KR20190028476A - Water treatment method using reverse osmosis membrane - Google Patents
Water treatment method using reverse osmosis membrane Download PDFInfo
- Publication number
- KR20190028476A KR20190028476A KR1020197003798A KR20197003798A KR20190028476A KR 20190028476 A KR20190028476 A KR 20190028476A KR 1020197003798 A KR1020197003798 A KR 1020197003798A KR 20197003798 A KR20197003798 A KR 20197003798A KR 20190028476 A KR20190028476 A KR 20190028476A
- Authority
- KR
- South Korea
- Prior art keywords
- reverse osmosis
- osmosis membrane
- water
- bromine
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000012528 membrane Substances 0.000 title claims abstract description 139
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 58
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 67
- -1 sulfamic acid compound Chemical class 0.000 claims abstract description 67
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 62
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000007800 oxidant agent Substances 0.000 claims abstract description 56
- 239000000460 chlorine Substances 0.000 claims abstract description 50
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 49
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 48
- 239000003899 bactericide agent Substances 0.000 claims abstract description 47
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 239000003206 sterilizing agent Substances 0.000 claims description 17
- 239000005416 organic matter Substances 0.000 claims description 6
- 239000000645 desinfectant Substances 0.000 claims description 4
- 230000006866 deterioration Effects 0.000 abstract description 15
- 238000011109 contamination Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 46
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000007795 chemical reaction product Substances 0.000 description 18
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 14
- 230000035699 permeability Effects 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 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
- 238000002360 preparation method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 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
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 102100026794 Carboxypeptidase A5 Human genes 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 101000910789 Homo sapiens Carboxypeptidase A5 Proteins 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
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 description 3
- YGNOYUCUPMACDT-UHFFFAOYSA-N dimethylsulfamic acid Chemical group CN(C)S(O)(=O)=O YGNOYUCUPMACDT-UHFFFAOYSA-N 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 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
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 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
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 102100030621 Carboxypeptidase A4 Human genes 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
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 108091006676 Monovalent cation:proton antiporter-3 Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WOHVONCNVLIHKY-UHFFFAOYSA-L [Ba+2].[O-]Cl=O.[O-]Cl=O Chemical class [Ba+2].[O-]Cl=O.[O-]Cl=O WOHVONCNVLIHKY-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 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
- 235000019270 ammonium chloride Nutrition 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 group OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct 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
- 239000004202 carbamide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BAQKWXACUNEBOT-UHFFFAOYSA-N dibutylsulfamic acid Chemical group CCCCN(S(O)(=O)=O)CCCC BAQKWXACUNEBOT-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XRVWREPFYXZOPK-UHFFFAOYSA-N dipropylsulfamic acid Chemical group CCCN(S(O)(=O)=O)CCC XRVWREPFYXZOPK-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XVBSDZVOYDKINF-UHFFFAOYSA-N ethyl n,n-diethylsulfamate Chemical group CCOS(=O)(=O)N(CC)CC XVBSDZVOYDKINF-UHFFFAOYSA-N 0.000 description 1
- IOISAJSHULNACL-UHFFFAOYSA-N ethyl(methyl)sulfamic acid Chemical group 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
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 238000000691 measurement method Methods 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical group CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 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
- 159000000001 potassium salts Chemical class 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HLIBNTOXKQCYMV-UHFFFAOYSA-N propylsulfamic acid Chemical group CCCNS(O)(=O)=O HLIBNTOXKQCYMV-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/022—Membrane sterilisation
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- 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
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
역침투막의 2차 측에 있어서도 슬라임 오염을 억제하고, 그리고 역침투막의 산화 열화를 억제하는 역침투막을 이용하는 수처리 방법을 제공한다. 피처리수를 역침투막으로 처리하는, 역침투막을 이용하는 수처리 방법으로서, 암모니아를 함유하는 피처리수 중에, 브로민계 산화제 또는 염소계 산화제와 설팜산 화합물을 포함하는 살균제를 존재시키는, 역침투막을 이용하는 수처리 방법이다.A water treatment method using a reverse osmosis membrane that suppresses slime contamination even on the secondary side of a reverse osmosis membrane and suppresses oxidation deterioration of a reverse osmosis membrane is provided. There is provided a water treatment method using a reverse osmosis membrane for treating water to be treated with a reverse osmosis membrane using a reverse osmosis membrane in which a bromine-based oxidizing agent or a bactericide containing a chlorine-based oxidizing agent and a sulfamic acid compound is present in water to be treated containing ammonia It is water treatment method.
Description
본 발명은 역침투막(RO막)을 이용하는 수처리 방법에 관한 것이다.The present invention relates to a water treatment method using a reverse osmosis membrane (RO membrane).
역침투막(RO막)을 이용하는 수처리 방법에 있어서, 바이오파울링 대책으로서 각종 살균제(슬라임 억제제)가 사용되는 것이 일반적이다. 차아염소산 등의 염소계 산화제는 대표적인 살균제이며, 계 내의 살균 목적으로 통상은 역침투막의 전단에 첨가된다. 염소계 산화제는 역침투막을 열화시킬 가능성이 높기 때문에, 일반적으로는 역침투막의 직전에 염소계 산화제를 환원 분해시키거나, 간헐적으로 염소계 산화제를 역침투막에 유입시킴으로써 운용되고 있다.In the water treatment method using the reverse osmosis membrane (RO membrane), various sanitizers (slime inhibitors) are generally used as countermeasures against biofouling. Chlorine-based oxidizing agents such as hypochlorous acid are typical bactericides and are usually added to the shear of the reverse osmosis membrane for sterilization purposes in the system. Since the chlorine-based oxidizing agent is highly likely to deteriorate the reverse osmosis membrane, it is generally operated by reducing the chlorine-based oxidizing agent immediately before the reverse osmosis membrane or intermittently introducing the chlorine-based oxidizing agent into the reverse osmosis membrane.
