrate outlet 32 is connected to the second concentrate outlet.
低分子有機物を含有する被処理水は、被処理水配管２４を通して第１逆浸透膜処理装置２０に供給され、第１逆浸透膜処理装置２０において、第１逆浸透膜を用いて被処理水の逆浸透膜処理が行われる（第１逆浸透膜処理工程）。第１逆浸透膜処理で得られた第１濃縮水は、第１濃縮水配管２８を通して排出される。第１逆浸透膜処理で得られた第１透過水は、第１透過水配管２６を通して第２逆浸透膜処理装置２２に供給され、第２逆浸透膜処理装置２２において、第２逆浸透膜を用いて第１透過水の逆浸透膜処理が行われる（第２逆浸透膜処理工程）。第２逆浸透膜処理で得られた第２透過水は、第２透過水配管３０を通して排出され、第２濃縮水は、第２濃縮水配管３２を通して排出される。
The treated water containing the low molecular organic substance is supplied to the first reverse osmosis membrane treatment device 20 through the treated water pipe 24, and the first reverse osmosis membrane treatment device 20 uses the first reverse osmosis membrane to treat the treated water. The reverse osmosis membrane treatment is performed (first reverse osmosis membrane treatment step). The first concentrated water obtained by the first reverse osmosis membrane treatment is discharged through the first concentrated water pipe 28. The first permeate obtained by the first reverse osmosis membrane treatment is supplied to the second reverse osmosis membrane treatment device 22 through the first permeate piping 26, and the second reverse osmosis membrane treatment device 22 uses the second reverse osmosis membrane treatment device 22. Is used to perform the reverse osmosis membrane treatment of the first permeated water (second reverse osmosis membrane treatment step). The second permeated water obtained by the second reverse osmosis membrane treatment is discharged through the second permeated water pipe 30, and the second concentrated water is discharged through the second concentrated water pipe 32.
図１の処理システム１および図２の処理システム３において、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された逆浸透膜を用いることによって、低分子有機物を含有する被処理水を、高い阻止率で逆浸透膜処理することができる。この改質方法により、逆浸透膜の劣化を抑制しつつ、逆浸透膜の阻止率を向上させ、透過水質を改善することができる。安定化次亜臭素酸組成物がポリアミド系の逆浸透膜を劣化させることがほとんどないため、一時的な水質改善ではなく、安定化次亜臭素酸組成物を含む水を長期的にポリアミド系の逆浸透膜に通水して接触しても、逆浸透膜の劣化が抑制され、逆浸透膜の阻止率の低下、すなわち水質の低下が抑制される。
In the treatment system 1 of FIG. 1 and the treatment system 3 of FIG. 2, the modified hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound is contacted with a polyamide-based reverse osmosis membrane and modified reverse. By using the osmosis membrane, the water to be treated containing the low-molecular organic substance can be subjected to the reverse osmosis membrane treatment with a high rejection rate. By this reforming method, it is possible to improve the reverse osmosis membrane rejection rate and improve the permeated water quality while suppressing the deterioration of the reverse osmosis membrane. Since the stabilized hypobromite composition hardly degrades the polyamide-based reverse osmosis membrane, the water containing the stabilized hypobromite composition is not used for a long time. Even if water is passed through and contacted with the reverse osmosis membrane, the deterioration of the reverse osmosis membrane is suppressed, and the reduction in the rejection rate of the reverse osmosis membrane, that is, the reduction in water quality is suppressed.
上記の通り、本実施形態に係る低分子有機物含有水の処理方法および処理システムにおいて、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜を用いる。「臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物」は、「臭素系酸化剤」と「スルファミン酸化合物」との混合物を含む安定化次亜臭素酸組成物であってもよいし、「臭素系酸化剤とスルファミン酸化合物との反応生成物」を含む安定化次亜臭素酸組成物であってもよい。ここで、本明細書における逆浸透膜の「改質」とは、透過水質の改善、すなわち阻止率の向上を指す。
As described above, in the method and system for treating low molecular organic substance-containing water according to the present embodiment, a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound is brought into contact with a polyamide-based reverse osmosis membrane. A modified membrane is used. The “stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound” is a stabilized hypobromite composition containing a mixture of a “bromine-based oxidant” and a “sulfamic acid compound”. Alternatively, it may be a stabilized hypobromite composition containing a “reaction product of a bromine-based oxidant and a sulfamic acid compound”. Here, “reformation” of the reverse osmosis membrane in the present specification refers to improvement of permeated water quality, that is, improvement of the rejection rate.
すなわち、本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜は、ポリアミド系の逆浸透膜への給水、洗浄水等の中に、改質剤として「臭素系酸化剤」と「スルファミン酸化合物」との混合物を存在させてポリアミド系の逆浸透膜に接触させる方法によって改質された膜である。これにより、給水等の中で、安定化次亜臭素酸組成物が生成すると考えられる。
That is, the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water according to the present embodiment includes a bromine-based oxidant as a modifier in the feed water, washing water, and the like to the polyamide-based reverse osmosis membrane. ”And a“ sulfamic acid compound ”in the presence of a mixture and contacted with a polyamide-based reverse osmosis membrane. Thereby, it is thought that the stabilized hypobromite composition produces | generates in water supply etc.
また、本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜は、ポリアミド系の逆浸透膜への給水、洗浄水等の中に、改質剤として「臭素系酸化剤とスルファミン酸化合物との反応生成物」である安定化次亜臭素酸組成物を存在させてポリアミド系の逆浸透膜に接触させる方法によって改質された膜である。
Further, the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water according to the present embodiment includes a bromine-based oxidant as a modifier in water supply to the polyamide-based reverse osmosis membrane, washing water, and the like. It is a membrane modified by a method in which a stabilized hypobromite composition which is a “reaction product of a sulfamic acid compound” is present and brought into contact with a polyamide-based reverse osmosis membrane.
具体的には本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜は、ポリアミド系の逆浸透膜への給水等の中に、例えば、「臭素」、「塩化臭素」、「次亜臭素酸」または「臭化ナトリウムと次亜塩素酸との反応物」と、「スルファミン酸化合物」との混合物を存在させてポリアミド系の逆浸透膜に接触させる方法によって改質された膜である。
Specifically, the reverse osmosis membrane in the low molecular organic substance-containing water treatment method and treatment system according to the present embodiment includes, for example, “bromine”, “bromine chloride” in the water supply to the polyamide-based reverse osmosis membrane. Modified by a method in which a mixture of “hypobromite” or “reaction product of sodium bromide and hypochlorous acid” and “sulfamic acid compound” is present and brought into contact with a polyamide-based reverse osmosis membrane. Film.
また、本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜は、ポリアミド系の逆浸透膜への給水等の中に、例えば、「臭素とスルファミン酸化合物との反応生成物」、「塩化臭素とスルファミン酸化合物との反応生成物」、「次亜臭素酸とスルファミン酸化合物との反応生成物」、または「臭化ナトリウムと次亜塩素酸との反応物と、スルファミン酸化合物と、の反応生成物」である安定化次亜臭素酸組成物を存在させてポリアミド系の逆浸透膜に接触させる方法によって改質された膜である。
In addition, the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water according to the present embodiment includes, for example, “reaction product of bromine and a sulfamic acid compound in water supply to a polyamide-based reverse osmosis membrane. Product "," reaction product of bromine chloride and sulfamic acid compound "," reaction product of hypobromous acid and sulfamic acid compound ", or" reaction product of sodium bromide and hypochlorous acid, and sulfamine It is a membrane modified by a method in which a stabilized hypobromite composition, which is a reaction product of an acid compound, is present and brought into contact with a polyamide-based reverse osmosis membrane.
本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜の改質は、例えば、ポリアミド系の逆浸透膜を備える逆浸透膜装置の運転の際に、逆浸透膜への給水等の中に、「臭素系酸化剤」と「スルファミン酸化合物」とを薬注ポンプ等により注入すればよい。「臭素系酸化剤」と「スルファミン酸化合物」とは別々に給水等の中に添加してもよく、または、原液同士で混合させてから給水等の中に添加してもよい。また、例えば、「臭素系酸化剤」と「スルファミン酸化合物」とを添加した水中に、ポリアミド系の逆浸透膜を所定の時間、浸漬して接触させてもよい。
The modification of the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water according to the present embodiment is performed, for example, when the reverse osmosis membrane device including a polyamide-based reverse osmosis membrane is operated. What is necessary is just to inject | pour "bromine-type oxidizing agent" and "sulfamic acid compound" into a water supply etc. with a chemical injection pump. The “bromine-based oxidant” and the “sulfamic acid compound” may be added separately to the water supply or the like, or may be added to the water supply after mixing the stock solutions. Further, for example, a polyamide-based reverse osmosis membrane may be immersed and contacted in water to which “bromine-based oxidizing agent” and “sulfamic acid compound” are added for a predetermined time.
