TW201817684A - Treatment method and treatment system for water containing low-molecular weight organic matter - Google Patents
Treatment method and treatment system for water containing low-molecular weight organic matter Download PDFInfo
- Publication number
- TW201817684A TW201817684A TW106125793A TW106125793A TW201817684A TW 201817684 A TW201817684 A TW 201817684A TW 106125793 A TW106125793 A TW 106125793A TW 106125793 A TW106125793 A TW 106125793A TW 201817684 A TW201817684 A TW 201817684A
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- Prior art keywords
- reverse osmosis
- osmosis membrane
- water
- treatment
- molecular
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000005416 organic matter Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000012528 membrane Substances 0.000 claims abstract description 272
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 238
- 239000000203 mixture Substances 0.000 claims abstract description 79
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 71
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 67
- -1 sulfamic acid compound Chemical class 0.000 claims abstract description 63
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000007800 oxidant agent Substances 0.000 claims abstract description 34
- HVBSAKJJOYLTQU-UHFFFAOYSA-N Sulfanilic acid Natural products NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 48
- 229950000244 sulfanilic acid Drugs 0.000 claims description 40
- 229920000768 polyamine Polymers 0.000 claims description 37
- 230000001590 oxidative effect Effects 0.000 claims description 31
- 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
- 239000003513 alkali Substances 0.000 claims description 9
- 239000012466 permeate Substances 0.000 claims description 9
- 238000010612 desalination reaction Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 2
- 230000003204 osmotic effect Effects 0.000 claims 2
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 abstract description 11
- 229920002647 polyamide Polymers 0.000 abstract description 8
- 239000004952 Polyamide Substances 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 description 26
- 230000004048 modification Effects 0.000 description 22
- 238000012986 modification Methods 0.000 description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 18
- 239000007795 chemical reaction product Substances 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 18
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 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
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000008400 supply water Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 4
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 4
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- 150000003456 sulfonamides Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910001919 chlorite Inorganic materials 0.000 description 3
- 229910052619 chlorite group Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002715 modification method 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
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 3
- VCUYQZSUSFMZHI-UHFFFAOYSA-N 4-amino-2-ethylbenzenesulfonic acid Chemical group CCC1=CC(N)=CC=C1S(O)(=O)=O VCUYQZSUSFMZHI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 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
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ISAOUZVKYLHALD-UHFFFAOYSA-N 1-chloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)NC(=O)NC1=O ISAOUZVKYLHALD-UHFFFAOYSA-N 0.000 description 1
- 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
- DUUNFVJJUXEDSS-UHFFFAOYSA-N 4-(butylamino)benzenesulfonic acid Chemical group CCCCNC1=CC=C(S(O)(=O)=O)C=C1 DUUNFVJJUXEDSS-UHFFFAOYSA-N 0.000 description 1
- QJLINHJJWGSSBJ-UHFFFAOYSA-N 4-(dibutylamino)benzenesulfonic acid Chemical compound CCCCN(CCCC)C1=CC=C(S(O)(=O)=O)C=C1 QJLINHJJWGSSBJ-UHFFFAOYSA-N 0.000 description 1
- IVZFUJYJXUATPL-UHFFFAOYSA-N 4-(diethylamino)benzenesulfonic acid Chemical compound CCN(CC)C1=CC=C(S(O)(=O)=O)C=C1 IVZFUJYJXUATPL-UHFFFAOYSA-N 0.000 description 1
- KZVBBVPCVQEVQK-UHFFFAOYSA-N 4-(dimethylamino)benzenesulfonic acid Chemical compound CN(C)C1=CC=C(S(O)(=O)=O)C=C1 KZVBBVPCVQEVQK-UHFFFAOYSA-N 0.000 description 1
- QRAXZXPSAGQUNP-UHFFFAOYSA-N 4-(methylamino)benzenesulfonic acid Chemical group CNC1=CC=C(S(O)(=O)=O)C=C1 QRAXZXPSAGQUNP-UHFFFAOYSA-N 0.000 description 1
- CQRJBGVRCUHROE-UHFFFAOYSA-N 4-(propan-2-ylamino)benzenesulfonic acid Chemical group CC(C)NC1=CC=C(S(O)(=O)=O)C=C1 CQRJBGVRCUHROE-UHFFFAOYSA-N 0.000 description 1
- SFQLRTLUQYWUQH-UHFFFAOYSA-N 4-(propylamino)benzenesulfonic acid Chemical group CCCNC1=CC=C(S(O)(=O)=O)C=C1 SFQLRTLUQYWUQH-UHFFFAOYSA-N 0.000 description 1
- HYKDWGUFDOYDGV-UHFFFAOYSA-N 4-anilinobenzenesulfonic acid Chemical group C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=CC=C1 HYKDWGUFDOYDGV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MLJBXBAQIMTRNP-UHFFFAOYSA-N CCCN(CCC)c1ccc(cc1)S(O)(=O)=O Chemical compound CCCN(CCC)c1ccc(cc1)S(O)(=O)=O MLJBXBAQIMTRNP-UHFFFAOYSA-N 0.000 description 1
- IDOGCOHIPQKGFN-UHFFFAOYSA-N CN(C1=CC=C(S(=O)(=O)O)C=C1)CCC Chemical group CN(C1=CC=C(S(=O)(=O)O)C=C1)CCC IDOGCOHIPQKGFN-UHFFFAOYSA-N 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
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- PNNLHGFFNNLCHM-UHFFFAOYSA-M azanium tetramethylazanium dihydroxide Chemical class [NH4+].[OH-].[OH-].C[N+](C)(C)C PNNLHGFFNNLCHM-UHFFFAOYSA-M 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
- 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
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 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 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
- 238000001139 pH measurement Methods 0.000 description 1
- 239000002245 particle Substances 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
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 159000000008 strontium salts Chemical class 0.000 description 1
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D61/10—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
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Abstract
Description
本發明關於使用逆滲透膜的包含低分子有機物之含有低分子有機物的水之處理方法及處理系統。The present invention relates to a method and a system for treating low-molecular organic-containing water using a reverse osmosis membrane and containing low-molecular organic.
用於逆滲透膜(RO膜)之通透水質改善等的改質方法存在有多種。其中，有使含溴之游離氯接觸逆滲透膜預定的時間而改善性能的方法。There are various modification methods for improving the permeability of reverse osmosis membranes (RO membranes) and the like. Among them, there is a method in which free chlorine containing bromine is contacted with a reverse osmosis membrane for a predetermined time to improve performance.
例如，專利文獻1中記載了以下之逆滲透膜元件之處理方法：在搭載有具聚醯胺皮層之逆滲透膜元件的膜分離裝置中，將逆滲透膜元件填充至膜分離裝置內之壓力容器，然後使含溴之游離氯水溶液接觸該逆滲透膜元件。For example, Patent Document 1 describes a method for processing a reverse osmosis membrane element: in a membrane separation device equipped with a reverse osmosis membrane element having a polyurethane skin layer, a pressure for filling the reverse osmosis membrane element into the membrane separation device Container, and then a bromine-containing free chlorine aqueous solution is contacted with the reverse osmosis membrane element.
但，專利文獻1之方法雖可暫時改善水質，但長期通入含溴之游離氯水溶液的話，逆滲透膜會發生劣化，水質會降低。However, although the method of Patent Document 1 can temporarily improve the water quality, if the free chlorine aqueous solution containing bromine is passed for a long time, the reverse osmosis membrane will be deteriorated and the water quality will be reduced.
尤其被處理水含有低分子(例如，分子量200以下)有機物時，逆滲透膜的低分子有機物之阻擋率低，故尋求能以高阻擋率進行逆滲透膜處理的處理方法。 [先前技術文獻] [專利文獻]In particular, when the water to be treated contains low-molecular-weight organic matter (for example, a molecular weight of 200 or less), the low-molecular-weight organic matter of the reverse osmosis membrane has a low barrier rate. Therefore, a treatment method capable of performing reverse osmosis membrane treatment with a high barrier rate is sought. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本特開2003-088730號公報[Patent Document 1] Japanese Patent Laid-Open No. 2003-088730
[發明所欲解決之課題] 本發明之目的在於提供能將包含低分子有機物的被處理水以高阻擋率進行逆滲透膜處理的含有低分子有機物的水之處理方法及處理系統。 [解決課題之手段][Problems to be Solved by the Invention] An object of the present invention is to provide a method and a system for treating low-molecular-organic-containing water capable of performing reverse osmosis membrane treatment on treated water containing low-molecular-weight organics at a high barrier rate. [Means for solving problems]
本發明係一種含有低分子有機物的水之處理方法，包括將包含低分子有機物的被處理水以逆滲透膜進行處理的逆滲透膜處理步驟；該逆滲透膜，係使含有溴系氧化劑與磺胺酸化合物之穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的膜。The invention relates to a method for treating low-molecular-weight organic matter-containing water, comprising a reverse osmosis membrane treatment step of treating to-be-treated water containing low-molecular-weight organic matter with a reverse osmosis membrane; the reverse osmosis membrane comprises a bromine-based oxidant and sulfa The stabilized hypobromous acid composition of an acid compound is a membrane obtained by contacting a polyamine-based reverse osmosis membrane.