또한, 살균제(슬라임 억제제)로서 염소계 산화제와 설팜산 화합물로 이루어진 결합 염소제를 역침투막의 피처리수 중에 존재시키는 방법(특허문헌 1 참조)이나, 브로민계 산화제, 또는 브로민화합물과 염소계 산화제와의 반응물과, 설팜산 화합물의 혼합물 혹은 반응 생성물을 피처리수에 첨가하는 방법(특허문헌 2 참조)이 알려져 있다.It is also possible to use a method in which a binding chlorine agent composed of a chlorine-based oxidizing agent and a sulfamic acid compound as a bactericide (slime inhibitor) is caused to exist in the water to be treated in a reverse osmosis membrane (see Patent Document 1), a bromine-based oxidizing agent, And a method of adding a mixture or reaction product of a sulfamic acid compound to the water to be treated (see Patent Document 2).
염소계 산화제 또는 브로민계 산화제와 설팜산 화합물을 포함하는 살균제는, 살균 능력이 높은 동시에 폴리아마이드계의 역침투막을 산화 열화시키기 어렵고, 역침투막에서의 저지율도 높으며, 후단의 처리수(투과수)질에 영향이 적기 때문에 유효하다.A chloric oxidizing agent or a bactericide containing a bromine-based oxidizing agent and a sulfamic acid compound has a high sterilizing ability and is difficult to oxidize the polyamide-based reverse osmosis membrane and has a high rejection rate in the reverse osmosis membrane, It is effective because it has little influence on quality.
그러나, 역침투막에 의해 살균제의 대부분이 저지되어 버리므로, 역침투막의 1차 측에서는 살균제가 유효한 경우에도 2차 측의 투과수 라인이 슬라임 오염을 받는 일이 있다. 특히 피처리수가 저분자(예를 들면, 분자량 200 이하)의 유기물을 포함할 경우, 저분자의 유기물은 역침투막에 의한 저지율이 낮기 때문에, 역침투막의 1차 측에서는 살균제가 유효할 경우에도 2차 측에서 저분자의 유기물에 기인하는 슬라임 오염이 발생하는 일이 있다.However, since most of the sterilizing agent is blocked by the reverse osmosis membrane, the permeate line on the secondary side may be slime contaminated even if the sterilizing agent is effective on the primary side of the reverse osmosis membrane. Particularly, when the water to be treated contains an organic substance having a low molecular weight (for example, a molecular weight of 200 or less), the low molecular weight organic matter has a low rejection rate due to the reverse osmosis membrane. Therefore, on the primary side of the reverse osmosis membrane, There is a case where slime contamination due to low-molecular organic matters occurs.
본 발명의 목적은, 역침투막의 2차 측에 있어서도 슬라임 오염을 억제하고, 그리고 역침투막의 산화 열화를 억제하는, 역침투막을 이용하는 수처리 방법을 제공하는 것에 있다.An object of the present invention is to provide a water treatment method using a reverse osmosis membrane that suppresses slime contamination even in the secondary side of a reverse osmosis membrane and suppresses oxidation deterioration of a reverse osmosis membrane.
본 발명은, 피처리수를 역침투막으로 처리하는, 역침투막을 이용하는 수처리 방법으로서, 암모니아를 함유하는 상기 피처리수 중에, 브로민계 산화제 또는 염소계 산화제와 설팜산 화합물을 포함하는 살균제를 존재시키는, 역침투막을 이용하는 수처리 방법이다.The present invention relates to a water treatment method using a reverse osmosis membrane for treating water to be treated as a reverse osmosis membrane, wherein a bromine-based oxidizing agent or a bactericide containing a chlorine-based oxidizing agent and a sulfamic acid compound is present in the water containing ammonia , And a reverse osmosis membrane.
또한, 본 발명은, 피처리수를 역침투막으로 처리하는, 역침투막을 이용하는 수처리 방법이며, 암모니아를 함유하는 상기 피처리수 중에, 브로민과 설팜산 화합물을 포함하는 살균제를 존재시키는, 역침투막을 이용하는 수처리 방법이다.The present invention also provides a water treatment method using a reverse osmosis membrane that treats for-treatment water with a reverse osmosis membrane, and is characterized in that a sterilizing agent containing bromine and a sulfamic acid compound is present in the water to be treated containing ammonia This is a water treatment method using a permeable membrane.
상기 역침투막을 이용하는 수처리 방법에 있어서, 상기 피처리수 중의 전체 염소 농도에 대한 상기 암모니아의 농도의 비가, 0.01 내지 1의 범위가 되도록 상기 살균제 또는 상기 암모니아의 농도를 조정하는 것이 바람직하다.In the water treatment method using the reverse osmosis membrane, it is preferable to adjust the concentration of the bactericide or the ammonia so that the ratio of the concentration of ammonia to the total chlorine concentration in the for-treatment water is in the range of 0.01 to 1.
상기 역침투막을 이용하는 수처리 방법에 있어서, 상기 역침투막이 음이온 하전막인 것이 바람직하다.In the water treatment method using the reverse osmosis membrane, it is preferable that the reverse osmosis membrane is an anion-lower membrane.
상기 역침투막을 이용하는 수처리 방법에 있어서, 상기 피처리수가 상기 역침투막을 투과하는 유기물을 0.5㎎/ℓ 이상 포함하는 것이 바람직하다.In the water treatment method using the reverse osmosis membrane, it is preferable that the for-treatment water contains 0.5 mg / L or more of organic matter permeating the reverse osmosis membrane.
상기 역침투막을 이용하는 수처리 방법에 있어서, 투과수를 사용점에서 사용하지 않을 때에만 상기 살균제를 첨가해서 상기 피처리수 중에 존재시키는 것이 바람직하다.In the water treatment method using the reverse osmosis membrane, it is preferable that the sterilizing agent is added to the treated water only when the permeated water is not used at the point of use.
본 발명에서는, 역침투막의 2차 측에 있어서도 슬라임 오염을 억제하고, 그리고 역침투막의 산화 열화를 억제할 수 있다.In the present invention, slime contamination can be suppressed even in the secondary side of the reverse osmosis membrane, and oxidation deterioration of the reverse osmosis membrane can be suppressed.