また、例えば、ポリアミド系の逆浸透膜への給水等の中に、「臭素系酸化剤とスルファミン酸化合物との反応生成物」、または「臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物」を薬注ポンプ等により注入してもよい。また、例えば、「臭素系酸化剤とスルファミン酸化合物との反応生成物」、または「臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物」を添加した水中に、ポリアミド系の逆浸透膜を所定の時間、浸漬して接触させてもよい。
In addition, for example, in the water supply to a polyamide-based reverse osmosis membrane, “reaction product of bromine-based oxidant and sulfamic acid compound” or “reaction product of bromine-based compound and chlorine-based oxidant and sulfamine” You may inject | pour a reaction product of an acid compound "with a chemical injection pump. In addition, for example, in a water to which “reaction product of bromine-based oxidant and sulfamic acid compound” or “reaction product of bromine-based compound and chlorine-based oxidant and sulfamic acid compound” is added. Alternatively, the polyamide-based reverse osmosis membrane may be immersed and contacted for a predetermined time.
安定化次亜臭素酸組成物による改質は、例えば、ポリアミド系の逆浸透膜を備える逆浸透膜装置の運転の際に逆浸透膜への給水等の中に、上記安定化次亜臭素酸組成物を連続的または間欠的に添加してもよいし、逆浸透膜の阻止率が低下した場合に、逆浸透膜への給水等の中に上記安定化次亜臭素酸組成物を連続的または間欠的に添加したり、安定化次亜臭素酸組成物を含む水中に逆浸透膜を浸漬してもよい。
The modification with the stabilized hypobromite composition is, for example, the above-mentioned stabilized hypobromite in the water supply to the reverse osmosis membrane during the operation of the reverse osmosis membrane device including the polyamide-based reverse osmosis membrane. The composition may be added continuously or intermittently, and when the blocking rate of the reverse osmosis membrane is reduced, the stabilized hypobromite composition is continuously added to the water supply to the reverse osmosis membrane. Or you may add intermittently or immerse a reverse osmosis membrane in the water containing a stabilized hypobromite composition.
逆浸透膜への安定化次亜臭素酸組成物の接触は、常圧条件下、加圧条件下または減圧条件下で行えばよいが、逆浸透膜装置を停止しなくても改質を行うことができる、逆浸透膜の改質を確実に行うことができる等の点から、加圧条件下で行うことが好ましい。逆浸透膜への安定化次亜臭素酸組成物の接触は、例えば、０．１ＭＰａ～８．０ＭＰａの範囲の加圧条件下で行うことが好ましい。
The contact of the stabilized hypobromite composition with the reverse osmosis membrane may be performed under normal pressure, pressurized or reduced pressure conditions, but the modification is performed without stopping the reverse osmosis membrane device. It is preferable to carry out the reaction under pressure from the viewpoint that the reverse osmosis membrane can be reliably modified. The contact of the stabilized hypobromite composition with the reverse osmosis membrane is preferably performed under a pressurized condition in the range of 0.1 MPa to 8.0 MPa, for example.
逆浸透膜への安定化次亜臭素酸組成物の接触は、例えば、５℃～３５℃の範囲の温度条件下で行えばよい。
The contact of the stabilized hypobromite composition with the reverse osmosis membrane may be performed under a temperature condition in the range of 5 ° C to 35 ° C, for example.
「臭素系酸化剤」の当量に対する「スルファミン酸化合物」の当量の比は、１以上であることが好ましく、１以上２以下の範囲であることがより好ましい。「臭素系酸化剤」の当量に対する「スルファミン酸化合物」の当量の比が１未満であると、逆浸透膜を劣化させる可能性があり、２を超えると、製造コストが増加する場合がある。
The ratio of the equivalent of the “sulfamic acid compound” to the equivalent of the “bromine-based oxidant” is preferably 1 or more, and more preferably in the range of 1 or more and 2 or less. If the ratio of the equivalent amount of the “sulfamic acid compound” to the equivalent amount of the “bromine-based oxidizing agent” is less than 1, the reverse osmosis membrane may be deteriorated, and if it exceeds 2, the production cost may increase.
逆浸透膜に接触する全塩素濃度は有効塩素濃度換算で、０．０１～１００ｍｇ／Ｌであることが好ましい。０．０１ｍｇ／Ｌ未満であると、十分な改質効果を得ることができない場合があり、１００ｍｇ／Ｌより多いと、逆浸透膜の劣化、配管等の腐食を引き起こす可能性がある。
The total chlorine concentration in contact with the reverse osmosis membrane is preferably 0.01 to 100 mg / L in terms of effective chlorine concentration. If it is less than 0.01 mg / L, a sufficient reforming effect may not be obtained. If it exceeds 100 mg / L, reverse osmosis membrane deterioration and piping corrosion may occur.
被処理水が、低分子の有機物を０．０１ｍｇ／Ｌ以上含む場合、特に０．１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下含む場合に、本実施形態に係る低分子有機物含有水の処理方法および処理システムをより好適に適用することができる。
When the water to be treated contains 0.01 mg / L or more of a low molecular organic substance, particularly when containing 0.1 mg / L or more and 100 mg / L or less, the method and system for treating low molecular organic substance-containing water according to the present embodiment Can be applied more suitably.
低分子の有機物とは、分子量が２００以下の有機物を指し、例えば、分子量が２００以下の、メタノール、エタノール、イソプロピルアルコール等のアルコール化合物、モノエタノールアミン、尿素等のアミン化合物、水酸化テトラメチルアンモニム等のテトラアルキルアンモニウム塩、酢酸等のカルボン酸等が挙げられる。
The low molecular organic substance refers to an organic substance having a molecular weight of 200 or less, for example, an alcohol compound such as methanol, ethanol or isopropyl alcohol, an amine compound such as monoethanolamine or urea, a tetramethylammonium hydroxide having a molecular weight of 200 or less. And tetraalkylammonium salts such as acetic acid, and carboxylic acids such as acetic acid.
臭素系酸化剤としては、臭素（液体臭素）、塩化臭素、臭素酸、臭素酸塩、次亜臭素酸等が挙げられる。次亜臭素酸は、臭化ナトリウム等の臭化物と次亜塩素酸等の塩素系酸化剤とを反応させて生成させたものであってもよい。
Examples of bromine-based oxidizing agents include bromine (liquid bromine), bromine chloride, bromic acid, bromate, and hypobromite. Hypobromous acid may be produced by reacting a bromide such as sodium bromide with a chlorine-based oxidizing agent such as hypochlorous acid.
これらのうち、臭素を用いた「臭素とスルファミン酸化合物（臭素とスルファミン酸化合物の混合物）」または「臭素とスルファミン酸化合物との反応生成物」の製剤は、「次亜塩素酸と臭素化合物とスルファミン酸」の製剤および「塩化臭素とスルファミン酸」の製剤等に比べて、塩化物イオンが少なく、ポリアミド系の逆浸透膜をより劣化させず、配管等の金属材料の腐食を引き起こす可能性が低いため、より好ましい。
Among these, the preparation of “bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound)” or “reaction product of bromine and sulfamic acid compound” using bromine is composed of “hypochlorous acid and bromine compound and Compared to sulfamic acid preparations and bromine chloride and sulfamic acid preparations, etc., there is less chloride ion, which does not degrade polyamide reverse osmosis membranes more and may cause corrosion of metal materials such as piping. Since it is low, it is more preferable.
すなわち、本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜は、ポリアミド系の逆浸透膜に、臭素とスルファミン酸化合物とを接触させる（臭素とスルファミン酸化合物の混合物を接触させる）、または、臭素とスルファミン酸化合物との反応生成物を接触させる方法によって改質された膜であることが好ましい。
That is, the reverse osmosis membrane in the low molecular organic substance-containing water treatment method and treatment system according to the present embodiment brings bromine and a sulfamic acid compound into contact with a polyamide-based reverse osmosis membrane (a mixture of bromine and a sulfamic acid compound). It is preferable that the film be modified by a method in which the reaction product of bromine and a sulfamic acid compound is contacted.