又，本發明係一種含有低分子有機物的水之處理方法，包括將包含低分子有機物的被處理水以逆滲透膜進行處理的逆滲透膜處理步驟；該逆滲透膜，係使含有溴與磺胺酸化合物之穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的膜。In addition, the present invention is a method for treating low-molecular-weight organic matter-containing water, including a reverse osmosis membrane treatment step of treating a water containing low-molecular-weight organic matter with a reverse osmosis membrane; the reverse osmosis membrane is made of bromine and sulfonamide The stabilized hypobromous acid composition of an acid compound is a membrane obtained by contacting a polyamine-based reverse osmosis membrane.
前述含有低分子有機物的水之處理方法中，該穩定化次溴酸組成物宜為利用包括在鈍性氣體環境下於含有水、鹼及磺胺酸化合物之混合液中添加溴之步驟的方法而獲得者較佳。In the aforementioned method for treating low-molecular-weight organic-containing water, the stabilized hypobromous acid composition is preferably a method including the step of adding bromine to a mixed solution containing water, an alkali, and a sulfanilic acid compound in a passive gas environment. The winner is better.
前述含有低分子有機物的水之處理方法中，該接觸宜於比起該被處理水之pH更低的pH進行較佳。In the aforementioned method for treating low-molecular-weight organic matter-containing water, the contacting is preferably performed at a pH lower than that of the water to be treated.
前述含有低分子有機物的水之處理方法中，宜對於該逆滲透膜處理步驟之被處理水，實施脱氣處理、離子交換處理、UV殺菌處理中之至少1種處理較佳。In the aforementioned method for treating low-molecular-weight organic matter-containing water, it is preferable to perform at least one of deaeration treatment, ion exchange treatment, and UV sterilization treatment on the water to be treated in the reverse osmosis membrane treatment step.
前述含有低分子有機物的水之處理方法中，該逆滲透膜處理步驟宜包括以下步驟：第1逆滲透膜處理步驟，將該被處理水以第1逆滲透膜進行處理；以及第2逆滲透膜處理步驟，將該第1逆滲透膜處理步驟之通透水以第2逆滲透膜進行處理；且該第1逆滲透膜及該第2逆滲透膜中之至少1者為使該穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的膜較佳。In the aforementioned method for treating low-molecular organic matter-containing water, the reverse osmosis membrane treatment step preferably includes the following steps: a first reverse osmosis membrane treatment step, the treated water is treated with a first reverse osmosis membrane; and a second reverse osmosis; A membrane treatment step in which the permeated water of the first reverse osmosis membrane treatment step is treated with a second reverse osmosis membrane; and at least one of the first reverse osmosis membrane and the second reverse osmosis membrane is to stabilize the A membrane obtained by contacting a hypobromous acid composition with a polyamine-based reverse osmosis membrane for modification is preferred.
前述含有低分子有機物的水之處理方法中，宜對於該第1逆滲透膜處理步驟之通透水及該第2逆滲透膜處理步驟之通透水中之至少1者，實施離子交換處理、 電脫鹽處理、UV殺菌處理、UV氧化處理、微粒去除處理、第3逆滲透膜處理中之至少1種處理較佳。In the aforementioned method for treating low-molecular-weight organic matter-containing water, it is preferred that 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 be subjected to ion exchange treatment, electricity At least one of desalination treatment, UV sterilization treatment, UV oxidation treatment, particle removal treatment, and third reverse osmosis membrane treatment is preferred.
本發明係一種含有低分子有機物的水之處理系統，具備將包含低分子有機物的被處理水以逆滲透膜進行處理的逆滲透膜處理裝置；該逆滲透膜，係使含有溴系氧化劑與磺胺酸化合物之穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的膜。The present invention relates to a low-molecular-weight organic matter-containing water treatment system including a reverse osmosis membrane treatment device for treating a water containing low-molecular organic matter with a reverse osmosis membrane. The reverse osmosis membrane is made of bromine-based oxidant and sulfonamide. The stabilized hypobromous acid composition of an acid compound is a membrane obtained by contacting a polyamine-based reverse osmosis membrane.
又，本發明係一種含有低分子有機物的水之處理系統，具備將包含低分子有機物的被處理水以逆滲透膜進行處理的逆滲透膜處理裝置；該逆滲透膜，係使含有溴與磺胺酸化合物之穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的膜。The present invention relates to a low-molecular-weight organic matter-containing water treatment system including a reverse osmosis membrane treatment device for treating a water containing low-molecular organic matter with a reverse osmosis membrane. The reverse osmosis membrane is made of bromine and sulfonamide. The stabilized hypobromous acid composition of an acid compound is a membrane obtained by contacting a polyamine-based reverse osmosis membrane.
前述含有低分子有機物的水之處理系統中，該穩定化次溴酸組成物，宜為利用包括在鈍性氣體環境下於含有水、鹼及磺胺酸化合物之混合液中添加溴之步驟的方法而獲得者較佳。In the aforementioned low-molecular-weight organic-containing water treatment system, the stabilized hypobromous acid composition is preferably a method including a step of adding bromine to a mixed solution containing water, an alkali, and a sulfanilic acid compound in an inert gas environment. The winner is better.
前述含有低分子有機物的水之處理系統中，該接觸宜於比起該被處理水之pH更低的pH進行較佳。In the aforementioned treatment system for water containing low-molecular organic matter, the contacting is preferably performed at a lower pH than the pH of the water to be treated.
前述含有低分子有機物的水之處理系統中，宜具備對於該逆滲透膜處理裝置之被處理水進行處理的脱氣處理裝置、離子交換處理裝置、UV殺菌處理裝置中之至少1種裝置較佳。It is preferred that at least one of the above-mentioned low-molecular-weight organic-containing water treatment system includes a degassing treatment device, an ion exchange treatment device, and a UV sterilization treatment device for treating the water to be treated in the reverse osmosis membrane treatment device. .
前述含有低分子有機物的水之處理系統中，該逆滲透膜處理裝置宜包括以下裝置：第1逆滲透膜處理裝置，將該被處理水以第1逆滲透膜進行處理；以及第2逆滲透膜處理裝置，將該第1逆滲透膜處理裝置之通透水以第2逆滲透膜進行處理；且該第1逆滲透膜及該第2逆滲透膜中之至少1者宜為使該穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的膜較佳。In the aforementioned low-molecular organic matter-containing water treatment system, the reverse osmosis membrane treatment device preferably includes the following devices: a first reverse osmosis membrane treatment device for treating the treated water with a first reverse osmosis membrane; and a second reverse osmosis A membrane treatment device that processes the permeated water of the first reverse osmosis membrane treatment device with a second reverse osmosis membrane; and at least one of the first reverse osmosis membrane and the second reverse osmosis membrane is preferably to stabilize the The modified hypobromous acid composition is preferably a membrane obtained by contacting a polyamine-based reverse osmosis membrane for modification.
前述含有低分子有機物的水之處理系統中，宜具備對於該第1逆滲透膜處理裝置之通透水及該第2逆滲透膜處理裝置之通透水中之至少1者進行處理的離子交換處理裝置、電脫鹽處理裝置、UV殺菌處理裝置、UV氧化處理裝置、微粒去除處理裝置、第3逆滲透膜處理裝置中之至少1種裝置較佳。 [發明之效果]The above-mentioned low-molecular-weight organic-containing water treatment system preferably includes an ion exchange treatment for 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. At least one of the device, the electric desalination treatment device, the UV sterilization treatment device, the UV oxidation treatment device, the particulate removal treatment device, and the third reverse osmosis membrane treatment device is preferable. [Effect of the invention]
本發明中，可將包含低分子有機物的被處理水以高阻擋率進行逆滲透膜處理。In the present invention, the treated water containing a low-molecular organic substance can be subjected to a reverse osmosis membrane treatment with a high barrier ratio.
以下針對本發明之實施形態進行說明。本實施形態係實施本發明之一例，本發明並不限定於本實施形態。Hereinafter, embodiments of the present invention will be described. This embodiment is an example of implementing the present invention, and the present invention is not limited to this embodiment.
本發明之實施形態之含有低分子有機物的水之處理系統之一例的概略顯示於圖1，針對其構成進行說明。圖1之含有低分子有機物的水之處理系統1具備具有逆滲透膜之逆滲透膜處理裝置10，該逆滲透膜係使含有溴系氧化劑與磺胺酸化合物之穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得。An outline of an example of a low-molecular-weight organic substance-containing water treatment system according to an embodiment of the present invention is shown in FIG. 1 and its configuration will be described. The low-molecular organic-matter-containing water treatment system 1 shown in FIG. 1 includes a reverse osmosis membrane treatment device 10 having a reverse osmosis membrane which contacts a stabilized hypobromous acid composition containing a bromine-based oxidant and a sulfanilic acid compound. The amidine series reverse osmosis membrane is obtained by modification.