도 1은 실시예에 있어서 역침투막에서의 저지율의 평가에 이용한 평막시험 장치의 개략 구성도이다.
도 2는 실시예 및 비교예에 있어서의 암모니아/살균제(전체 염소) 농도비에 대한 살균제 투과율(%)을 나타낸 도면이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of a flat membrane testing apparatus used for evaluation of a blocking ratio in a reverse osmosis membrane according to an embodiment. FIG.
2 is a graph showing the bactericidal permeability (%) to the ammonia / bactericide (total chlorine) concentration ratio in Examples and Comparative Examples.
본 발명의 실시형태에 대해서 이하 설명한다. 본 실시형태는 본 발명을 실시하는 일례이며, 본 발명은 본 실시형태로 한정되는 것은 아니다.Embodiments of the present invention will be described below. The present embodiment is an example of carrying out the present invention, and the present invention is not limited to this embodiment.
<역침투막을 이용하는 수처리 방법><Water treatment method using reverse osmosis membrane>
본 발명의 실시형태에 따른 역침투막을 이용하는 수처리 방법은, 암모니아를 함유하는 피처리수 중에, 브로민계 산화제 또는 염소계 산화제와 설팜산 화합물을 포함하는 살균제를 존재시키는 방법이다. "브로민계 산화제와 설팜산 화합물을 포함하는 살균제"는, "브로민계 산화제"와 "설팜산 화합물"의 혼합물을 포함하는 안정화 차아브로민산 조성물을 함유하는 살균제이어도 되고, "브로민계 산화제와 설팜산 화합물의 반응 생성물"을 포함하는 안정화 차아브로민산 조성물을 함유하는 살균제이어도 된다. "염소계 산화제와 설팜산 화합물을 포함하는 살균제"는, "염소계 산화제"와 "설팜산 화합물"의 혼합물을 포함하는 안정화 차아염소산 조성물을 함유하는 살균제이어도 되고, "염소계 산화제와 설팜산 화합물의 반응 생성물"을 포함하는 안정화 차아염소산 조성물을 함유하는 살균제이어도 된다.A water treatment method using a reverse osmosis membrane according to an embodiment of the present invention is a method in which a bromine-based oxidizing agent or a bactericide containing a chlorine-based oxidizing agent and a sulfamic acid compound is present in the water to be treated containing ammonia. &Quot; A bactericide comprising a bromine-based oxidizing agent and a sulfamic acid compound " may be a sterilizing agent containing a stabilized hypobromous acid composition comprising a mixture of " bromine-based oxidizing agent " and "Quot; reaction product of the compound " of the present invention. A " bactericide containing a chlorine-based oxidizing agent and a sulfamic acid compound " may be a bactericide containing a stabilized hypochlorous acid composition comprising a mixture of " chlorine-based oxidizing agent " and " ≪ / RTI > may be a sterilizing agent containing a stabilized hypochlorous acid composition.
즉, 본 발명의 실시형태에 따른 역침투막을 이용하는 수처리 방법은, 피처리수를 역침투막으로 처리하는 방법으로서, 암모니아를 함유하는 피처리수 중에, "브로민계 산화제"와 "설팜산 화합물"의 혼합물, 또는 "염소계 산화제"와 "설팜산 화합물"의 혼합물을 존재시키는 방법이다. 이것에 의해, 피처리수 중에서, 안정화 차아브로민산 조성물 또는 안정화 차아염소산 조성물이 생성되는 것으로 여겨진다.Namely, the water treatment method using the reverse osmosis membrane according to the embodiment of the present invention is a method of treating the for-treatment water with the reverse osmosis membrane, wherein the "bromine-based oxidizer" and "sulfamate compound" , Or a mixture of " chloric oxidizer " and " sulfamic acid compound " is present. Thus, it is considered that a stabilized hypobromous acid composition or a stabilized hypochlorous acid composition is produced in the water to be treated.
또한, 본 발명의 실시형태에 따른 역침투막을 이용하는 수처리 방법은, 피처리수를 역침투막으로 처리하는 방법으로서, 암모니아를 함유하는 피처리수 중에, "브로민계 산화제와 설팜산 화합물의 반응 생성물"인 안정화 차아브로민산 조성물, 또는 "염소계 산화제와 설팜산 화합물의 반응 생성물"인 안정화 차아염소산 조성물을 존재시키는 방법이다.Further, the water treatment method using the reverse osmosis membrane according to the embodiment of the present invention is a method of treating the for-treatment water with a reverse osmosis membrane, wherein the water to be treated containing ammonia is subjected to a treatment such that the reaction product of the bromine- Quot ;, or a " reaction product of a chlorinated oxidizing agent with a sulfamic acid compound ", in the presence of a stabilizing hypochlorous acid composition.
구체적으로는 본 발명의 실시형태에 따른 역침투막을 이용하는 수처리 방법은, 피처리수를 역침투막으로 처리하는 방법으로서, 암모니아를 함유하는 피처리수 중에, "브로민", "염화 브로민", "차아브로민산" 또는 "브로민화나트륨과 차아염소산의 반응물"과, "설팜산 화합물"의 혼합물을 존재시키는 방법이다. 또는 암모니아를 함유하는 피처리수 중에, "차아염소산"과, "설팜산 화합물"의 혼합물을 존재시키는 방법이다.More specifically, the water treatment method using the reverse osmosis membrane according to the embodiment of the present invention is a method of treating the for-treatment water with a reverse osmosis membrane, wherein "bromine", "bromine chloride" , &Quot; hypobromic acid " or " a reaction product of sodium bromide and hypochlorous acid " and a " sulfamic acid compound " Or a mixture of " hypochlorous acid " and " sulfamic acid compound " is present in the water to be treated containing ammonia.