臭素化合物としては、臭化ナトリウム、臭化カリウム、臭化リチウム、臭化アンモニウムおよび臭化水素酸等が挙げられる。これらのうち、製剤コスト等の点から、臭化ナトリウムが好ましい。
Examples of bromine compounds include sodium bromide, potassium bromide, lithium bromide, ammonium bromide and hydrobromic acid. Of these, sodium bromide is preferable from the viewpoint of formulation cost and the like.
塩素系酸化剤としては、例えば、塩素ガス、二酸化塩素、次亜塩素酸またはその塩、亜塩素酸またはその塩、塩素酸またはその塩、過塩素酸またはその塩、塩素化イソシアヌル酸またはその塩等が挙げられる。これらのうち、塩としては、例えば、次亜塩素酸ナトリウム、次亜塩素酸カリウム等の次亜塩素酸アルカリ金属塩、次亜塩素酸カルシウム、次亜塩素酸バリウム等の次亜塩素酸アルカリ土類金属塩、亜塩素酸ナトリウム、亜塩素酸カリウム等の亜塩素酸アルカリ金属塩、亜塩素酸バリウム等の亜塩素酸アルカリ土類金属塩、亜塩素酸ニッケル等の他の亜塩素酸金属塩、塩素酸アンモニウム、塩素酸ナトリウム、塩素酸カリウム等の塩素酸アルカリ金属塩、塩素酸カルシウム、塩素酸バリウム等の塩素酸アルカリ土類金属塩等が挙げられる。これらの塩素系酸化剤は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。塩素系酸化剤としては、取り扱い性等の点から、次亜塩素酸ナトリウムを用いるのが好ましい。
Examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, chlorinated isocyanuric acid or a salt thereof. Etc. Among these, examples of the salt include alkali metal hypochlorites such as sodium hypochlorite and potassium hypochlorite, alkaline earth hypochlorite such as calcium hypochlorite and barium hypochlorite. Metal salts, alkali metal chlorites such as sodium chlorite and potassium chlorite, alkaline earth metal chlorites such as barium chlorite, and other metal chlorites such as nickel chlorite , Alkali metal chlorates such as ammonium chlorate, sodium chlorate and potassium chlorate, and alkaline earth metal chlorates such as calcium chlorate and barium chlorate. These chlorine-based oxidants may be used alone or in combination of two or more. As the chlorine-based oxidant, sodium hypochlorite is preferably used from the viewpoint of handleability.
スルファミン酸化合物は、以下の一般式（１）で示される化合物である。
Ｒ２ＮＳＯ３Ｈ （１）
（式中、Ｒは独立して水素原子または炭素数１～８のアルキル基である。） The sulfamic acid compound is a compound represented by the following general formula (1).
R 2 NSO 3 H (1)
(In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
Ｒ２ＮＳＯ３Ｈ （１）
（式中、Ｒは独立して水素原子または炭素数１～８のアルキル基である。） The sulfamic acid compound is a compound represented by the following general formula (1).
R 2 NSO 3 H (1)
(In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
スルファミン酸化合物としては、例えば、２個のＲ基の両方が水素原子であるスルファミン酸（アミド硫酸）の他に、Ｎ－メチルスルファミン酸、Ｎ－エチルスルファミン酸、Ｎ－プロピルスルファミン酸、Ｎ－イソプロピルスルファミン酸、Ｎ－ブチルスルファミン酸等の２個のＲ基の一方が水素原子であり、他方が炭素数１～８のアルキル基であるスルファミン酸化合物、Ｎ，Ｎ－ジメチルスルファミン酸、Ｎ，Ｎ－ジエチルスルファミン酸、Ｎ，Ｎ－ジプロピルスルファミン酸、Ｎ，Ｎ－ジブチルスルファミン酸、Ｎ－メチル－Ｎ－エチルスルファミン酸、Ｎ－メチル－Ｎ－プロピルスルファミン酸等の２個のＲ基の両方が炭素数１～８のアルキル基であるスルファミン酸化合物、Ｎ－フェニルスルファミン酸等の２個のＲ基の一方が水素原子であり、他方が炭素数６～１０のアリール基であるスルファミン酸化合物、またはこれらの塩等が挙げられる。スルファミン酸塩としては、例えば、ナトリウム塩、カリウム塩等のアルカリ金属塩、カルシウム塩、ストロンチウム塩、バリウム塩等のアルカリ土類金属塩、マンガン塩、銅塩、亜鉛塩、鉄塩、コバルト塩、ニッケル塩等の他の金属塩、アンモニウム塩およびグアニジン塩等が挙げられる。スルファミン酸化合物およびこれらの塩は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。スルファミン酸化合物としては、環境負荷等の点から、スルファミン酸（アミド硫酸）を用いるのが好ましい。
Examples of the sulfamic acid compound include sulfamic acid (amidosulfuric acid) in which both two R groups are hydrogen atoms, N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N- A sulfamic acid compound in which one of two R groups such as isopropylsulfamic acid and N-butylsulfamic acid is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, N, N-dimethylsulfamic acid, N, Two R groups such as N-diethylsulfamic acid, N, N-dipropylsulfamic acid, N, N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid, etc. One of two R groups such as a sulfamic acid compound, N-phenylsulfamic acid and the like, both of which are alkyl groups having 1 to 8 carbon atoms Is a hydrogen atom and the other sulfamic acid compound or a salt thereof, such as an aryl group having 6 to 10 carbon atoms. Examples of the sulfamate include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, strontium salt and barium salt, manganese salt, copper salt, zinc salt, iron salt, cobalt salt, Other metal salts such as nickel salts, ammonium salts, guanidine salts and the like can be mentioned. The sulfamic acid compounds and salts thereof may be used alone or in combination of two or more. As the sulfamic acid compound, sulfamic acid (amidosulfuric acid) is preferably used from the viewpoint of environmental load.
本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜の改質において、さらにアルカリを存在させてもよい。アルカリとしては、水酸化ナトリウム、水酸化カリウム等の水酸化アルカリ等が挙げられる。低温時の製品安定性等の点から、水酸化ナトリウムと水酸化カリウムとを併用してもよい。また、アルカリは、固形でなく、水溶液として用いてもよい。
In the modification of the reverse osmosis membrane in the method and system for treating low molecular organic substance-containing water according to this embodiment, an alkali may be further present. Examples of the alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. From the viewpoint of product stability at low temperatures, sodium hydroxide and potassium hydroxide may be used in combination. Further, the alkali is not solid and may be used as an aqueous solution.
本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜の改質方法は、逆浸透膜として昨今主流であるポリアミド系高分子膜に適用することができる。ポリアミド系高分子膜は、酸化剤に対する耐性が比較的低く、遊離塩素等をポリアミド系高分子膜に連続的に接触させると、膜性能の著しい低下が起こる。しかしながら、安定化次亜臭素酸組成物を用いる逆浸透膜の改質方法ではポリアミド高分子膜においても、このような著しい膜性能の低下はほとんど起こらない。
The treatment method for low molecular organic substance-containing water and the modification method for the reverse osmosis membrane in the treatment system according to the present embodiment can be applied to polyamide polymer membranes that are currently mainstream as reverse osmosis membranes. Polyamide polymer membranes have a relatively low resistance to oxidizing agents, and when free chlorine or the like is continuously brought into contact with the polyamide polymer membrane, the membrane performance is significantly reduced. However, in the method for reforming a reverse osmosis membrane using a stabilized hypobromite composition, such a remarkable decrease in membrane performance hardly occurs even in a polyamide polymer membrane.