圖1之處理系統1中，被處理水配管12與逆滲透膜處理裝置10之入口連接。逆滲透膜處理裝置10之通透水出口與通透水配管14連接，濃縮水出口與濃縮水配管16連接。In the treatment system 1 shown in FIG. 1, the treated water pipe 12 is connected to the inlet of the reverse osmosis membrane treatment device 10. The water-permeable outlet of the reverse osmosis membrane processing device 10 is connected to the water-permeable pipe 14, and the concentrated water outlet is connected to the concentrated water pipe 16.
針對本實施形態之含有低分子有機物的水之處理方法及含有低分子有機物的水之處理系統1的動作進行說明。The operation of the low molecular organic matter-containing water treatment method and the low molecular organic matter-containing water treatment system 1 of this embodiment will be described.
包含低分子有機物的被處理水，通過被處理水配管12供給至逆滲透膜處理裝置10，在逆滲透膜處理裝置10中，利用經改質之逆滲透膜進行被處理水的逆滲透膜處理(逆滲透膜處理步驟)。於逆滲透膜處理中獲得之通透水通過通透水配管14排出，濃縮水通過濃縮水配管16排出。The treated water containing low-molecular organic matter is supplied to the reverse osmosis membrane treatment device 10 through the treated water pipe 12, and the reverse osmosis membrane treatment device 10 uses the modified reverse osmosis membrane to perform reverse osmosis membrane treatment on the treated water. (Reverse osmosis membrane treatment step). The permeated water obtained in 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.
本發明之實施形態之含有低分子有機物的水之處理系統之另一例的概略顯示於圖2。圖2之含有低分子有機物的水之處理系統3具備：具有第1逆滲透膜之第1逆滲透膜處理裝置20、以及具有第2逆滲透膜之第2逆滲透膜處理裝置22。第1逆滲透膜及第2逆滲透膜中之至少1者為使含有溴系氧化劑與磺胺酸化合物之穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的膜。The outline of another example of the low-molecular-weight organic substance containing water treatment system which concerns on embodiment of this invention is shown in FIG. The low molecular organic matter-containing water treatment system 3 shown 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 obtained by subjecting a stabilized hypobromous acid composition containing a bromine-based oxidant and a sulfanilic acid compound to a polyamine-based reverse osmosis membrane for modification. membrane.
圖2之處理系統3中，被處理水配管24與第1逆滲透膜處理裝置20之入口連接。第1逆滲透膜處理裝置20之第1通透水出口和第2逆滲透膜處理裝置22之入口，藉由第1通透水配管26連接。第1逆滲透膜處理裝置20之第1濃縮水出口與第1濃縮水配管28連接。第2逆滲透膜處理裝置22之第2通透水出口與第2通透水配管30連接，第2濃縮水出口與第2濃縮水配管32連接。In the treatment system 3 shown in FIG. 2, the treated water pipe 24 is connected to the inlet of the first reverse osmosis membrane treatment device 20. The first permeable membrane outlet of the first reverse osmosis membrane processing apparatus 20 and the inlet of the second reverse osmosis membrane processing apparatus 22 are connected by a first permeable pipe 26. The first concentrated water outlet of the first reverse osmosis membrane processing device 20 is connected to the first concentrated water pipe 28. The second permeate water outlet of the second reverse osmosis membrane processing device 22 is connected to the second permeate water pipe 30, and the second concentrated water outlet is connected to the second condensate water pipe 32.
包含低分子有機物的被處理水，通過被處理水配管24供給至第1逆滲透膜處理裝置20，在第1逆滲透膜處理裝置20中，利用第1逆滲透膜進行被處理水的逆滲透膜處理(第1逆滲透膜處理步驟)。於第1逆滲透膜處理中獲得之第1濃縮水，通過第1濃縮水配管28排出。於第1逆滲透膜處理中獲得之第1通透水，通過第1通透水配管26供給至第2逆滲透膜處理裝置22，在第2逆滲透膜處理裝置22中，利用第2逆滲透膜進行第1通透水的逆滲透膜處理(第2逆滲透膜處理步驟)。於第2逆滲透膜處理中獲得之第2通透水，通過第2通透水配管30排出，第2濃縮水通過第2濃縮水配管32排出。The treated water containing low-molecular-weight organic matter 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 perform reverse osmosis of the treated water. Membrane treatment (first reverse osmosis membrane treatment step). The first concentrated water obtained in the first reverse osmosis membrane treatment is discharged through a first concentrated water pipe 28. The first permeate obtained in 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 osmosis membrane is subjected to a first water-permeable reverse osmosis membrane treatment (a second reverse osmosis membrane treatment step). The second permeated water obtained in 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.
在圖1之處理系統1及圖2之處理系統3中，藉由使用使含有溴系氧化劑與磺胺酸化合物之穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的逆滲透膜，可將包含低分子有機物的被處理水以高阻擋率進行逆滲透膜處理。藉由該改質方法，逆滲透膜的劣化受到抑制，同時逆滲透膜的阻擋率提高，可改善通透水質。幾乎不會有穩定化次溴酸組成物使聚醯胺系之逆滲透膜劣化的情形，故即使將含有穩定化次溴酸組成物的水長期地通入至聚醯胺系之逆滲透膜並使其接觸，亦可抑制逆滲透膜的劣化，並可抑制逆滲透膜之阻擋率的降低，亦即抑制水質的降低，而非暫時的水質改善。In the processing system 1 of FIG. 1 and the processing system 3 of FIG. 2, a stabilized hypobromous acid composition containing a bromine-based oxidant and a sulfanilic acid compound is used to contact a polyamine-based reverse osmosis membrane for modification. With the obtained reverse osmosis membrane, the treated water containing low-molecular organic substances can be subjected to a reverse osmosis membrane treatment with a high blocking rate. By this modification method, deterioration of the reverse osmosis membrane is suppressed, and at the same time, the barrier ratio of the reverse osmosis membrane is improved, and water permeability can be improved. The stabilized hypobromous acid composition hardly deteriorates the polyammonium-based reverse osmosis membrane. Therefore, even if water containing the stabilized hypobromous acid composition is passed into the polyamine-based reverse osmosis membrane for a long period of time, And contacting it can also suppress the deterioration of the reverse osmosis membrane, and can also suppress the reduction of the barrier rate of the reverse osmosis membrane, that is, the reduction of the water quality, rather than the temporary improvement of the water quality.
如上述，在本實施形態之含有低分子有機物的水之處理方法及處理系統中， 係使用使含有溴系氧化劑與磺胺酸化合物之穩定化次溴酸組成物接觸聚醯胺系之逆滲透膜以進行改質而得的膜。「含有溴系氧化劑與磺胺酸化合物之穩定化次溴酸組成物」，可為含有「溴系氧化劑」與「磺胺酸化合物」之混合物的穩定化次溴酸組成物，亦可為含有「溴系氧化劑與磺胺酸化合物之反應生成物」的穩定化次溴酸組成物。此處，本說明書中之逆滲透膜的「改質」，係指通透水質的改善，亦即係指阻擋率的提高。As described above, in the method and system for treating low-molecular-weight organic-containing water in this embodiment, a stabilized hypobromous acid composition containing a bromine-based oxidant and a sulfanilic acid compound is used in contact with a polyamine-based reverse osmosis membrane. In order to modify the membrane. The "stabilized hypobromous acid composition containing a bromine-based oxidant and a sulfamic acid compound" may be a stabilized hypobromous acid composition containing a mixture of a "bromine-based oxidant" and a "sulfonate compound", or a "bromine It is a stabilized hypobromous acid composition which is a reaction product of an oxidant and a sulfanilic acid compound. Here, the "modification" of the reverse osmosis membrane in this specification refers to the improvement of the water permeability, that is, the improvement of the blocking rate.
亦即，本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜，係利用以下方法進行改質而得的膜：使供給至聚醯胺系之逆滲透膜的水、洗淨水等中存在有作為改質劑之「溴系氧化劑」與「磺胺酸化合物」之混合物，並使其接觸聚醯胺系之逆滲透膜。藉此，據認為在供給水等中有穩定化次溴酸組成物生成。That is, the method for treating low-molecular-weight organic-containing water and the reverse osmosis membrane in the treatment system of the present embodiment are membranes modified by the following method: water supplied to a polyamide-type reverse osmosis membrane There is a mixture of "bromine-based oxidant" and "sulfanilic acid compound" as modifiers in washing water, etc., and it is brought into contact with a polyamine-based reverse osmosis membrane. Accordingly, it is considered that a stabilized hypobromous acid composition is formed in the supply water or the like.