또한, 본 발명의 실시형태에 따른 역침투막을 이용하는 수처리 방법은, 피처리수를 역침투막으로 처리하는 방법으로서, 암모니아를 함유하는 피처리수 중에, 예를 들면, "브로민과 설팜산 화합물의 반응 생성물", "염화 브로민과 설팜산 화합물의 반응 생성물", "차아브로민산과 설팜산 화합물의 반응 생성물", 또는 "브로민화나트륨과 차아염소산의 반응물과, 설팜산 화합물의 반응 생성물"인 안정화 차아브로민산 조성물을 존재시키는 방법이다. 또는 암모니아를 함유하는 피처리수 중에, "차아염소산과 설팜산 화합물의 반응 생성물"인 안정화 차아염소산 조성물을 존재시키는 방법이다.The water treatment method using the reverse osmosis membrane according to the embodiment of the present invention is a method for treating the for-treatment water with a reverse osmosis membrane, and is characterized in that, for example, "bromine and sulfamic acid compounds Reaction product of sodium bromide and hypochlorous acid and reaction product of sulfamic acid compound ", " reaction product of sodium bromide and hypochlorous acid ", " reaction product of sodium bromide and hypochlorous acid compound & ≪ / RTI > in the presence of a stabilized hypobromous acid composition. Or a reaction product of hypochlorous acid and a sulfamic acid compound in the water to be treated containing ammonia.
본 발명자들은 검토를 거듭한 바, 피처리수에 암모니아가 포함될 때, 안정화 차아브로민산 조성물 또는 안정화 차아염소산 조성물을 포함하는 살균제가 역침투막을 투과하기 쉬워지는 것을 찾아냈다. 이 현상을 이용해서, 암모니아를 함유하는 피처리수 중에, 브로민계 산화제 또는 염소계 산화제와 설팜산 화합물을 포함하는 살균제를 존재시키는 것에 의해, 피처리수를 역침투막으로 처리하는 수처리 방법에 있어서, 역침투막의 2차 측에 있어서도 슬라임 오염을 억제하고, 또한 역침투막의 산화 열화를 억제할 수 있다.The present inventors have repeatedly found that when the water to be treated contains ammonia, the sterilizing agent containing the stabilized hypobromous acid composition or the stabilized hypochlorous acid composition is easily permeated through the reverse osmosis membrane. In the water treatment method for treating the for-treatment water with a reverse osmosis membrane by causing a bromine-based oxidizing agent or a bactericide containing a chlorine-based oxidizing agent and a sulfamic acid compound to exist in the water to be treated containing ammonia by using this phenomenon, The slime contamination can be suppressed even on the secondary side of the reverse osmosis membrane and oxidation deterioration of the reverse osmosis membrane can be suppressed.
이와 같이, 본 실시형태에 따른 역침투막을 이용하는 수처리 방법에 있어서, 안정화 차아브로민산 조성물 또는 안정화 차아염소산 조성물은 차아염소산 등의 염소계 산화제와 동등 이상의 슬라임 억제 효과를 발휘함에도 불구하고, 염소계 산화제와 비교하면, 역침투막에의 열화 영향이 낮기 때문에, 역침투막에서의 파울링을 억제하면서, 역침투막의 산화 열화를 억제할 수 있다. 이 때문에, 본 실시형태에 따른 역침투막을 이용하는 수처리 방법에 이용되는 안정화 차아브로민산 조성물 또는 안정화 차아염소산 조성물은, 피처리수를 역침투막으로 처리하는 수처리 방법에 이용되는 슬라임 억제제로서는 적합하다.As described above, in the water treatment method using the reverse osmosis membrane according to the present embodiment, the stabilized hypobromous acid composition or the stabilized hypochlorous acid composition exhibits a slime suppressing effect equal to or higher than that of the chlorinated oxidizing agent such as hypochlorous acid, It is possible to suppress the oxidation deterioration of the reverse osmosis membrane while suppressing fouling in the reverse osmosis membrane because the influence of deterioration on the reverse osmosis membrane is low. Therefore, the stabilized hypobromous acid composition or the stabilized hypochlorous acid composition used in the water treatment method using the reverse osmosis membrane according to the present embodiment is suitable as a slime inhibitor used in a water treatment method for treating a for-treatment water with a reverse osmosis membrane.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법 중, "브로민계 산화제와 설팜산 화합물을 포함하는 살균제"의 경우, 염소계 산화제가 존재하지 않으므로, 역침투막에의 열화 영향이 보다 낮다. 염소계 산화제를 포함할 경우에는, 염소산의 생성이 염려된다.Among the water treatment methods using the reverse osmosis membrane according to the present embodiment, in the case of the " bactericide containing a bromine-based oxidizing agent and a sulfamic acid compound ", there is no chlorine-based oxidizing agent and the influence of deterioration on the reverse osmosis membrane is lower. When a chlorine-based oxidizing agent is contained, generation of chloric acid is a concern.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법 중, "브로민계 산화제"가 브로민일 경우, 염소계 산화제가 존재하지 않으므로, 역침투막에의 열화 영향이 현저하게 낮다.Among the water treatment methods using the reverse osmosis membrane according to the present embodiment, when the "bromine-based oxidizing agent" is bromine, the influence of deterioration on the reverse osmosis membrane is remarkably low because no chlorine-based oxidizing agent is present.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법에서는, 예를 들면, 암모니아를 함유하는 피처리수 중에, "브로민계 산화제" 또는 "염소계 산화제"와 "설팜산 화합물"을 약물 주입 펌프 등에 의해 주입해도 된다. "브로민계 산화제" 또는 "염소계 산화제"와 "설팜산 화합물"은 개별적으로 피처리수에 첨가해도 되고, 또는 원액끼리 혼합시키고 나서 피처리수에 첨가해도 된다.In the water treatment method using the reverse osmosis membrane according to the present embodiment, for example, even when "bromine-based oxidizing agent" or "chlorine-based oxidizing agent" and "sulfamic acid compound" are injected into the water to be treated containing ammonia by a drug injection pump or the like do. The "bromine-based oxidizing agent" or the "chlorine-based oxidizing agent" and the "sulfamic acid compound" may be separately added to the for-treatment water, or may be added to the for-treatment water after mixing the undiluted solutions.