本実施形態に係る低分子有機物含有水の処理方法および処理システムにおける逆浸透膜の改質方法において、ポリアミド系の逆浸透膜への安定化次亜臭素酸組成物の接触が、被処理水のｐＨより低いｐＨで行われることが好ましい。逆浸透膜の改質後、被処理水の通水のときに安定化次亜臭素酸組成物をスライム抑制剤として連続添加した場合、被処理水のｐＨが改質のときのｐＨよりも高い（すなわち、改質のときのｐＨが被処理水のｐＨよりも低い）と、改質効果が維持され、被処理水の透過流量の変動を抑制することができる。逆浸透膜の改質後、被処理水の通水のときに安定化次亜臭素酸組成物をスライム抑制剤として連続添加した場合、被処理水のｐＨが改質のときのｐＨよりも低い（すなわち、改質のときのｐＨが被処理水のｐＨよりも高い）と、改質効果と被処理水の透過流量の変動が起こる場合がある。ポリアミド系の逆浸透膜への安定化次亜臭素酸組成物の接触は、例えば、ｐＨ３超、８未満の範囲で行われ、またはｐＨ４～６．５の範囲で行われる。安定化次亜臭素酸組成物の接触のときのｐＨが低いほど、膜の改質効果が高くなり、阻止率が向上し、透過水質を改善することができる。
In the method for treating a low molecular organic substance-containing water according to the present embodiment and the method for modifying a reverse osmosis membrane in a treatment system, the contact of the stabilized hypobromite composition with the polyamide-based reverse osmosis membrane is treated water. It is preferable to be carried out at a pH lower than pH. After the reverse osmosis membrane modification, when the stabilized hypobromite composition is continuously added as a slime inhibitor when the treated water is passed, the pH of the treated water is higher than the pH during the modification. If the pH during the reforming is lower than the pH of the water to be treated, the reforming effect is maintained and fluctuations in the permeate flow rate of the water to be treated can be suppressed. After the reverse osmosis membrane modification, when the stabilized hypobromite composition is continuously added as a slime inhibitor when the treated water is passed, the pH of the treated water is lower than the pH at the time of the modification. If the pH during the reforming is higher than the pH of the water to be treated, the reforming effect and the flow rate of the water to be treated may fluctuate. The contact of the stabilized hypobromite composition with the polyamide-based reverse osmosis membrane is performed, for example, in the range of more than pH 3, less than 8, or in the range of pH 4 to 6.5. The lower the pH at the time of contact with the stabilized hypobromite composition, the higher the membrane reforming effect, the higher the rejection, and the permeated water quality.
逆浸透膜装置において、逆浸透膜への給水のｐＨ５．５以上でスケールが発生する場合には、スケール抑制のために分散剤を安定化次亜臭素酸組成物と併用してもよい。分散剤としては、例えば、ポリアクリル酸、ポリマレイン酸、ホスホン酸等が挙げられる。分散剤の給水への添加量は、例えば、ＲＯ濃縮水中の濃度として０．１～１，０００ｍｇ／Ｌの範囲である。
In the reverse osmosis membrane device, when scale is generated at pH 5.5 or higher of the water supplied to the reverse osmosis membrane, a dispersant may be used in combination with the stabilized hypobromite composition for scale suppression. Examples of the dispersant include polyacrylic acid, polymaleic acid, and phosphonic acid. The amount of the dispersant added to the feed water is, for example, in the range of 0.1 to 1,000 mg / L as the concentration in the RO concentrated water.
また、分散剤を使用せずにスケールの発生を抑制するためには、例えば、ＲＯ濃縮水中のシリカ濃度を溶解度以下に、カルシウムスケールの指標であるランゲリア指数を０以下になるように、逆浸透膜装置の回収率等の運転条件を調整することが挙げられる。
In addition, in order to suppress the occurrence of scale without using a dispersant, for example, reverse osmosis is performed so that the silica concentration in RO concentrated water is less than the solubility and the Langeria index, which is a calcium scale index, is less than 0. Adjusting the operating conditions such as the recovery rate of the membrane device.
逆浸透膜装置の用途としては、例えば、純水製造、海水淡水化、排水回収等が挙げられる。
Examples of the use of the reverse osmosis membrane device include pure water production, seawater desalination, and wastewater collection.
本実施形態に係る低分子有機物含有水の処理方法および処理システム１において、逆浸透膜処理装置１０の被処理水について処理を行う、脱気処理装置、イオン交換処理装置、ＵＶ殺菌処理装置のうちの少なくとも１つの装置を備え、逆浸透膜処理装置１０（逆浸透膜処理工程）の被処理水について、脱気処理、イオン交換処理、ＵＶ殺菌処理のうちの少なくとも１つの処理を行ってもよい。
Among the degassing treatment apparatus, ion exchange treatment apparatus, and UV sterilization treatment apparatus for treating the water to be treated of the reverse osmosis membrane treatment apparatus 10 in the treatment method and treatment system 1 for low molecular organic substance-containing water according to the present embodiment. The reverse osmosis membrane treatment apparatus 10 (reverse osmosis membrane treatment step) water to be treated may be subjected to at least one of degassing treatment, ion exchange treatment, and UV sterilization treatment. .
本実施形態に係る低分子有機物含有水の処理方法および処理システム３において、第１逆浸透膜処理装置２０の被処理水について処理を行う、脱気処理装置、イオン交換処理装置、ＵＶ殺菌処理装置のうちの少なくとも１つの装置を備え、第１逆浸透膜処理装置２０（第１逆浸透膜処理工程）の被処理水について、脱気処理、イオン交換処理、ＵＶ殺菌処理のうちの少なくとも１つの処理を行ってもよい。
In the treatment method and the treatment system 3 for low molecular organic substance-containing water according to the present embodiment, a deaeration treatment device, an ion exchange treatment device, and a UV sterilization treatment device that perform treatment on the treated water of the first reverse osmosis membrane treatment device 20 Of the first reverse osmosis membrane treatment apparatus 20 (first reverse osmosis membrane treatment step), and the water to be treated is at least one of degassing treatment, ion exchange treatment, and UV sterilization treatment. Processing may be performed.
また、本実施形態に係る低分子有機物含有水の処理方法および処理システム３において、第１逆浸透膜処理装置２０の透過水および第２逆浸透膜処理装置２２の透過水のうちの少なくとも１つについて処理を行う、イオン交換処理装置、電気式脱塩処理装置、ＵＶ殺菌処理装置、ＵＶ酸化処理装置、微粒子除去処理装置、第３逆浸透膜処理装置のうちの少なくとも１つの装置を備え、第１逆浸透膜処理装置２０（第１逆浸透膜処理工程）の透過水および第２逆浸透膜処理装置２２（第２逆浸透膜処理工程）の透過水のうちの少なくとも１つについて、イオン交換処理、電気式脱塩処理、ＵＶ殺菌処理、ＵＶ酸化処理、微粒子除去処理、第３逆浸透膜処理のうちの少なくとも１つの処理を行ってもよい。
In the method and system 3 for treating low molecular organic substance-containing water according to this embodiment, at least one of the permeated water of the first reverse osmosis membrane treatment device 20 and the permeated water of the second reverse osmosis membrane treatment device 22 is used. The apparatus comprises at least one of an ion exchange treatment device, an electrical desalination treatment device, a UV sterilization treatment device, a UV oxidation treatment device, a fine particle removal treatment device, and a third reverse osmosis membrane treatment device, Ion exchange is performed on at least one of the permeated water of the first reverse osmosis membrane treatment device 20 (first reverse osmosis membrane treatment step) and the permeated water of the second reverse osmosis membrane treatment device 22 (second reverse osmosis membrane treatment step). At least one of processing, electrical desalting, UV sterilization, UV oxidation, particulate removal, and third reverse osmosis membrane may be performed.
＜ポリアミド系逆浸透膜用改質剤組成物＞
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、「臭素系酸化剤」と「スルファミン酸化合物」との混合物を含む安定化次亜臭素酸組成物を含有するものであり、さらにアルカリを含有してもよい。 <Polyamide-based reverse osmosis membrane modifier composition>
The polyamide-based reverse osmosis membrane modifier composition according to the present embodiment contains a stabilized hypobromite composition containing a mixture of a “bromine-based oxidant” and a “sulfamic acid compound”, Furthermore, you may contain an alkali.
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、「臭素系酸化剤」と「スルファミン酸化合物」との混合物を含む安定化次亜臭素酸組成物を含有するものであり、さらにアルカリを含有してもよい。 <Polyamide-based reverse osmosis membrane modifier composition>
The polyamide-based reverse osmosis membrane modifier composition according to the present embodiment contains a stabilized hypobromite composition containing a mixture of a “bromine-based oxidant” and a “sulfamic acid compound”, Furthermore, you may contain an alkali.
また、本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、「臭素系酸化剤とスルファミン酸化合物との反応生成物」を含む安定化次亜臭素酸組成物を含有するものであり、さらにアルカリを含有してもよい。
Further, the polyamide reverse osmosis membrane modifier composition according to the present embodiment contains a stabilized hypobromite composition containing a “reaction product of a bromine-based oxidant and a sulfamic acid compound”. Yes, it may further contain an alkali.