又，本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜，係利用以下方法進行改質而得的膜：使供給至聚醯胺系之逆滲透膜的水、洗淨水等中存在有作為改質劑之「溴系氧化劑與磺胺酸化合物之反應生成物」的穩定化次溴酸組成物，並使其接觸聚醯胺系之逆滲透膜。In addition, the method for treating low-molecular-weight organic matter-containing water and the reverse osmosis membrane in the present embodiment are membranes modified by the following methods: water supplied to a polyamide-type reverse osmosis membrane, There is a stabilized hypobromous acid composition of "reaction product of bromine-based oxidant and sulfanilic acid compound" as a modifier in washing water and the like, and it is brought into contact with a polyamine-based reverse osmosis membrane.
具體而言，本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜，係利用以下方法進行改質而得的膜：使供給至聚醯胺系之逆滲透膜的水等中存在有例如「溴」、「氯化溴」、「次溴酸」或「溴化鈉與次氯酸之反應產物」與「磺胺酸化合物」之混合物，並使其接觸聚醯胺系之逆滲透膜。Specifically, the method for treating low-molecular-weight organic-containing water and the reverse osmosis membrane in the treatment system of this embodiment are membranes modified by the following methods: There is a mixture of "bromide", "bromine chloride", "hypobromous acid" or "reaction product of sodium bromide and hypochlorous acid" and "sulfanilic acid compound" in water, etc., and contact it with polyamide Department of reverse osmosis membrane.
又，本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜，係利用以下方法進行改質而得的膜：使供給至聚醯胺系之逆滲透膜的水等中存在有例如「溴與磺胺酸化合物之反應生成物」、「氯化溴與磺胺酸化合物之反應生成物」、「次溴酸與磺胺酸化合物之反應生成物」、或「溴化鈉與次氯酸之反應產物和磺胺酸化合物之反應生成物」即穩定化次溴酸組成物，並使其接觸聚醯胺系之逆滲透膜。The method for treating low-molecular-weight organic-containing water and the reverse osmosis membrane in the present embodiment are membranes modified by the following methods: water, etc. supplied to a polyamide-based reverse osmosis membrane There are, for example, "the reaction product of bromine and sulfanilic acid compounds", "the reaction product of bromine chloride and sulfanilic acid compounds", "the reaction product of hypobromous acid and sulfanilic acid compounds", or "sodium bromide and sulfanilic acid compounds" The reaction product of hypochlorous acid and the reaction product of sulfanilic acid compound "is to stabilize the hypobromous acid composition and contact it with a polyamine-based reverse osmosis membrane.
本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜的改質，只要例如於具備聚醯胺系之逆滲透膜的逆滲透膜裝置運轉時，在供給至逆滲透膜的水等中，利用藥液注入泵等注入「溴系氧化劑」與「磺胺酸化合物」即可。「溴系氧化劑」與「磺胺酸化合物」可分別添加至供給水等中，亦可將原液彼此予以混合後添加至供給水等中。又，亦可於例如添加有「溴系氧化劑」與「磺胺酸化合物」的水中，使聚醯胺系之逆滲透膜浸漬預定的時間以使其接觸。In the method for treating low-molecular-weight organic matter-containing water and the modification of the reverse osmosis membrane in the present embodiment, as long as, for example, a reverse osmosis membrane device including a polyimide-based reverse osmosis membrane is operated, it is supplied to the reverse osmosis. Membrane water and the like may be injected with a "bromine-based oxidant" and a "sulfonate compound" using a chemical solution injection pump or the like. The "bromine-based oxidant" and the "sulfonate compound" may be separately added to the supply water or the like, or the raw liquids may be mixed with each other and added to the supply water or the like. In addition, for example, a polyamine-based reverse osmosis membrane may be immersed in water to which a "bromine-based oxidant" and a "sulfanilic compound" are added for a predetermined period of time to be brought into contact.
又，例如亦可在供給至聚醯胺系之逆滲透膜的水等中，利用藥液注入泵等注入「溴系氧化劑與磺胺酸化合物之反應生成物」、或「溴化合物與氯系氧化劑之反應產物和磺胺酸化合物之反應生成物」。又，例如亦可在添加有「溴系氧化劑與磺胺酸化合物之反應生成物」、或「溴化合物與氯系氧化劑之反應產物和磺胺酸化合物之反應生成物」的水中，使聚醯胺系之逆滲透膜浸漬預定的時間以使其接觸。In addition, for example, "the reaction product of a bromine-based oxidant and a sulfanilic acid compound" or "bromide and a chlorine-based oxidant" may be injected into a water or the like supplied to a polyamine-based reverse osmosis membrane using a chemical solution injection pump or the like. Reaction products and reaction products of sulfanilic acid compounds. " In addition, for example, polyamine-based water may be added to water to which "the reaction product of a bromine-based oxidant and a sulfanilic compound" or "the reaction product of a bromine compound and a chlorine-based oxidant and a sulfanilic compound" is added. The reverse osmosis membrane is immersed for a predetermined time to make it contact.
利用穩定化次溴酸組成物所為之改質，例如可於具備聚醯胺系之逆滲透膜的逆滲透膜裝置運轉時，在供給至逆滲透膜的水等中連續地或間歇性地添加上述穩定化次溴酸組成物；亦可於逆滲透膜之阻擋率降低時，在供給至逆滲透膜的水等中連續地或間歇性地添加上述穩定化次溴酸組成物，或使逆滲透膜浸漬於含有穩定化次溴酸組成物的水中。Modified by the stabilized hypobromous acid composition. For example, it can be continuously or intermittently added to water or the like supplied to a reverse osmosis membrane when a reverse osmosis membrane device having a polyamine-based reverse osmosis membrane is operated. The stabilized hypobromous acid composition may be added continuously or intermittently to water or the like supplied to the reverse osmosis membrane when the barrier ratio of the reverse osmosis membrane is reduced, or The permeable membrane is immersed in water containing a stabilized hypobromous acid composition.
穩定化次溴酸組成物朝逆滲透膜的接觸，可在常壓條件下、加壓條件下或減壓條件下進行，考量即使不停止逆滲透膜裝置亦可進行改質，可確實地進行逆滲透膜之改質等的觀點，宜於加壓條件下進行較佳。穩定化次溴酸組成物朝逆滲透膜的接觸，例如宜於0.1MPa~8.0MPa之範圍的加壓條件下進行較佳。The contact of the stabilized hypobromous acid composition toward the reverse osmosis membrane can be performed under normal pressure conditions, pressurized conditions, or reduced pressure conditions. It can be modified without considering stopping the reverse osmosis membrane device, and it can be performed reliably. From the viewpoint of modification of the reverse osmosis membrane, it is preferable to carry out under pressure. The contact of the stabilized hypobromous acid composition toward the reverse osmosis membrane is preferably performed under a pressure condition in the range of 0.1 MPa to 8.0 MPa, for example.
穩定化次溴酸組成物朝逆滲透膜的接觸，例如，只要在5℃~35℃之範圍之溫度條件下進行即可。The contact of the stabilized hypobromous acid composition toward the reverse osmosis membrane may be performed, for example, under a temperature range of 5 ° C to 35 ° C.
「磺胺酸化合物」之當量相對於「溴系氧化劑」之當量的比宜為1以上較佳，為1以上2以下之範圍更佳。「磺胺酸化合物」之當量相對於「溴系氧化劑」之當量的比未達1的話，會有逆滲透膜劣化的可能性，超過2的話，會有製造成本增加的情況。The ratio of the equivalent of the "sulfanilic 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 weight of the "sulfanilic acid compound" to the equivalent weight of the "bromine-based oxidant" is less than 1, the reverse osmosis membrane may be deteriorated. If it exceeds 2, the manufacturing cost may increase.
接觸逆滲透膜之全氯濃度，按有效氯濃度換算宜為0.01~100mg/L較佳。未達0.01mg/L的話，會有無法獲得充分的改質效果的情況，多於100mg/L的話，會有導致逆滲透膜劣化、配管等腐蝕的可能性。The total chlorine concentration of the contacting reverse osmosis membrane should preferably be 0.01 ~ 100mg / L in terms of effective chlorine concentration. If it is less than 0.01 mg / L, a sufficient modification effect may not be obtained. If it is more than 100 mg / L, the reverse osmosis membrane may deteriorate, and piping may be corroded.
被處理水含有0.01mg/L以上之低分子有機物時，尤其含有0.1mg/L以上100 mg/L以下時，可更加理想地適用本實施形態之含有低分子有機物的水之處理方法及處理系統。When the water to be treated contains low-molecular-weight organic matter of 0.01 mg / L or more, especially when it contains 0.1 mg / L or more and 100 mg / L or less, the method and system for treating low-molecular-weight organic matter-containing water in this embodiment can be more ideally applied. .
低分子有機物，係指分子量為200以下之有機物，例如可列舉：分子量為200以下的甲醇、乙醇、異丙醇等醇化合物；單乙醇胺、尿素等胺化合物；四甲基氫氧化銨等四烷基銨鹽；乙酸等羧酸等。Low molecular organic matter refers to organic matter having a molecular weight of 200 or less, and examples thereof include alcohol compounds such as methanol, ethanol, and isopropanol having a molecular weight of 200 or less; amine compounds such as monoethanolamine and urea; and tetraalkane such as tetramethylammonium hydroxide Ammonium salts; carboxylic acids such as acetic acid, etc.