또한, 예를 들면, 암모니아를 함유하는 피처리수 중에, "브로민계 산화제와 설팜산 화합물의 반응 생성물" 또는 "염소계 산화제와 설팜산 화합물의 반응 생성물"을 약물 주입 펌프 등에 의해 주입해도 된다.Further, for example, the reaction product of the bromine-based oxidizing agent and the sulfamic acid compound or the reaction product of the chlorine-based oxidizing agent and the sulfamic acid compound may be injected into the water to be treated containing ammonia by a drug injection pump or the like.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법에 있어서, "브로민계 산화제" 또는 "염소계 산화제"의 당량에 대한 "설팜산 화합물"의 당량의 비는, 1 이상인 것이 바람직하고, 1 이상 2 이하의 범위인 것이 보다 바람직하다.In the water treatment method using the reverse osmosis membrane according to the present embodiment, the equivalent ratio of the "sulfamic acid compound" to the equivalent of "bromine-based oxidizer" or "chlorine-based oxidizer" is preferably 1 or more, Is more preferable.
"브로민계 산화제" 또는 "염소계 산화제"의 당량에 대한 "설팜산 화합물"의 당량의 비가 1 미만이면, 막을 열화시킬 가능성이 있고, 2를 초과하면, 제조 비용이 증가될 경우가 있다.If the ratio of the equivalents of the "sulfamic acid compound" to the equivalents of the "bromine-based oxidizing agent" or "chlorinated oxidizing agent" is less than 1, there is a possibility of deteriorating the film, and if it exceeds 2, the production cost may be increased.
역침투막에 접촉하는 전체 염소 농도는 유효염소 농도 환산으로, 0.01 내지 100㎎/ℓ인 것이 바람직하다. 0.01㎎/ℓ 미만이면, 충분한 슬라임 억제 효과를 얻을 수 없는 경우가 있고, 100㎎/ℓ보다 많다면, 역침투막의 열화, 배관 등의 부식을 일으킬 가능성이 있다.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 slime inhibiting effect may not be obtained. If it is more than 100 mg / L, deterioration of the reverse osmosis membrane and corrosion such as piping may occur.
피처리수 중의 전체 염소 농도에 대한 암모니아의 농도의 비(암모니아 농도(㎎/ℓ)/살균제 농도(전체 염소 농도: ㎎/ℓ))가 0.01 내지 1의 범위가 되도록 살균제를 존재시키는 것이 바람직하고, 0.01 내지 0.5의 범위가 되도록 살균제를 존재시키는 것이 보다 바람직하다. 피처리수 중의 암모니아의 농도에 대한 전체 염소 농도의 비가 0.01 이상이 되도록 살균제를 존재시키면, 살균제의 투과율 향상의 효과가 충분히 나타나므로 바람직하다. 피처리수 중의 암모니아의 농도에 대한 전체 염소 농도의 비가 0.01 미만이면, 살균제의 투과율 향상의 효과가 충분히 나타나지 않을 경우가 있고, 1을 초과해서 존재시켜도, 암모니아 첨가에 의한 살균제의 투과율의 향상 효과가 나타나기 어려워진다.It is preferable that the bactericide is present such that the ratio of the concentration of ammonia to the total chlorine concentration in the for-treatment water (ammonia concentration (mg / l) / bactericide concentration (total chlorine concentration: mg / l) , And more preferably 0.01 to 0.5. The presence of the bactericide so that the ratio of the total chlorine concentration to the concentration of ammonia in the for-treatment water is 0.01 or more is preferable because the effect of improving the permeability of the bactericide is sufficiently exhibited. If the ratio of the total chlorine concentration to the concentration of ammonia in the water to be treated is less than 0.01, the effect of improving the permeability of the bactericide may not be sufficiently shown in some cases. Even if the ratio exceeds 1, the effect of improving the permeability of the bactericide by adding ammonia It becomes difficult to appear.
피처리수에 암모니아가 함유되어 있지 않을 경우에는, 암모니아염을 첨가해도 되고, 다른 암모니아 함유수를 혼합해도 된다.When ammonia is not contained in the for-treatment water, an ammonia salt may be added or other ammonia-containing water may be mixed.
피처리수가, 역침투막을 투과하는 유기물을 0.5㎎/ℓ 이상 포함할 경우, 특히 1.0㎎/ℓ 이상 500㎎/ℓ 이하 포함할 경우에, 본 실시형태에 따른 역침투막을 이용하는 수처리 방법이 보다 적합하게 적용할 수 있다. 피처리수 중의, 역침투막을 투과하는 유기물의 함유량이 0.5㎎/ℓ 미만이면, 역침투막의 2차 측에 있어서 슬라임 오염이 발생하기 어렵다.The water treatment method using the reverse osmosis membrane according to the present embodiment is more preferable when the water to be treated contains 0.5 mg / L or more of organic matter permeating through the reverse osmosis membrane, in particular 1.0 mg / L or more and 500 mg / L or less . If the content of the organic matter permeating the reverse osmosis membrane in the for-treatment water is less than 0.5 mg / l, slime contamination on the secondary side of the reverse osmosis membrane is unlikely to occur.
본 명세서에 있어서 저분자의 유기물이란, 분자량이 200 이하인 유기물을 가리키고, 예를 들면, 분자량이 200 이하인, 메탄올, 에탄올, 아이소프로필 알코올 등의 알코올 화합물, 모노에탄올아민, 요소 등의 아민 화합물, 수산화테트라메틸암모늄 등의 테트라메틸암모늄염을 들 수 있다.The term "low molecular organic matter" as used herein refers to an organic substance having a molecular weight of 200 or less. Examples thereof include alcohol compounds such as methanol, ethanol and isopropyl alcohol, molecular compounds having a molecular weight of 200 or less, amine compounds such as monoethanolamine and urea, And tetramethylammonium salts such as methylammonium.