臭素系酸化剤、臭素化合物、塩素系酸化剤およびスルファミン酸化合物については、上述した通りである。
The bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent, and sulfamic acid compound are as described above.
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物としては、ポリアミド系逆浸透膜をより劣化させず、ＲＯ透過水への有効ハロゲンのリーク量がより少ないため、臭素と、スルファミン酸化合物とを含有するもの（臭素とスルファミン酸化合物の混合物を含有するもの）、例えば、臭素とスルファミン酸化合物とアルカリと水との混合物、または、臭素とスルファミン酸化合物との反応生成物を含有するもの、例えば、臭素とスルファミン酸化合物との反応生成物と、アルカリと、水との混合物が好ましい。
As the polyamide-based reverse osmosis membrane modifier composition according to this embodiment, since the polyamide-based reverse osmosis membrane is not further deteriorated and the amount of effective halogen leaked into RO permeated water is smaller, bromine and sulfamic acid Containing a compound (containing a mixture of bromine and sulfamic acid compound), for example, containing a mixture of bromine, sulfamic acid compound, alkali and water, or a reaction product of bromine and sulfamic acid compound Preferred are, for example, a mixture of a reaction product of bromine and a sulfamic acid compound, an alkali and water.
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、次亜塩素酸や、臭素を含む遊離塩素等の改質剤と比較すると、ポリアミド系の逆浸透膜の改質効果を有しながらも、次亜塩素酸や、臭素を含む遊離塩素のような著しい膜劣化をほとんど引き起こすことがない。通常の使用濃度では、膜劣化への影響は実質的に無視することができる。このため、ポリアミド系の逆浸透膜の改質剤としては最適である。
The polyamide-based reverse osmosis membrane modifier composition according to the present embodiment has an effect of modifying a polyamide-based reverse osmosis membrane as compared with a modifier such as hypochlorous acid or free chlorine containing bromine. However, it hardly causes significant film deterioration such as hypochlorous acid and free chlorine containing bromine. At normal use concentrations, the effect on film degradation can be substantially ignored. Therefore, it is optimal as a modifier for polyamide-based reverse osmosis membranes.
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、次亜塩素酸や、臭素を含む遊離塩素等とは異なり、逆浸透膜をほとんど透過しないため、処理水水質への影響がほとんどない。また、次亜塩素酸等と同様に現場で濃度を測定することができるため、より正確な濃度管理が可能である。
The polyamide-based reverse osmosis membrane modifier composition according to the present embodiment, unlike hypochlorous acid, free chlorine containing bromine and the like, hardly permeates the reverse osmosis membrane, and therefore has an effect on the quality of treated water. rare. Further, since the concentration can be measured on site in the same manner as hypochlorous acid or the like, more accurate concentration management is possible.
改質剤組成物のｐＨは、例えば、１３．０超であり、１３．２超であることがより好ましい。改質剤組成物のｐＨが１３．０以下であると改質剤組成物中の有効ハロゲンが不安定になる場合がある。
The pH of the modifier composition is, for example, more than 13.0, and more preferably more than 13.2. When the pH of the modifier composition is 13.0 or less, the effective halogen in the modifier composition may become unstable.
ポリアミド系逆浸透膜用改質剤組成物中の臭素酸濃度は、５ｍｇ／ｋｇ未満であることが好ましい。ポリアミド系逆浸透膜用改質剤組成物中の臭素酸濃度が５ｍｇ／ｋｇ以上であると、ＲＯ透過水の臭素酸イオンの濃度が高くなる場合がある。
The bromic acid concentration in the polyamide reverse osmosis membrane modifier composition is preferably less than 5 mg / kg. When the bromate concentration in the polyamide-based reverse osmosis membrane modifier composition is 5 mg / kg or more, the concentration of bromate ions in the RO permeate may increase.
＜ポリアミド系逆浸透膜用改質剤組成物の製造方法＞
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、臭素系酸化剤とスルファミン酸化合物とを混合することにより得られ、さらにアルカリを混合してもよい。 <Method for Producing Polyamide-based Reverse Osmosis Membrane Modifier Composition>
The modifier composition for a polyamide-based reverse osmosis membrane according to this embodiment is obtained by mixing a bromine-based oxidant and a sulfamic acid compound, and may further be mixed with an alkali.
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、臭素系酸化剤とスルファミン酸化合物とを混合することにより得られ、さらにアルカリを混合してもよい。 <Method for Producing Polyamide-based Reverse Osmosis Membrane Modifier Composition>
The modifier composition for a polyamide-based reverse osmosis membrane according to this embodiment is obtained by mixing a bromine-based oxidant and a sulfamic acid compound, and may further be mixed with an alkali.
臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を含有する、逆浸透膜用改質剤組成物の製造方法としては、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加して反応させる工程、または、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加する工程を含むことが好ましい。不活性ガス雰囲気下で添加して反応させる、または、不活性ガス雰囲気下で添加することにより、改質剤組成物中の臭素酸イオン濃度が低くなり、ＲＯ透過水中の臭素酸イオン濃度が低くなる。
As a method for producing a reverse osmosis membrane modifier composition containing a stabilized hypobromite composition containing bromine and a sulfamic acid compound, bromine is not added to a mixed liquid containing water, an alkali and a sulfamic acid compound. It is preferable to include a step of adding and reacting under an active gas atmosphere or a step of adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound under an inert gas atmosphere. By adding and reacting under an inert gas atmosphere or adding under an inert gas atmosphere, the bromate ion concentration in the modifier composition is lowered, and the bromate ion concentration in the RO permeated water is lowered. Become.
用いる不活性ガスとしては限定されないが、製造等の面から窒素およびアルゴンのうち少なくとも１つが好ましく、特に製造コスト等の面から窒素が好ましい。
Although the inert gas to be used is not limited, at least one of nitrogen and argon is preferable from the viewpoint of manufacturing and the like, and nitrogen is particularly preferable from the viewpoint of manufacturing cost and the like.
臭素の添加の際の反応器内の酸素濃度は６％以下が好ましいが、４％以下がより好ましく、２％以下がさらに好ましく、１％以下が特に好ましい。臭素の反応の際の反応器内の酸素濃度が６％を超えると、反応系内の臭素酸の生成量が増加する場合がある。
The oxygen concentration in the reactor during the addition of bromine is preferably 6% or less, more preferably 4% or less, further preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reactor during the bromine reaction exceeds 6%, the amount of bromic acid produced in the reaction system may increase.
臭素の添加率は、改質剤組成物全体の量に対して２５重量％以下であることが好ましく、１重量％以上２０重量％以下であることがより好ましい。臭素の添加率が改質剤組成物全体の量に対して２５重量％を超えると、反応系内の臭素酸の生成量が増加する場合がある。１重量％未満であると、改質効果が劣る場合がある。
The addition ratio of bromine is preferably 25% by weight or less, more preferably 1% by weight or more and 20% by weight or less, based on the total amount of the modifier composition. If the bromine addition rate exceeds 25% by weight based on the total amount of the modifier composition, the amount of bromic acid produced in the reaction system may increase. If it is less than 1% by weight, the reforming effect may be inferior.
臭素添加の際の反応温度は、０℃以上２５℃以下の範囲に制御することが好ましいが、製造コスト等の面から、０℃以上１５℃以下の範囲に制御することがより好ましい。臭素添加の際の反応温度が２５℃を超えると、反応系内の臭素酸の生成量が増加する場合があり、０℃未満であると、凍結する場合がある。
The reaction temperature at the time of bromine addition is preferably controlled in the range of 0 ° C. to 25 ° C., but more preferably in the range of 0 ° C. to 15 ° C. from the viewpoint of production cost. When the reaction temperature at the time of bromine addition exceeds 25 degreeC, the production amount of the bromic acid in a reaction system may increase, and when it is less than 0 degreeC, it may freeze.
以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
［安定化次亜臭素酸組成物の調製］
窒素雰囲気下で、液体臭素：１６．９重量％（ｗｔ％）、スルファミン酸：１０．７重量％、水酸化ナトリウム：１２．９重量％、水酸化カリウム：３．９４重量％、水：残分を混合して、安定化次亜臭素酸組成物を調製した。安定化次亜臭素酸組成物のｐＨは１４、有効ハロゲン濃度（有効塩素換算濃度）は７．５重量％であった。安定化次亜臭素酸組成物の詳細な調製方法は以下の通りである。 [Preparation of Stabilized Hypobromite Composition]
Under nitrogen atmosphere, liquid bromine: 16.9% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.94% by weight, water: remaining Minutes were mixed to prepare a stabilized hypobromite composition. The stabilized hypobromite composition had a pH of 14, and an effective halogen concentration (effective chlorine equivalent concentration) of 7.5% by weight. The detailed method for preparing the stabilized hypobromite composition is as follows.