溴系氧化劑可列舉：溴(液體溴)、氯化溴、溴酸、溴酸鹽、次溴酸等。次溴酸亦可為使溴化鈉等溴化物與次氯酸等氯系氧化劑反應而生成者。Examples of the bromine-based oxidant include bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromic acid, and the like. Hypobromic acid may be produced by reacting a bromide such as sodium bromide with a chlorine-based oxidant such as hypochlorous acid.
該等中，使用溴的「溴與磺胺酸化合物(溴與磺胺酸化合物之混合物)」或「溴與磺胺酸化合物之反應生成物」之製劑，相較於「次氯酸與溴化合物與磺胺酸」之製劑及「氯化溴與磺胺酸」之製劑等，氯化物離子較少，不會使聚醯胺系之逆滲透膜進一步劣化，導致配管等金屬材料腐蝕的可能性較低，故更佳。Among these, the preparation of "bromide and sulfanilic acid compound (mixture of bromine and sulfanilic acid compound)" or "reaction product of bromine and sulfanilic acid compound" using bromine is compared with "hypochlorous acid and bromine compound and sulfonamide "Acid" preparations and "Bromochloride and Sulfamic acid" preparations have fewer chloride ions, which will not further degrade the polyimide-based reverse osmosis membrane, and cause the possibility of corrosion of metal materials such as piping. Better.
亦即，本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜，宜為利用使溴與磺胺酸化合物接觸(使溴與磺胺酸化合物之混合物接觸)聚醯胺系之逆滲透膜、或使溴與磺胺酸化合物之反應生成物接觸聚醯胺系之逆滲透膜的方法進行改質而得的膜較佳。That is, the method for treating low-molecular-weight organic matter-containing water and the reverse osmosis membrane in the treatment system of this embodiment are preferably polyamines by contacting bromine with a sulfanilic acid compound (contacting a mixture of bromine and a sulfanilic acid compound). A modified reverse osmosis membrane or a method obtained by contacting a reaction product of bromine and a sulfanilic acid compound with a polyamine-based reverse osmosis membrane is preferred.
溴化合物可列舉溴化鈉、溴化鉀、溴化鋰、溴化銨及氫溴酸等。該等中，考量製劑成本等的觀點，宜為溴化鈉較佳。Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide, and hydrobromic acid. Among these, sodium bromide is preferred from the viewpoint of the cost of the preparation.
就氯系氧化劑而言，例如可列舉：氯氣、二氧化氯、次氯酸或其鹽、亞氯酸或其鹽、氯酸或其鹽、過氯酸或其鹽、氯化異氰脲酸或其鹽等。該等中，就鹽而言，例如可列舉：次氯酸鈉、次氯酸鉀等次氯酸鹼金屬鹽；次氯酸鈣、次氯酸鋇等次氯酸鹼土類金屬鹽；亞氯酸鈉、亞氯酸鉀等亞氯酸鹼金屬鹽；亞氯酸鋇等亞氯酸鹼土類金屬鹽；亞氯酸鎳等其他亞氯酸金屬鹽；氯酸銨、氯酸鈉、氯酸鉀等氯酸鹼金屬鹽；氯酸鈣、氯酸鋇等氯酸鹼土類金屬鹽等。該等氯系氧化劑可單獨使用1種，亦可將2種以上組合使用。就氯系氧化劑而言，考量操作性等的觀點，宜使用次氯酸鈉較佳。Examples of the chlorine-based oxidant 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, and chloroisocyanuric acid. Or its salt, etc. Among these, examples of the salt include alkali metal salts of hypochlorite such as sodium hypochlorite and potassium hypochlorite; alkaline earth metal salts of hypochlorite such as calcium hypochlorite and barium hypochlorite; Alkali metal salts of chlorite such as potassium chlorate; Alkaline earth metal salts of chlorite such as barium chlorite; Other metal salts of chlorite such as nickel chlorite; Alkali metal salts of chlorate such as ammonium chlorate, sodium chlorate and potassium chlorate ; Alkaline chloric acid metal salts such as calcium chlorate and barium chlorate. These chlorine-based oxidants may be used singly or in combination of two or more kinds. From the viewpoint of operability, etc., from the viewpoint of chlorine-based oxidant, sodium hypochlorite is preferably used.
磺胺酸化合物係以下列通式(1)表示之化合物。 R2 NSO3 H (1) (式中，R獨立地為氫原子或碳數1~8之烷基。)The sulfanilic acid compound is a compound represented by the following general formula (1). R 2 NSO 3 H (1) (wherein R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
就磺胺酸化合物而言，例如除可列舉2個R基之兩者皆為氫原子的磺胺酸(胺基磺酸(amidosulfuric acid))外，還可列舉：N-甲基磺胺酸、N-乙基磺胺酸、N-丙基磺胺酸、N-異丙基磺胺酸、N-丁基磺胺酸等2個R基中之一個為氫原子，另一個為碳數1~8之烷基的磺胺酸化合物；N,N-二甲基磺胺酸、N,N-二乙基磺胺酸、N,N-二丙基磺胺酸、N,N-二丁基磺胺酸、N-甲基-N-乙基磺胺酸、N-甲基-N-丙基磺胺酸等2個R基之兩者皆為碳數1~8之烷基的磺胺酸化合物；N-苯基磺胺酸等2個R基中之一個為氫原子，另一個為碳數6~10之芳基的磺胺酸化合物；或該等的鹽等。作為磺胺酸鹽，例如可列舉：鈉鹽、鉀鹽等鹼金屬鹽；鈣鹽、鍶鹽、鋇鹽等鹼土類金屬鹽；錳鹽、銅鹽、鋅鹽、鐵鹽、鈷鹽、鎳鹽等其他金屬鹽；銨鹽及胍鹽等。磺胺酸化合物及該等的鹽可單獨使用1種，亦可將2種以上組合使用。就磺胺酸化合物而言，考量環境負荷等的觀點，宜使用磺胺酸(胺基磺酸)較佳。For the sulfamic acid compound, for example, in addition to two sulfanilic acids (amidosulfuric acid) in which both R groups are hydrogen atoms, N-methylsulfanilic acid, N- One of the two R groups such as ethylsulfanilic acid, N-propylsulfanilic acid, N-isopropylsulfanilic acid, and N-butylsulfanilic acid is a hydrogen atom, and the other is an alkyl group having 1 to 8 carbon atoms. Sulfamic acid compounds; N, N-dimethylsulfanilic acid, N, N-diethylsulfanilic acid, N, N-dipropylsulfanilic acid, N, N-dibutylsulfanilic acid, N-methyl-N -Sulfamate compounds in which two R groups such as ethylsulfanilic acid, N-methyl-N-propylsulfanilic acid are alkyl groups having 1 to 8 carbons; 2 R groups such as N-phenylsulfanilic acid One of the groups is a hydrogen atom, and the other is a sulfanilic acid compound having an aryl group having 6 to 10 carbon atoms; or a salt thereof. Examples of the sulfamates include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts, strontium salts, and barium salts; manganese salts, copper salts, zinc salts, iron salts, cobalt salts, and nickel salts And other metal salts; ammonium and guanidine salts. The sulfanilic acid compound and these salts may be used alone or in combination of two or more. In view of the sulfamic acid compound, considering the environmental load and the like, it is preferable to use a sulfamic acid (aminosulfonic acid).
在本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜的改質中，亦可進一步存在有鹼。鹼可列舉氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物等。考量低溫時之製品穩定性等的觀點，亦可倂用氫氧化鈉與氫氧化鉀。又，鹼亦能以水溶液的形式而非固體的形式使用。In the method for treating low-molecular-weight organic matter-containing water and the modification of the reverse osmosis membrane in the treatment system of this embodiment, an alkali may be further present. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. In consideration of the stability of the product at a low temperature, sodium hydroxide and potassium hydroxide may also be used. Also, the base can be used in the form of an aqueous solution instead of a solid.
關於本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜的改質方法，就逆滲透膜而言，可適用近來係主流之聚醯胺系高分子膜。聚醯胺系高分子膜對於氧化劑的耐性相對較低，若使游離氯等連續接觸聚醯胺系高分子膜，會發生膜性能的顯著降低。但，使用穩定化次溴酸組成物的逆滲透膜之改質方法中，即使是聚醯胺高分子膜，亦幾乎不會發生如此顯著之膜性能的降低。Regarding the method for treating low-molecular-weight organic-containing water and the method for modifying the reverse osmosis membrane in the treatment system of the present embodiment, as for the reverse osmosis membrane, a recent mainstream polyamide polymer membrane is applicable. Polyamine-based polymer membranes have relatively low resistance to oxidants. If continuous chlorine or the like is allowed to continuously contact polyamine-based polymer membranes, a significant decrease in membrane performance will occur. However, in a modification method of a reverse osmosis membrane using a stabilized hypobromous acid composition, even if it is a polyamide polymer membrane, such a significant decrease in membrane performance does not occur.