브로민계 산화제로서는, 브로민(액체 브로민), 염화 브로민, 브로민산, 브로민산염, 차아브로민산 등을 들 수 있다. 차아브로민산은, 브로민화나트륨 등의 브리민화물과 차아염소산 등의 염소계 산화제를 반응시켜서 생성시킨 것이어도 된다.Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, bromine acid, bromate, and hypobromous acid. The hypobromic acid may be produced by reacting a brominated compound such as sodium bromide with a chlorinated oxidizing agent such as hypochlorous acid.
이들 중, 브로민을 이용한 "브로민과 설팜산 화합물(브로민과 설팜산 화합물의 혼합물)" 또는 "브로민과 설팜산 화합물의 반응 생성물"의 제제는, "차아염소산과 브로민 화합물과 설팜산"의 제제 및 "염화브로민과 설팜산"의 제제 등에 비해서, 브로민산의 부생이 적고, 역침투막을 보다 열화시키지 않으므로, 역침투막용 슬라임 억제제로서는 보다 바람직하다.Among them, the preparation of "the reaction product of bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound)" or "bromine and sulfamic acid compound" using bromine is "a mixture of hypochlorous acid and bromine compound Fumaric acid " and a preparation of " bromine chloride and sulfamic acid ", it is more preferable as a slime inhibitor for a reverse osmosis membrane because the byproduct life of bromic acid is small and the reverse osmosis membrane is not further deteriorated.
즉, 본 발명의 실시형태에 따른 역침투막을 이용하는 수처리 방법은, 암모니아를 함유하는 피처리수 중에, 브로민과, 설팜산 화합물을 존재시키는(브로민과 설팜산 화합물의 혼합물을 존재시키는) 것이 바람직하다. 또한, 피처리수 중에, 브로민과 설팜산 화합물의 반응 생성물을 존재시키는 것이 바람직하다.That is, a water treatment method using a reverse osmosis membrane according to an embodiment of the present invention is a method in which bromine and a sulfamic acid compound are present (a mixture of a bromine and a sulfamic acid compound is present) in water to be treated containing ammonia desirable. Further, it is preferable that a reaction product of bromine and a sulfamic acid compound is present in the water to be treated.
브로민 화합물로서는, 브로민화나트륨, 브로민화칼륨, 브로민화리튬, 브로민화암모늄 및 브로민화수소산 등을 들 수 있다. 이들 중, 제제 비용 등의 점에서, 브로민화나트륨이 바람직하다.Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide and hydrobromic acid. Among them, sodium bromide is preferable in terms of preparation cost and the like.
염소계 산화제로서는, 예를 들면, 염소가스, 이산화염소, 차아염소산 또는 이의 염, 아염소산 또는 이의 염, 염소산 또는 이의 염, 과염소산 또는 이의 염, 염소화아이소사이아누르산 또는 이의 염 등을 들 수 있다. 이들 중, 염으로서는, 예를 들면, 차아염소산 나트륨, 차아염소산 칼륨 등의 차아염소산 알칼리 금속염, 차아염소산 칼슘, 차아염소산 바륨 등의 차아염소산 알칼리 토류 금속염, 아염소산 나트륨, 아염소산 칼륨 등의 아염소산 알칼리 금속염, 아염소산 바륨 등의 아염소산 알칼리 토류 금속염, 아염소산 니켈 등의 다른 아염소산금속염, 염소산 암모늄, 염소산 나트륨, 염소산 칼륨 등의 염소산 알칼리 금속염, 염소산 칼슘, 염소산 바륨 등의 염소산 알칼리 토류 금속염 등을 들 수 있다. 이들 염소계 산화제는, 1종을 단독으로 이용해도, 2종 이상을 조합시켜서 이용해도 된다. 염소계 산화제로서는, 취급성 등의 점에서, 차아염소산 나트륨을 이용하는 것이 바람직하다.The chlorine-based oxidizing agent includes, for example, chlorine gas, chlorine dioxide, hypochlorous acid or its salt, chlorous acid or its salt, chloric acid or its salt, perchloric acid or its salt, chlorinated isocyanuric acid or its salt . Among them, examples of the salt include alkali metal hypochlorite such as sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, alkaline earth metal hypochlorite such as barium hypochlorite, sodium chlorite such as sodium chlorite and potassium chlorite, Alkaline earth metal salts such as alkali metal salts and barium chlorites, other metal chlorites such as nickel chlorite, alkali metal chlorides such as ammonium chlorate, sodium chlorate and potassium chlorate, alkaline earth metal chlorides such as calcium chlorate and barium chlorate, etc. . These chlorine-based oxidizing agents may be used singly or in combination of two or more kinds. As the chlorine-based oxidizing agent, sodium hypochlorite is preferably used from the viewpoint of handleability and the like.
설팜산 화합물은, 이하의 일반식 (1)로 표시되는 화합물이다:The sulfamic acid compound is a compound represented by the following general formula (1):
R2NSO3H （1)R 2 NSO 3 H (1)
(식 중, R은 독립적으로 수소 원자 또는 탄소수 1 내지 8의 알킬기이다).(Wherein R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).