窒素雰囲気下で、液体臭素：１６．９重量％（ｗｔ％）、スルファミン酸：１０．７重量％、水酸化ナトリウム：１２．９重量％、水酸化カリウム：３．９４重量％、水：残分を混合して、安定化次亜臭素酸組成物を調製した。安定化次亜臭素酸組成物のｐＨは１４、有効ハロゲン濃度（有効塩素換算濃度）は７．５重量％であった。安定化次亜臭素酸組成物の詳細な調製方法は以下の通りである。 [Preparation of Stabilized Hypobromite Composition]
Under nitrogen atmosphere, liquid bromine: 16.9% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.94% by weight, water: remaining Minutes were mixed to prepare a stabilized hypobromite composition. The stabilized hypobromite composition had a pH of 14, and an effective halogen concentration (effective chlorine equivalent concentration) of 7.5% by weight. The detailed method for preparing the stabilized hypobromite composition is as follows.
反応容器内の酸素濃度が１％に維持されるように、窒素ガスの流量をマスフローコントローラでコントロールしながら連続注入で封入した２Ｌの４つ口フラスコに１４３６ｇの水、３６１ｇの水酸化ナトリウムを加え混合し、次いで３００ｇのスルファミン酸を加え混合した後、反応液の温度が０～１５℃になるように冷却を維持しながら、４７３ｇの液体臭素を加え、さらに４８％水酸化カリウム溶液２３０ｇを加え、組成物全体の量に対する重量比でスルファミン酸１０．７％、臭素１６．９％、臭素の当量に対するスルファミン酸の当量比が１．０４である、目的の安定化次亜臭素酸組成物を得た。生じた溶液のｐＨは、ガラス電極法にて測定したところ、１４であった。生じた溶液の臭素含有率は、臭素をヨウ化カリウムによりヨウ素に転換後、チオ硫酸ナトリウムを用いて酸化還元滴定する方法により測定したところ１６．９％であり、理論含有率（１６．９％）の１００．０％であった。また、臭素反応の際の反応容器内の酸素濃度は、株式会社ジコー製の「酸素モニタＪＫＯ－０２ ＬＪＤＩＩ」を用いて測定した。なお、臭素酸濃度は５ｍｇ／ｋｇ未満であった。
Add 1436 g of water and 361 g of sodium hydroxide to a 2 L four-necked flask sealed by continuous injection while controlling the flow rate of nitrogen gas with a mass flow controller so that the oxygen concentration in the reaction vessel is maintained at 1%. Next, after adding 300 g of sulfamic acid and mixing, 473 g of liquid bromine was added while maintaining cooling so that the temperature of the reaction solution was 0 to 15 ° C., and 230 g of 48% potassium hydroxide solution was added. A target stabilized hypobromite composition having a sulfamic acid 10.7% by weight ratio relative to the total amount of the composition, 16.9% bromine, and an equivalent ratio of sulfamic acid to the equivalent of bromine of 1.04. Obtained. The pH of the resulting solution was 14 as measured by the glass electrode method. The bromine content of the resulting solution was 16.9% as measured by a redox titration method using sodium thiosulfate after bromine was converted to iodine with potassium iodide, and the theoretical content (16.9% ) Of 100.0%. The oxygen concentration in the reaction vessel during the bromine reaction was measured using “Oxygen Monitor JKO-02 LJDII” manufactured by Zico Corporation. The bromic acid concentration was less than 5 mg / kg.
なお、ｐＨの測定は、以下の条件で行った。
電極タイプ：ガラス電極式
ｐＨ測定計：東亜ディーケーケー社製、ＩＯＬ－３０型
電極の校正：関東化学社製中性リン酸塩ｐＨ（６．８６）標準液（第２種）、同社製ホウ酸塩ｐＨ（９．１８）標準液（第２種）の２点校正で行った
測定温度：２５℃
測定値：測定液に電極を浸漬し、安定後の値を測定値とし、３回測定の平均値 The pH was measured under the following conditions.
Electrode type: Glass electrode type pH meter: IOL-30, manufactured by Toa DKK Corporation Electrode calibration: Neutral phosphate pH (6.86) standard solution (type 2) manufactured by Kanto Chemical Co., boric acid manufactured by the same company Salt temperature (9.18) Standard solution (type 2) was measured by two-point calibration Measurement temperature: 25 ° C
Measurement value: Immerse the electrode in the measurement solution and use the value after stabilization as the measurement value.
電極タイプ：ガラス電極式
ｐＨ測定計：東亜ディーケーケー社製、ＩＯＬ－３０型
電極の校正：関東化学社製中性リン酸塩ｐＨ（６．８６）標準液（第２種）、同社製ホウ酸塩ｐＨ（９．１８）標準液（第２種）の２点校正で行った
測定温度：２５℃
測定値：測定液に電極を浸漬し、安定後の値を測定値とし、３回測定の平均値 The pH was measured under the following conditions.
Electrode type: Glass electrode type pH meter: IOL-30, manufactured by Toa DKK Corporation Electrode calibration: Neutral phosphate pH (6.86) standard solution (type 2) manufactured by Kanto Chemical Co., boric acid manufactured by the same company Salt temperature (9.18) Standard solution (type 2) was measured by two-point calibration Measurement temperature: 25 ° C
Measurement value: Immerse the electrode in the measurement solution and use the value after stabilization as the measurement value.
＜実施例１、比較例１，２＞
上記で調製した安定化次亜臭素酸組成物（実施例１）、次亜塩素酸（比較例１）、次亜臭素酸（臭化ナトリウムと次亜塩素酸の混合物）（比較例２）を改質剤としてそれぞれ用いて、ポリアミド系高分子逆浸透膜（日東電工（株）製「ＳＷＣ４＋」、φ７５ｍｍの平膜、尿素阻止率＝６０％に低下させたもの）の改質を行った。改質は、この逆浸透膜を備える逆浸透膜装置に、操作圧１．０ＭＰａで、上記改質剤を１０ｐｐｍ添加した水をｐＨ＝４、２５±１℃で１時間通水して実施した。その後、操作圧１．０ＭＰａで、尿素（分子量６０）をＴＯＣ値として１０ｐｐｍと、１０ｐｐｍの上記改質剤とを添加した水を、ｐＨ＝７、２５±１℃でＣＴ（Ｃｏｎｃｅｎｔｒａｔｉｏｎ Ｔｉｍｅ）値＝１４０００［ｐｐｍ・ｈ］となるまで連続通水した。原水および透過水のＴＯＣ濃度をＴＯＣ計によって測定し、下記の尿素阻止率を算出した。ＣＴ値は下記の通り算出した。結果を表１に示す。なお、比較例２では、改質剤として、臭化ナトリウム：１５重量％、１２％次亜塩素酸ナトリウム水溶液：４２．４重量％を水中に別々に添加した。
尿素阻止率［%］＝１００－［透過水ＴＯＣ濃度÷｛（給水ＴＯＣ濃度＋濃縮水ＴＯＣ濃度）÷２｝×１００］
ＣＴ値［ｐｐｍ・ｈ］＝（遊離塩素濃度）×（接触時間） <Example 1, Comparative Examples 1 and 2>
The stabilized hypobromite composition (Example 1), hypochlorous acid (Comparative Example 1), and hypobromite (a mixture of sodium bromide and hypochlorous acid) (Comparative Example 2) prepared above. Each was used as a modifier to modify a polyamide polymer reverse osmosis membrane (“SWC4 +” manufactured by Nitto Denko Corporation, flat membrane of φ75 mm, reduced to urea rejection = 60%). The reforming was carried out by passing water with 10 ppm of the above modifier added to the reverse osmosis membrane device having the reverse osmosis membrane at an operating pressure of 1.0 MPa for 1 hour at pH = 4, 25 ± 1 ° C. . Thereafter, water with 10 ppm of urea (molecular weight 60) as TOC value and 10 ppm of the above modifier was added at an operating pressure of 1.0 MPa, and a CT (Concentration Time) value of pH = 7, 25 ± 1 ° C. = The water was continuously passed until it reached 14000 [ppm · h]. The TOC concentration of raw water and permeated water was measured with a TOC meter, and the following urea rejection was calculated. The CT value was calculated as follows. The results are shown in Table 1. In Comparative Example 2, sodium bromide: 15% by weight, 12% sodium hypochlorite aqueous solution: 42.4% by weight were added separately as water as modifiers.