本實施形態之含有低分子有機物的水之處理方法及處理系統中之逆滲透膜的改質方法中，穩定化次溴酸組成物朝聚醯胺系之逆滲透膜的接觸，宜於比起被處理水之pH更低的pH進行較佳。於逆滲透膜之改質後，在通入被處理水時連續添加穩定化次溴酸組成物作為黏質抑制劑的情況下，被處理水的pH比起改質時的pH更高(亦即，改質時的pH比起被處理水的pH更低)的話，可維持改質效果，並可抑制被處理水之通透流量的變動。於逆滲透膜之改質後，在通入被處理水時連續添加穩定化次溴酸組成物作為黏質抑制劑的情況下，被處理水的pH比起改質時的pH更低(亦即，改質時的pH比起被處理水的pH更高)的話，會有改質效果與被處理水之通透流量發生變動的情況。穩定化次溴酸組成物朝聚醯胺系之逆滲透膜的接觸，例如於pH超過3、未達8之範圍進行，或於pH4~6.5之範圍內進行。穩定化次溴酸組成物在接觸時的pH越低，膜的改質效果越高，阻擋率提高，可改善通透水質。In the method for treating low-molecular-weight organic matter-containing water and the method for reforming the reverse osmosis membrane in the treatment system of this embodiment, the contact of the hypobromous acid composition toward the polyamide-based reverse osmosis membrane is stabilized, which is more suitable than The pH of the treated water is preferably lower. After the reverse osmosis membrane is modified, when the stabilized hypobromous acid composition is continuously added as a viscosity inhibitor when the treated water is passed in, the pH of the treated water is higher than that during the modification (also That is, if the pH at the time of the modification is lower than that of the water to be treated), the effect of the modification can be maintained, and the permeation flow rate of the water to be treated can be suppressed. After the reverse osmosis membrane is modified, when the stabilized hypobromous acid composition is continuously added as a viscosity inhibitor when the treated water is passed in, the pH of the treated water is lower than that during the modification (also That is, if the pH at the time of the modification is higher than the pH of the water to be treated), the effect of the modification and the permeate flow rate of the water to be treated may be changed. The contact of the stabilized hypobromous acid composition toward the polyamine-based reverse osmosis membrane is performed, for example, at a pH range of 3 to 8, or a pH range of 4 to 6.5. The lower the pH of the stabilized hypobromous acid composition during contact, the higher the membrane modification effect, the higher the blocking rate, and the better the water permeability.
在逆滲透膜裝置中，供給至逆滲透膜的水於pH5.5以上產生積垢時，為了抑制積垢，亦可將分散劑與穩定化次溴酸組成物倂用。就分散劑而言，例如可列舉：聚丙烯酸、聚馬來酸、膦酸等。分散劑於供給水中的添加量，例如按RO濃縮水中之濃度算為0.1~1,000mg/L之範圍。In a reverse osmosis membrane device, when the water supplied to the reverse osmosis membrane causes fouling at a pH of 5.5 or more, a dispersant and a stabilized hypobromous acid composition may also be used in order to suppress fouling. Examples of the dispersant include polyacrylic acid, polymaleic acid, and phosphonic acid. The amount of the dispersant added to the supply water is, for example, in the range of 0.1 to 1,000 mg / L based on the concentration of the RO concentrated water.
又，為了不使用分散劑而抑制積垢的產生，例如可列舉調整逆滲透膜裝置之回收率等運轉條件，以使RO濃縮水中之二氧化矽濃度成為溶解度以下，並使鈣積垢之指標即藍氏指數成為0以下。In addition, in order to suppress the generation of scale without using a dispersant, for example, adjusting the operating conditions such as the recovery rate of the reverse osmosis membrane device so that the concentration of silicon dioxide in the RO concentrated water becomes less than the solubility and an index of calcium scale That is, the Lans index becomes 0 or less.
作為逆滲透膜裝置的用途，例如可列舉純水製造、海水淡化、排放水回收等。Examples of applications of the reverse osmosis membrane device include production of pure water, desalination of seawater, and recovery of discharged water.
本實施形態之含有低分子有機物的水之處理方法及處理系統1中，具備對於逆滲透膜處理裝置10之被處理水進行處理的脱氣處理裝置、離子交換處理裝置、 UV殺菌處理裝置中之至少1種裝置，對於逆滲透膜處理裝置10(逆滲透膜處理步驟)之被處理水，可實施脱氣處理、離子交換處理、UV殺菌處理中之至少1種處理。The method and system 1 for treating low-molecular-weight organic matter-containing water according to this embodiment include one of a degassing treatment device, an ion exchange treatment device, and a UV sterilization treatment device for treating the water to be treated in the reverse osmosis membrane treatment device 10. At least one type of device. At least one of deaeration treatment, ion exchange treatment, and UV sterilization treatment can be performed on the water to be treated in the reverse osmosis membrane treatment device 10 (reverse osmosis membrane treatment step).
本實施形態之含有低分子有機物的水之處理方法及處理系統3中，具備對於第1逆滲透膜處理裝置20之被處理水進行處理的脱氣處理裝置、離子交換處理裝置、UV殺菌處理裝置中之至少1種裝置，對於第1逆滲透膜處理裝置20(第1逆滲透膜處理步驟)之被處理水，可實施脱氣處理、離子交換處理、UV殺菌處理中之至少1種處理。The method and system 3 for treating low-molecular-weight organic matter-containing water according to this embodiment include a degassing treatment device, an ion exchange treatment device, and a UV sterilization treatment device for treating the water to be treated in the first reverse osmosis membrane treatment device 20. At least one of these devices can perform at least one of deaeration treatment, ion exchange treatment, and UV sterilization treatment on the water to be treated in the first reverse osmosis membrane treatment device 20 (the first reverse osmosis membrane treatment step).
又，本實施形態之含有低分子有機物的水之處理方法及處理系統3中，具備對於第1逆滲透膜處理裝置20之通透水及第2逆滲透膜處理裝置22之通透水中之至少1者進行處理的離子交換處理裝置、電脫鹽處理裝置、UV殺菌處理裝置、UV氧化處理裝置、微粒去除處理裝置、第3逆滲透膜處理裝置中之至少1種裝置， 對於第1逆滲透膜處理裝置20(第1逆滲透膜處理步驟)之通透水及第2逆滲透膜處理裝置22(第2逆滲透膜處理步驟)之通透水中之至少1者，可實施離子交換處理、電脫鹽處理、UV殺菌處理、UV氧化處理、微粒去除處理、第3逆滲透膜處理中之至少1種處理。The method and system 3 for treating low-molecular-weight organic matter-containing water according to the present embodiment include at least at least one of water permeable to the first reverse osmosis membrane treatment device 20 and water permeable to the second reverse osmosis membrane treatment device 22. At least one of an ion exchange treatment device, an electric desalination treatment device, a UV sterilization treatment device, a UV oxidation treatment device, a particulate removal treatment device, and a third reverse osmosis membrane treatment device for one treatment. For the first reverse osmosis membrane, At least one of the permeable water in the processing device 20 (the first reverse osmosis membrane processing step) and the permeable water in the second reverse osmosis membrane processing device 22 (the second reverse osmosis membrane processing step) may be subjected to ion exchange treatment, electricity At least one of desalination treatment, UV sterilization treatment, UV oxidation treatment, particulate removal treatment, and third reverse osmosis membrane treatment.
＜聚醯胺系逆滲透膜用改質劑組成物＞ 本實施形態之聚醯胺系逆滲透膜用改質劑組成物，係包括含有「溴系氧化劑」與「磺胺酸化合物」之混合物的穩定化次溴酸組成物，亦可進一步含有鹼。<Polyamine-based modifier for reverse osmosis membranes> The modifier for polyamines for reverse osmosis membranes of this embodiment includes a mixture containing a "bromine-based oxidant" and a "sulfonate compound" The stabilized hypobromous acid composition may further contain a base.
又，本實施形態之聚醯胺系逆滲透膜用改質劑組成物，係包括含有「溴系氧化劑與磺胺酸化合物之反應生成物」的穩定化次溴酸組成物，亦可進一步含有鹼。In addition, the polyamine-based reverse osmosis membrane modifier composition of this embodiment is a stabilized hypobromous acid composition including a "reaction product of a bromine-based oxidant and a sulfanilic acid compound", and may further contain an alkali. .
關於溴系氧化劑、溴化合物、氯系氧化劑及磺胺酸化合物，如上述。The bromine-based oxidant, bromine compound, chlorine-based oxidant, and sulfanilic acid compound are as described above.