설팜산 화합물로서는, 예를 들면, 2개의 R기의 양쪽이 수소원자인 설팜산(아마이드 황산) 이외에, N-메틸설팜산, N-에틸설팜산, N-프로필설팜산, N-아이소프로필 설팜산, N-부틸설팜산 등의 2개의 R기 중 한쪽이 수소원자이며, 다른 쪽이 탄소수 1 내지 8의 알킬기인 설팜산 화합물, N,N-다이메틸설팜산, N,N-다이에틸설팜산, N,N-다이프로필설팜산, N,N-다이부틸설팜산, N-메틸-N-에틸 설팜산, N-메틸-N-프로필설팜산 등의 2개의 R기의 양쪽이 탄소수 1 내지 8의 알킬기인 설팜산 화합물, N-페닐설팜산 등의 2개의 R기 중 한쪽이 수소원자이며, 다른 쪽이 탄소수 6 내지 10의 아릴기인 설팜산 화합물, 또는 이들의 염 등을 들 수 있다. 설팜산염으로서는, 예를 들면, 나트륨염, 칼륨염 등의 알칼리 금속염, 칼슘염, 스트론튬염, 바륨염 등의 알칼리 토류 금속염, 망간염, 구리염, 아연염, 철염, 코발트염, 니켈염 등의 다른 금속염, 암모늄염 및 구아니딘염 등을 들 수 있다. 설팜산 화합물 및 이들의 염은, 1종을 단독으로 이용해도, 2종 이상을 조합시켜서 이용해도 된다. 설팜산 화합물로서는, 환경부하 등의 점에서, 설팜산(아마이드 황산)을 이용하는 것이 바람직하다.As the sulfamoic acid compound, for example, there may be mentioned sulfamic acid (amide sulfuric acid) in which two R groups are hydrogen atoms, and N-methylsulfamic acid, N- ethylsulfamic acid, N-propylsulfamic acid, N- Sulfamic acid, N, N-dimethylsulfamic acid, N, N-diethylethylsulfamic acid, N, N-dimethylsulfamic acid, and N, N-dimethylsulfamic acid, wherein one of the two R groups is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms. Two R groups such as fumaric acid, N, N-dipropylsulfamic acid, N, N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid and N- A sulfamic acid compound in which one of two R groups such as a sulfamic acid compound and an N-phenyl sulfamic acid group is a hydrogen atom and the other is an aryl group having 6 to 10 carbon atoms, or a salt thereof, and the like can be given . Examples of sulfamates are 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 Other metal salts, ammonium salts, and guanidine salts. The sulfamic acid compound and salts thereof may be used singly or in combination of two or more kinds. As the sulfamic acid compound, sulfamic acid (amide sulfuric acid) is preferably used in view of environmental load and the like.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법에 있어서, 알칼리를 더 존재시켜도 된다. 알칼리로서는, 수산화나트륨, 수산화칼륨 등의 수산화알칼리 등을 들 수 있다. 저온 시의 제품 안정성 등의 점에서, 수산화나트륨과 수산화칼륨을 병용해도 된다. 또한, 알칼리는, 고형이 아니라, 수용액으로서 이용해도 된다.In the water treatment method using the reverse osmosis membrane according to the present embodiment, an alkali may be further present. Examples of the alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. Sodium hydroxide and potassium hydroxide may be used in combination in view of the stability of the product at low temperatures and the like. The alkali may be used not as a solid but as an aqueous solution.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법은, 역침투막으로서 요즈음 주류인 폴리아마이드계 고분자막에 적합하게 적용할 수 있다. 폴리아마이드계 고분자막은, 산화제에 대한 내성이 비교적 낮고, 유리 염소 등을 폴리아마이드계 고분자막에 연속적으로 접촉시키면, 막 성능의 현저한 저하가 일어난다. 그러나, 본 실시형태에 따른 역침투막을 이용하는 수처리 방법에서는 폴리아마이드 고분자막에 있어서도, 이러한 현저한 막 성능의 저하는 거의 일어나지 않는다.The water treatment method using the reverse osmosis membrane according to the present embodiment can be suitably applied to a polyamide-based high molecular membrane as a reverse osmosis membrane in recent years. The polyamide-based polymer membrane has a relatively low resistance to an oxidizing agent, and if the free chlorine or the like is continuously brought into contact with the polyamide-based polymer membrane, the membrane performance is remarkably lowered. However, in the water treatment method using the reverse osmosis membrane according to the present embodiment, the remarkable deterioration of the membrane performance hardly occurs even in the polyamide polymer membrane.
역침투막에는, 중성막, 음이온 하전막 및 양이온 하전막이 있다. 본 명세서에서는, 중성막은, 후술하는 실시예에 기재한 제타 전위의 측정 방법에 의해 구한, pH 7.0에 있어서의 제타 전위가 -5 내지 5(mV)의 범위인 것을 가리키고, 음이온 하전막은, pH 7.0에 있어서의 제타 전위가 -5(mV) 미만인 것을 가리킨다.The reverse osmosis membrane includes a neutral membrane, an anion sub-membrane and a cationic charge membrane. In the present specification, the neutral film indicates that the zeta potential at pH 7.0 is in the range of -5 to 5 (mV), which is obtained by the method for measuring the zeta potential described in Examples described later, Is less than -5 (mV).
시판의 중성막으로서는, 예를 들면, BW30XFR(다우 케미컬(Dow chemical)사 제품), LFC3(닛토덴코(日東電工) 주식회사 제품), TML20(토레 주식회사 제품) 등을 들 수 있다.Examples of commercially available neutral films include BW30XFR (manufactured by Dow Chemical), LFC3 (manufactured by Nitto Denko Corporation), TML20 (manufactured by Toray Industries, Inc.), and the like.
시판의 음이온 하전막으로서는, 예를 들면, OFR-625(이상, 오르가노 주식회사 제품), ES15, ES20, CPA3, CPA5(이상, 닛토덴코 주식회사 제품), RE-8040BLN(운진(ウンジン)사 제품) 등을 들 수 있다.Examples of commercially available negative ion charge-controlling membranes include OFR-625 (manufactured by ORGANO CORPORATION), ES15, ES20, CPA3 and CPA5 (manufactured by NITTO DENKO CO., LTD.) And RE-8040BLN And the like.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법에서는, 음이온 하전막을 이용한 경우, 중성막을 이용한 경우에 비해서, 살균제의 투과율이 높고, 역침투막의 2차 측에 있어서도 슬라임 오염을 보다 억제할 수 있다.In the water treatment method using the reverse osmosis membrane according to the present embodiment, when the anion charged membrane is used, the permeability of the sterilizing agent is high and the slime contamination can be further suppressed even on the secondary side of the reverse osmosis membrane, as compared with the case of using a neutral membrane.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법에서는, 투과수를 사용점에서 사용하지 않을 때에는, 얻은 RO 투과수를 RO 농축수와 함께 역침투막의 1차 측에 순환시켜도 되고, 투과수를 사용점에서 사용하지 않을 때에만 살균제를 첨가해서 피처리수 중에 존재시키는 것이 바람직하다. 이것에 의해, RO 투과수 라인의 살균을 행하면서, 투과수를 사용하는 때에는 투과수에 살균제가 포함되지 않게 된다는 효과가 있다.In the water treatment method using the reverse osmosis membrane according to the present embodiment, when the permeated water is not used at the point of use, the obtained RO permeated water may be circulated along with the RO concentrated water to the primary side of the reverse osmosis membrane, It is preferable to add a sterilizing agent only when it is not used in water to be present in the water to be treated. This has the effect of sterilizing the RO permeated water line and preventing the sterilizing agent from being included in the permeated water when permeated water is used.