Urea rejection rate [%] = 100− [permeated water TOC concentration ÷ {(feed water TOC concentration + concentrated water TOC concentration) ÷ 2} × 100]
CT value [ppm · h] = (Free chlorine concentration) × (Contact time)
上記で調製した安定化次亜臭素酸組成物（実施例１）、次亜塩素酸（比較例１）、次亜臭素酸（臭化ナトリウムと次亜塩素酸の混合物）（比較例２）を改質剤としてそれぞれ用いて、ポリアミド系高分子逆浸透膜（日東電工（株）製「ＳＷＣ４＋」、φ７５ｍｍの平膜、尿素阻止率＝６０％に低下させたもの）の改質を行った。改質は、この逆浸透膜を備える逆浸透膜装置に、操作圧１．０ＭＰａで、上記改質剤を１０ｐｐｍ添加した水をｐＨ＝４、２５±１℃で１時間通水して実施した。その後、操作圧１．０ＭＰａで、尿素（分子量６０）をＴＯＣ値として１０ｐｐｍと、１０ｐｐｍの上記改質剤とを添加した水を、ｐＨ＝７、２５±１℃でＣＴ（Ｃｏｎｃｅｎｔｒａｔｉｏｎ Ｔｉｍｅ）値＝１４０００［ｐｐｍ・ｈ］となるまで連続通水した。原水および透過水のＴＯＣ濃度をＴＯＣ計によって測定し、下記の尿素阻止率を算出した。ＣＴ値は下記の通り算出した。結果を表１に示す。なお、比較例２では、改質剤として、臭化ナトリウム：１５重量％、１２％次亜塩素酸ナトリウム水溶液：４２．４重量％を水中に別々に添加した。
尿素阻止率［%］＝１００－［透過水ＴＯＣ濃度÷｛（給水ＴＯＣ濃度＋濃縮水ＴＯＣ濃度）÷２｝×１００］
ＣＴ値［ｐｐｍ・ｈ］＝（遊離塩素濃度）×（接触時間） <Example 1, Comparative Examples 1 and 2>
The stabilized hypobromite composition (Example 1), hypochlorous acid (Comparative Example 1), and hypobromite (a mixture of sodium bromide and hypochlorous acid) (Comparative Example 2) prepared above. Each was used as a modifier to modify a polyamide polymer reverse osmosis membrane (“SWC4 +” manufactured by Nitto Denko Corporation, flat membrane of φ75 mm, reduced to urea rejection = 60%). The reforming was carried out by passing water with 10 ppm of the above modifier added to the reverse osmosis membrane device having the reverse osmosis membrane at an operating pressure of 1.0 MPa for 1 hour at pH = 4, 25 ± 1 ° C. . Thereafter, water with 10 ppm of urea (molecular weight 60) as TOC value and 10 ppm of the above modifier was added at an operating pressure of 1.0 MPa, and a CT (Concentration Time) value of pH = 7, 25 ± 1 ° C. = The water was continuously passed until it reached 14000 [ppm · h]. The TOC concentration of raw water and permeated water was measured with a TOC meter, and the following urea rejection was calculated. The CT value was calculated as follows. The results are shown in Table 1. In Comparative Example 2, sodium bromide: 15% by weight, 12% sodium hypochlorite aqueous solution: 42.4% by weight were added separately as water as modifiers.
Urea rejection rate [%] = 100− [permeated water TOC concentration ÷ {(feed water TOC concentration + concentrated water TOC concentration) ÷ 2} × 100]
CT value [ppm · h] = (Free chlorine concentration) × (Contact time)
このように、実施例１の安定化次亜臭素酸組成物を改質剤として改質した膜を用いることにより、逆浸透膜の劣化を抑制しつつ、逆浸透膜の尿素の阻止率が向上した。低分子有機物を含有する低分子有機物含有水を、高い阻止率で逆浸透膜処理することができた。
Thus, by using the membrane modified with the stabilized hypobromite composition of Example 1 as a modifier, the reverse osmosis membrane can be prevented from deteriorating and the urea rejection rate of the reverse osmosis membrane is improved. did. It was possible to perform reverse osmosis membrane treatment of low molecular organic substance-containing water containing low molecular organic substances with a high rejection.
＜実施例２＞
上記で調製した安定化次亜臭素酸組成物として用いて、ポリアミド系高分子逆浸透膜（日東電工（株）製「ＳＷＣ４＋」、φ７５ｍｍの平膜、尿素阻止率＝６０％に低下させたもの）の改質を行った。改質は、この逆浸透膜を備える逆浸透膜装置に、操作圧１．０ＭＰａで、上記改質剤を１０ｐｐｍ添加した水を２５±１℃で１時間通水し、逆浸透膜への給水のｐＨの影響を調べた。 <Example 2>
Polyamide-based polymer reverse osmosis membrane (“SWC4 +” manufactured by Nitto Denko Corporation), φ75 mm flat membrane, urea rejection rate = 60%, used as the stabilized hypobromite composition prepared above ). In the reforming, the reverse osmosis membrane apparatus provided with the reverse osmosis membrane was supplied with 10 ppm of the above modifier at an operating pressure of 1.0 MPa for 1 hour at 25 ± 1 ° C. to supply water to the reverse osmosis membrane. The effect of pH was investigated.
上記で調製した安定化次亜臭素酸組成物として用いて、ポリアミド系高分子逆浸透膜（日東電工（株）製「ＳＷＣ４＋」、φ７５ｍｍの平膜、尿素阻止率＝６０％に低下させたもの）の改質を行った。改質は、この逆浸透膜を備える逆浸透膜装置に、操作圧１．０ＭＰａで、上記改質剤を１０ｐｐｍ添加した水を２５±１℃で１時間通水し、逆浸透膜への給水のｐＨの影響を調べた。 <Example 2>
Polyamide-based polymer reverse osmosis membrane (“SWC4 +” manufactured by Nitto Denko Corporation), φ75 mm flat membrane, urea rejection rate = 60%, used as the stabilized hypobromite composition prepared above ). In the reforming, the reverse osmosis membrane apparatus provided with the reverse osmosis membrane was supplied with 10 ppm of the above modifier at an operating pressure of 1.0 MPa for 1 hour at 25 ± 1 ° C. to supply water to the reverse osmosis membrane. The effect of pH was investigated.
このように、安定化次亜臭素酸組成物の接触のときのｐＨが低いほど、尿素阻止率の向上が大きいことがわかった。すなわち、安定化次亜臭素酸組成物の接触のときのｐＨが低いほど、膜の改質効果が高くなり、低分子有機物の阻止率が向上し、透過水質を改善することができることがわかった。
Thus, it was found that the lower the pH when contacting the stabilized hypobromite composition, the greater the improvement in urea rejection. That is, it was found that the lower the pH at the time of contact with the stabilized hypobromite composition, the higher the membrane modification effect, the higher the blocking rate of low-molecular organic substances, and the better the permeated water quality. .
１，３ 処理システム、１０ 逆浸透膜処理装置、１２，２４ 被処理水配管、１４ 透過水配管、１６ 濃縮水配管、２０ 第１逆浸透膜処理装置、２２ 第２逆浸透膜処理装置、２６ 第１透過水配管、２８ 第１濃縮水配管、３０ 第２透過水配管、３２ 第２濃縮水配管。
1, 3 treatment system, 10 reverse osmosis membrane treatment device, 12, 24 treated water piping, 14 permeate piping, 16 concentrated water piping, 20 first reverse osmosis membrane treatment device, 22 second reverse osmosis membrane treatment device, 26 1st permeate piping, 28 1st concentrated water piping, 30 2nd permeated water piping, 32 2nd concentrated water piping.