就本實施形態之聚醯胺系逆滲透膜用改質劑組成物而言，為了不使聚醯胺系逆滲透膜進一步劣化，且使有效鹵素滲漏到RO通透水的量更少，宜為含有溴與磺胺酸化合物者(含有溴與磺胺酸化合物之混合物者)，例如為溴、磺胺酸化合物、鹼、及水之混合物，或宜為含有溴與磺胺酸化合物之反應生成物者，例如為溴與磺胺酸化合物之反應生成物、鹼、及水之混合物較佳。With regard to the modifier composition for a polyamide-based reverse osmosis membrane of this embodiment, in order not to further degrade the polyamide-based reverse osmosis membrane, and to reduce the amount of effective halogen leakage to the RO permeate water, Those who contain bromine and sulfanilic acid compounds (those containing mixtures of bromine and sulfanilic acid compounds), such as bromine, sulfanilic acid compounds, bases, and water, or those containing reaction products of bromine and sulfanilic acid compounds For example, a mixture of a reaction product of bromine and a sulfanilic acid compound, a base, and water is preferred.
本實施形態之聚醯胺系逆滲透膜用改質劑組成物，相較於次氯酸、含溴之游離氯等改質劑，具有聚醯胺系之逆滲透膜之改質效果，同時也幾乎不會引起如次氯酸、含溴之游離氯之顯著的膜劣化。於通常之使用濃度，可基本忽略對於膜劣化的影響。因此，作為聚醯胺系之逆滲透膜的改質劑最理想。Compared with modifiers such as hypochlorous acid and bromine-containing free chlorine, the modifier composition for polyimide-based reverse osmosis membranes of this embodiment has the modification effect of polyimide-based reverse osmosis membranes. It also hardly causes significant film degradation such as hypochlorous acid and bromine-containing free chlorine. At normal concentrations, the effect on film degradation can be ignored. Therefore, it is most suitable as a modifier of a polyamine-based reverse osmosis membrane.
本實施形態之聚醯胺系逆滲透膜用改質劑組成物，和次氯酸、含溴之游離氯等不同，幾乎不會穿透逆滲透膜，故幾乎不會影響處理水水質。又，和次氯酸等同樣可現場測定濃度，故可更加正確地管理濃度。Unlike the hypochlorous acid and bromine-containing free chlorine, the modifier composition for a polyimide-based reverse osmosis membrane of this embodiment hardly penetrates the reverse osmosis membrane, and therefore, it hardly affects the quality of treated water. In addition, since the concentration can be measured on-site like hypochlorous acid and the like, the concentration can be managed more accurately.
改質劑組成物的pH，例如宜為超過13.0，為超過13.2更佳。改質劑組成物的pH為13.0以下的話，會有改質劑組成物中之有效鹵素變得不穩定的情況。The pH of the modifier composition is preferably, 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.
聚醯胺系逆滲透膜用改質劑組成物中之溴酸濃度宜為未達5mg/kg較佳。聚醯胺系逆滲透膜用改質劑組成物中之溴酸濃度為5mg/kg以上的話，會有RO通透水之溴酸離子的濃度變高的情況。The bromic acid concentration in the modifier composition for a polyamine-based reverse osmosis membrane is preferably less than 5 mg / kg. If the bromic acid concentration in the modifier composition for a polyamine-based reverse osmosis membrane is 5 mg / kg or more, there may be a case where the concentration of bromate ion in RO permeation water becomes high.
＜聚醯胺系逆滲透膜用改質劑組成物之製造方法＞ 本實施形態之聚醯胺系逆滲透膜用改質劑組成物，可藉由將溴系氧化劑與磺胺酸化合物予以混合而獲得，亦可進一步混合鹼。<Manufacturing Method of Modifier Composition for Polyamine-Based Reverse Osmosis Membrane> The modifier composition for polyamine-based reverse osmosis membrane according to this embodiment can be obtained by mixing a bromine-based oxidant and a sulfanilic acid compound. Obtained, and the base may be further mixed.
包括含有溴與磺胺酸化合物之穩定化次溴酸組成物的逆滲透膜用改質劑組成物之製造方法，宜包含在鈍性氣體環境下於含有水、鹼及磺胺酸化合物之混合液中添加溴並使其反應的步驟，或在鈍性氣體環境下於含有水、鹼及磺胺酸化合物之混合液中添加溴的步驟較佳。藉由在鈍性氣體環境下進行添加並使其反應，或在鈍性氣體環境下進行添加，改質劑組成物中之溴酸離子濃度變低，RO通透水中之溴酸離子濃度變低。A method for producing a modifier for a reverse osmosis membrane comprising a stabilized hypobromous acid composition containing bromine and a sulfanilic acid compound is preferably contained in a mixed solution containing water, an alkali, and a sulfanilic acid compound under an inert gas atmosphere. The step of adding bromine and reacting it, or the step of adding bromine in a mixed solution containing water, alkali, and sulfanilic acid compound under an inert gas environment is preferred. By adding and reacting in an inert gas environment, or by adding and reacting in an inert gas environment, the bromate ion concentration in the modifier composition becomes lower, and the bromate ion concentration in RO permeate water becomes lower. .
所使用之鈍性氣體並無限定，考量製造等的方面，宜為氮氣及氬氣中之至少1種較佳，考量製造成本等的方面，尤其為氮氣較佳。The inert gas to be used is not limited. Considering aspects such as manufacturing, it is preferably at least one of nitrogen and argon. Considering aspects such as manufacturing cost, nitrogen is particularly preferred.
溴添加時之反應器內的氧濃度宜為6%以下較佳，為4%以下更佳，為2%以下尤佳，為1%以下特佳。溴反應時之反應器內的氧濃度超過6%的話，會有反應系內之溴酸的生成量增加的情況。The oxygen concentration in the reactor when bromine is added is preferably less than 6%, more preferably less than 4%, more preferably less than 2%, and particularly preferably less than 1%. 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.
溴的添加率宜相對於改質劑組成物全體的量為25重量%以下較佳，為1重量%以上20重量%以下更佳。溴的添加率相對於改質劑組成物全體的量超過25重量%的話，會有反應系內之溴酸的生成量增加的情況。未達1重量%的話，會有改質效果不佳的情況。The addition rate of bromine is preferably 25% by weight or less with respect to the entire amount of the modifier composition, and more preferably 1% by weight or more and 20% by weight or less. When the addition rate of bromine 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 modification effect may be poor.
溴添加時之反應溫度宜控制在0℃以上25℃以下之範圍內較佳，考量製造成本等的方面，宜控制在0℃以上15℃以下之範圍內更佳。溴添加時之反應溫度超過25℃的話，會有反應系內之溴酸的生成量增加的情況，未達0℃的話，會有結凍的情況。 [實施例]The reaction temperature during the addition of bromine should preferably be controlled within the range of 0 ° C to 25 ° C. Considering aspects such as manufacturing costs, it should be controlled within the range of 0 ° C to 15 ° C. If the reaction temperature during the addition of bromine exceeds 25 ° C, the amount of bromic acid produced in the reaction system may increase, and if it does not reach 0 ° C, it may freeze. [Example]
以下，舉實施例及比較例對本發明進行更加具體且詳細地說明，但本發明並不限定於以下的實施例。Hereinafter, the present invention will be described more specifically and in detail with examples and comparative examples, but the present invention is not limited to the following examples.
[穩定化次溴酸組成物之製備] 於氮氣環境下，將液體溴：16.9重量%(wt%)、磺胺酸：10.7重量%、氫氧化鈉：12.9重量%、氫氧化鉀：3.94重量%、水：剩餘分量予以混合，製備穩定化次溴酸組成物。穩定化次溴酸組成物的pH為14，有效鹵素濃度(有效氯換算濃度)為7.5重量%。穩定化次溴酸組成物的詳細製備方法如下。[Preparation of stabilized hypobromous acid composition] Under a nitrogen environment, liquid bromine: 16.9% by weight (wt%), sulfanilic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.94% by weight Water: The remaining components are mixed to prepare a stabilized hypobromous acid composition. The pH of the stabilized hypobromous acid composition was 14, and the effective halogen concentration (effective chlorine equivalent concentration) was 7.5% by weight. The detailed production method of the stabilized hypobromous acid composition is as follows.
在邊以質量流量控制器控制流量邊連續注入並封入氮氣以使反應容器內的氧濃度維持在1%的2L之4口燒瓶中，加入1436g的水、361g的氫氧化鈉並混合，然後，加入300g的磺胺酸並混合，之後維持使反應液之溫度冷卻成為0~15℃的狀態，加入473g的液體溴，進一步加入48%氫氧化鉀溶液230g，獲得按相對於組成物全體的量之重量比計，胺磺酸為10.7%、溴為16.9%，胺磺酸之當量相對於溴之當量的比為1.04的目標穩定化次溴酸組成物。利用玻璃電極法測定生成之溶液的pH，結果為14。生成之溶液的含溴率，於將溴利用碘化鉀轉換為碘後，使用硫代硫酸鈉以氧化還原滴定之方法進行測定，結果為16.9%，為理論含有率(16. 9%)之100.0%。又，溴反應時之反應容器內的氧濃度，係利用Jikco(股)公司製的「Oxygen Monitor JKO-02 LJDII」進行測定。此外，溴酸濃度為未達5mg/kg。While continuously controlling the flow rate with a mass flow controller, nitrogen was continuously injected and sealed to maintain the oxygen concentration in the reaction vessel at a 1% 2 L 4-necked flask. 1436 g of water and 361 g of sodium hydroxide were added and mixed. 300 g of sulfanilic acid was added and mixed, and then the temperature of the reaction solution was cooled to 0 to 15 ° C. 473 g of liquid bromine was added, and 230 g of a 48% potassium hydroxide solution was further added to obtain an amount based on the entire composition. By weight ratio, the target stabilized hypobromous acid composition was 10.7% amine sulfonic acid, 16.9% bromine, and the ratio of the equivalent weight of aminesulfonic acid to the equivalent weight of bromine was 1.04. The pH of the produced solution was measured by the glass electrode method, and it was 14. The bromine content of the resulting solution was determined by redox titration using sodium thiosulfate after converting bromine to potassium iodide using iodide. The result was 16.9%, which was 100.0% of the theoretical content (16.9%). . The oxygen concentration in the reaction vessel during the bromine reaction was measured using "Oxygen Monitor JKO-02 LJDII" manufactured by Jikco Co., Ltd. The bromic acid concentration was less than 5 mg / kg.
此外，pH測定係於以下條件進行。 電極類型：玻璃電極式 pH測定計：東亞DKK公司製，IOL-30型 電極校正：以關東化學公司製中性磷酸鹽pH(6.86)標準液(第2種)、同公司製硼酸鹽pH(9.18)標準液(第2種)進行2點校正 測定溫度：25℃ 測定値：將電極浸入測定液，以穩定後的値作為測定値，3次測定的平均値The pH measurement was performed under the following conditions. Electrode type: Glass electrode type pH meter: manufactured by Toya DKK, IOL-30 type electrode calibration: neutral phosphate pH (6.86) standard solution (type 2) manufactured by Kanto Chemical Co., Ltd. 9.18) Two-point calibration of the standard solution (type 2). Measurement temperature: 25 ° C. Measurement: immerse the electrode in the measurement solution, use the stabilized 値 as the measurement 値, and average the three measurements.
＜實施例1、比較例1、2＞ 將上述製備之穩定化次溴酸組成物(實施例1)、次氯酸(比較例1)、次溴酸(溴化鈉與次氯酸之混合物)(比較例2)分別作為改質劑使用，進行聚醯胺系高分子逆滲透膜(日東電工(股)製「SWC4+」、φ75mm之平膜、降低成尿素阻擋率=60%者)的改質。就改質而言，係在具備該逆滲透膜之逆滲透膜裝置中，以操作壓力1.0 MPa，於pH=4、25±1℃通入添加有10ppm之上述改質劑的水1小時而實施。之後，以操作壓力1.0MPa，於pH=7、25±1℃連續通入添加有按TOC值算為10ppm之尿素(分子量60)、10ppm之上述改質劑的水，直到CT(Concentration Time)值=14000 [ppm･h]。利用TOC計測定原水及通透水的TOC濃度，算出下列尿素阻擋率。如下述般算出CT值。結果顯示於表1。此外，在比較例2中，就改質劑而言，於水中分別添加溴化鈉：15重量%、12%次氯酸鈉水溶液：42.4重量%。 尿素阻擋率[%]=100-[通透水TOC濃度÷{(供給水TOC濃度+濃縮水TOC濃度)÷2}×100] CT值[ppm･h]=(游離氯濃度)×(接觸時間)<Example 1, Comparative Example 1, 2> The stabilized hypobromous acid composition (Example 1), hypochlorous acid (Comparative Example 1), and hypobromous acid (a mixture of sodium bromide and hypochlorous acid) prepared as described above were prepared. ) (Comparative Example 2) Each was used as a modifier, and a polyamine-based polymer reverse osmosis membrane (a "SWC4 +" manufactured by Nitto Denko Corporation, a flat membrane of φ 75 mm, and a reduced urea blocking rate = 60%) Improved. In terms of modification, in a reverse osmosis membrane device provided with the reverse osmosis membrane, water with 10 ppm of the above-mentioned modifier added was operated at an operating pressure of 1.0 MPa at pH = 4 and 25 ± 1 ° C for one hour. Implementation. After that, the operating pressure was 1.0 MPa, and the water containing the urea with a TOC value of 10 ppm (molecular weight 60) and 10 ppm of the above-mentioned modifier was continuously passed at pH = 7, 25 ± 1 ° C, until CT (Concentration Time). Value = 14000 [ppm ･ h]. The TOC concentration of raw water and permeated water was measured with a TOC meter, and the following urea blocking ratios were calculated. The CT value was calculated as follows. The results are shown in Table 1. Further, in Comparative Example 2, as the modifier, sodium bromide: 15% by weight and 12% sodium hypochlorite aqueous solution: 42.4% by weight were added to water, respectively. Urea blocking rate [%] = 100- [Permeated water TOC concentration ÷ {(Supply water TOC concentration + Concentrated water TOC concentration) ÷ 2} × 100] CT value [ppm ･ h] = (Free chlorine concentration) × (Contact time)
【表1】
如此藉由使用將實施例1之穩定化次溴酸組成物作為改質劑以進行改質而得的膜，逆滲透膜的劣化受到抑制，而且逆滲透膜的尿素阻擋率提高。可將包含低分子有機物之含有低分子有機物的水以高阻擋率進行逆滲透膜處理。In this way, by using the membrane obtained by using the stabilized hypobromous acid composition of Example 1 as a modifier, the deterioration of the reverse osmosis membrane is suppressed, and the urea blocking rate of the reverse osmosis membrane is improved. The reverse osmosis membrane treatment can be performed on water containing low molecular organic matter and containing low molecular organic matter with a high blocking rate.
＜實施例2＞ 使用上述製備之穩定化次溴酸組成物，進行聚醯胺系高分子逆滲透膜(日東電工(股)製「SWC4+」、φ75mm之平膜、降低為尿素阻擋率=60%者)的改質。在具備該逆滲透膜之逆滲透膜裝置中，以操作壓力1.0MPa，於25±1℃通入添加有10ppm之上述改質劑的水1小時而實施改質，並調查供給水的pH對於逆滲透膜的影響。<Example 2> Using the stabilized hypobromous acid composition prepared as described above, a polyamine-based polymer reverse osmosis membrane ("SWC4 +" manufactured by Nitto Denko Corporation, a flat membrane of 75 mm in diameter, and reduced to urea barrier ratio = 60 %)). In a reverse osmosis membrane device equipped with this reverse osmosis membrane, water was added at 10 ± 1 ° C at an operating pressure of 1.0 MPa for 1 hour to perform modification, and the pH of the supplied water was investigated. Effect of reverse osmosis membrane.
【表2】
如此可知穩定化次溴酸組成物在接觸時的pH越低，尿素阻擋率的提高越大。 亦即，可知穩定化次溴酸組成物在接觸時的pH越低，膜的改質效果越高，低分子有機物的阻擋率提高，可改善通透水質。In this way, it can be seen that the lower the pH of the stabilized hypobromous acid composition upon contact, the greater the increase in the urea blocking rate. That is, it can be seen that the lower the pH of the stabilized hypobromous acid composition during contact, the higher the membrane modification effect, the higher the blocking rate of the low-molecular-weight organic matter, and the better the water permeability.
1、3‧‧‧處理系統1. 3‧‧‧ processing system
10‧‧‧逆滲透膜處理裝置10‧‧‧ reverse osmosis membrane treatment device
12、24‧‧‧被處理水配管12, 24‧‧‧ Piping for treated water
14‧‧‧通透水配管14‧‧‧ Permeable piping
16‧‧‧濃縮水配管16‧‧‧ Concentrated water piping
20‧‧‧第1逆滲透膜處理裝置20‧‧‧The first reverse osmosis membrane treatment device
22‧‧‧第2逆滲透膜處理裝置22‧‧‧The second reverse osmosis membrane treatment device
26‧‧‧第1通透水配管26‧‧‧The first permeable pipe
28‧‧‧第1濃縮水配管28‧‧‧The first concentrated water pipe
30‧‧‧第2通透水配管30‧‧‧ 2nd permeable pipe
32‧‧‧第2濃縮水配管32‧‧‧ 2nd concentrated water pipe
【圖1】係顯示本發明之實施形態之含有低分子有機物的水之處理系統之一例的概略構成圖。 【圖2】係顯示本發明之實施形態之含有低分子有機物的水之處理系統之另一例的概略構成圖。FIG. 1 is a schematic configuration diagram showing an example of a low-molecular-weight organic-containing water treatment system according to an embodiment of the present invention. FIG. 2 is a schematic configuration diagram showing another example of a low-molecular-weight organic-containing water treatment system according to an embodiment of the present invention.
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