Claims (14)
- 低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理工程を含み、
前記逆浸透膜は、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることを特徴とする低分子有機物含有水の処理方法。 Including a reverse osmosis membrane treatment step of treating water to be treated containing low molecular weight organic matter with a reverse osmosis membrane,
The reverse osmosis membrane is a low molecular weight film modified by bringing a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound into contact with a polyamide-based reverse osmosis membrane. A method for treating organic substance-containing water. - 低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理工程を含み、
前記逆浸透膜は、臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることを特徴とする低分子有機物含有水の処理方法。 Including a reverse osmosis membrane treatment step of treating water to be treated containing low molecular weight organic matter with a reverse osmosis membrane,
The reverse osmosis membrane is a membrane modified by bringing a stabilized hypobromite composition containing bromine and a sulfamic acid compound into contact with a polyamide-based reverse osmosis membrane, and contains low molecular organic substance-containing water. Processing method. - 請求項２に記載の低分子有機物含有水の処理方法であって、
前記安定化次亜臭素酸組成物は、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加する工程を含む方法により得られたものであることを特徴とする低分子有機物含有水の処理方法。 It is a processing method of the low molecular organic substance containing water of Claim 2,
The stabilized hypobromite composition is obtained by a method including a step of adding bromine in an inert gas atmosphere to a mixed solution containing water, an alkali, and a sulfamic acid compound. A method for treating water containing molecular organic substances. - 請求項１～３のいずれか１項に記載の低分子有機物含有水の処理方法であって、
前記接触が、前記被処理水のｐＨより低いｐＨで行われることを特徴とする低分子有機物含有水の処理方法。 A method for treating low molecular organic substance-containing water according to any one of claims 1 to 3,
The method for treating low molecular organic substance-containing water, wherein the contact is performed at a pH lower than the pH of the water to be treated. - 請求項１～４のいずれか１項に記載の低分子有機物含有水の処理方法であって、
前記逆浸透膜処理工程の被処理水について、脱気処理、イオン交換処理、ＵＶ殺菌処理のうちの少なくとも１つの処理を行うことを特徴とする低分子有機物含有水の処理方法。 The method for treating low molecular organic substance-containing water according to any one of claims 1 to 4,
A method for treating low-molecular-weight organic substance-containing water, wherein the water to be treated in the reverse osmosis membrane treatment step is subjected to at least one of deaeration treatment, ion exchange treatment, and UV sterilization treatment. - 請求項１～５のいずれか１項に記載の低分子有機物含有水の処理方法であって、
前記逆浸透膜処理工程が、前記被処理水を第１逆浸透膜で処理する第１逆浸透膜処理工程と、前記第１逆浸透膜処理工程の透過水を第２逆浸透膜で処理する第２逆浸透膜処理工程とを含み、
前記第１逆浸透膜および前記第２逆浸透膜のうちの少なくとも１つが、前記安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることを特徴とする低分子有機物含有水の処理方法。 A method for treating low molecular organic substance-containing water according to any one of claims 1 to 5,
In the reverse osmosis membrane treatment step, the first reverse osmosis membrane treatment step of treating the treated water with a first reverse osmosis membrane and the permeated water of the first reverse osmosis membrane treatment step with a second reverse osmosis membrane A second reverse osmosis membrane treatment step,
At least one of the first reverse osmosis membrane and the second reverse osmosis membrane is a membrane modified by bringing the stabilized hypobromite composition into contact with a polyamide-based reverse osmosis membrane. A method for treating low molecular organic substance-containing water. - 請求項６に記載の低分子有機物含有水の処理方法であって、
前記第１逆浸透膜処理工程の透過水および前記第２逆浸透膜処理工程の透過水のうちの少なくとも１つについて、イオン交換処理、電気式脱塩処理、ＵＶ殺菌処理、ＵＶ酸化処理、微粒子除去処理、第３逆浸透膜処理のうちの少なくとも１つの処理を行うことを特徴とする低分子有機物含有水の処理方法。 It is a processing method of the low molecular organic substance containing water of Claim 6, Comprising:
At least one of the permeated water in the first reverse osmosis membrane treatment step and the permeated water in the second reverse osmosis membrane treatment step, ion exchange treatment, electrical desalting treatment, UV sterilization treatment, UV oxidation treatment, fine particles A method for treating water containing a low molecular weight organic substance, comprising performing at least one of a removal treatment and a third reverse osmosis membrane treatment. - 低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理装置を備え、
前記逆浸透膜は、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることを特徴とする低分子有機物含有水の処理システム。 A reverse osmosis membrane treatment device that treats water to be treated containing low molecular organic substances with a reverse osmosis membrane,
The reverse osmosis membrane is a low molecular weight film modified by bringing a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound into contact with a polyamide-based reverse osmosis membrane. Organic matter-containing water treatment system. - 低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理装置を備え、
前記逆浸透膜は、臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることを特徴とする低分子有機物含有水の処理システム。 A reverse osmosis membrane treatment device that treats water to be treated containing low molecular organic substances with a reverse osmosis membrane,
The reverse osmosis membrane is a membrane modified by bringing a stabilized hypobromite composition containing bromine and a sulfamic acid compound into contact with a polyamide-based reverse osmosis membrane, and contains low molecular organic substance-containing water. Processing system. - 請求項９に記載の低分子有機物含有水の処理システムであって、
前記安定化次亜臭素酸組成物は、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加する工程を含む方法により得られたものであることを特徴とする低分子有機物含有水の処理システム。 The low molecular organic substance-containing water treatment system according to claim 9,
The stabilized hypobromite composition is obtained by a method including a step of adding bromine in an inert gas atmosphere to a mixed solution containing water, an alkali, and a sulfamic acid compound. Water treatment system containing molecular organic substances. - 請求項８～１０のいずれか１項に記載の低分子有機物含有水の処理システムであって、
前記接触が、前記被処理水のｐＨより低いｐＨで行われることを特徴とする低分子有機物含有水の処理システム。 The low molecular organic substance-containing water treatment system according to any one of claims 8 to 10,
The said contact is performed at pH lower than pH of the said to-be-processed water, The processing system of the low molecular organic substance containing water characterized by the above-mentioned. - 請求項８～１１のいずれか１項に記載の低分子有機物含有水の処理システムであって、
前記逆浸透膜処理装置の被処理水について処理を行う、脱気処理装置、イオン交換処理装置、ＵＶ殺菌処理装置のうちの少なくとも１つの装置を備えることを特徴とする低分子有機物含有水の処理システム。 The low molecular organic substance-containing water treatment system according to any one of claims 8 to 11,
Treatment of water containing low molecular weight organic matter, comprising at least one of a deaeration treatment device, an ion exchange treatment device, and a UV sterilization treatment device, which performs treatment on water to be treated by the reverse osmosis membrane treatment device system. - 請求項８～１２のいずれか１項に記載の低分子有機物含有水の処理システムであって、
前記逆浸透膜処理装置が、前記被処理水を第１逆浸透膜で処理する第１逆浸透膜処理装置と、前記第１逆浸透膜処理装置の透過水を第２逆浸透膜で処理する第２逆浸透膜処理装置とを含み、
前記第１逆浸透膜および前記第２逆浸透膜のうちの少なくとも１つが、前記安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることを特徴とする低分子有機物含有水の処理システム。 The low-molecular organic substance-containing water treatment system according to any one of claims 8 to 12,
The reverse osmosis membrane treatment device treats the water to be treated with a first reverse osmosis membrane, and treats the permeated water of the first reverse osmosis membrane treatment device with a second reverse osmosis membrane. A second reverse osmosis membrane treatment device,
At least one of the first reverse osmosis membrane and the second reverse osmosis membrane is a membrane modified by bringing the stabilized hypobromite composition into contact with a polyamide-based reverse osmosis membrane. A low-molecular organic substance-containing water treatment system. - 請求項１３に記載の低分子有機物含有水の処理システムであって、
前記第１逆浸透膜処理装置の透過水および前記第２逆浸透膜処理装置の透過水のうちの少なくとも１つについて処理を行う、イオン交換処理装置、電気式脱塩処理装置、ＵＶ殺菌処理装置、ＵＶ酸化処理装置、微粒子除去処理装置、第３逆浸透膜処理装置のうちの少なくとも１つの装置を備えることを特徴とする低分子有機物含有水の処理システム。 It is a processing system of low molecular organic substance content water according to claim 13,
An ion exchange treatment device, an electrical desalination treatment device, and a UV sterilization treatment device that perform treatment on at least one of the permeated water of the first reverse osmosis membrane treatment device and the permeate water of the second reverse osmosis membrane treatment device. A low molecular organic substance-containing water treatment system comprising at least one of a UV oxidation treatment device, a fine particle removal treatment device, and a third reverse osmosis membrane treatment device.
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