본 실시형태에 따른 역침투막을 이용하는 수처리 방법에 있어서, 역침투막을 구비하는 역침투막장치에 급수되는 피처리수의 pH가 5.5 이상인 것이 바람직하고, 6.0 이상인 것이 보다 바람직하며, 6.5 이상인 것이 더욱 바람직하다. 피처리수의 pH가 5.5 미만이면, 투과수량이 저하될 경우가 있다. 또한, 피처리수의 pH의 상한치에 대해서는, 통상의 역침투막의 적용 상한 pH(예를 들면, pH10) 이하이면 특별히 제한은 없지만, 칼슘 등의 경도성분의 스케일(scale) 석출을 고려하면, pH는 예를 들면 9.0 이하에서 운전하는 것이 바람직하다. 본 실시형태에 따른 역침투막을 이용하는 수처리 방법을 이용할 경우, 피처리수의 pH가 5.5 이상에서 운전하는 것에 의해, 역침투막의 열화, 처리수(투과수)의 수질 악화를 억제하고, 충분한 슬라임 억제 효과를 발휘하면서, 충분한 투과수량의 확보도 가능해진다.In the water treatment method using the reverse osmosis membrane according to the present embodiment, the pH of the water to be treated to be supplied to the reverse osmosis membrane device having a reverse osmosis membrane is preferably 5.5 or more, more preferably 6.0 or more, Do. If the pH of the water to be treated is less than 5.5, the permeation water may be lowered. The upper limit of the pH of the water to be treated is not particularly limited as far as it is not higher than the upper limit pH of application of a typical reverse osmosis membrane (for example, pH 10). However, considering scale precipitation of hardness components such as calcium, For example, 9.0 or less. When the water treatment method using the reverse osmosis membrane according to the present embodiment is used, deterioration of the reverse osmosis membrane and deterioration of water quality of the treated water (permeated water) can be suppressed by operating the pH of the for- It is possible to secure sufficient permeated water while exhibiting the effect.
역침투막장치에 있어서, 피처리수의 pH 5.5 이상에서 스케일이 발생할 경우에는, 스케일 억제를 위하여 분산제를 상기 살균제와 병용해도 된다. 분산제로서는, 예를 들면, 폴리아크릴산, 폴리말레산, 포스폰산 등을 들 수 있다. 분산제의 피처리수에의 첨가량은, 예를 들면, RO 농축수 중의 농도로서 0.1 내지 1,000㎎/ℓ의 범위이다.In the reverse osmosis membrane device, when a scale occurs at pH 5.5 or higher of the water to be treated, a dispersant may be used in combination with the above-mentioned bactericide for suppressing the scale. Examples of the dispersing agent include polyacrylic acid, polymaleic acid, and phosphonic acid. The amount of the dispersant to be added to the water to be treated is, for example, in the range of 0.1 to 1,000 mg / l as the concentration in the RO concentrated water.
또한, 분산제를 사용하지 않고 스케일의 발생을 억제하기 위해서는, 예를 들면, RO 농축수 중의 실리카 농도를 용해도 이하, 칼슘 스케일의 지표인 랑게리아 지수(LANGELIER INDEX)를 0 이하가 되도록, 역침투막장치의 회수율 등의 운전 조건을 조정하는 것을 들 수 있다.In order to suppress the generation of scale without using a dispersing agent, for example, it is preferable that the concentration of silica in the RO concentrated water be equal to or less than the solubility and the LANGELIER index (index of calcium scale) And adjusting the operating conditions such as the recovery rate of the apparatus.
역침투막장치의 용도로서는, 예를 들면, 순수 제조, 해수 담수화, 배수 회수 등을 들 수 있다.Examples of applications of the reverse osmosis membrane device include pure water production, seawater desalination, drainage recovery, and the like.
<살균제><Disinfectant>
본 실시형태에 따른 살균제는, "브로민계 산화제 또는 염소계 산화제"와 "설팜산 화합물"의 혼합물을 포함하는 안정화 차아브로민산 조성물 또는 안정화 차아염소산 조성물을 함유하는 것이며, 알칼리를 더 함유해도 된다.The bactericide according to the present embodiment contains a stabilized hypobromous acid composition or a stabilized hypochlorous acid composition containing a mixture of "bromine-based oxidizing agent or chlorine-based oxidizing agent" and "sulfamic acid compound", and may further contain an alkali.
또한, 본 실시형태에 따른 살균제는, "브로민계 산화제와 설팜산 화합물의 반응 생성물"을 포함하는 안정화 차아브로민산 조성물, 또는 "염소계 산화제와 설팜산 화합물의 반응 생성물"을 포함하는 안정화 차아염소산 조성물을 함유하는 것이며, 알칼리를 더 함유해도 된다.Further, the bactericide according to the present embodiment is a stabilized hypobromous acid composition comprising a " reaction product of a bromine-based oxidizing agent and a sulfamic acid compound " or a stabilized hypobromous acid composition comprising a " reaction product of a chlorine- And may further contain an alkali.
브로민계 산화제, 브로민화합물, 염소계 산화제 및 설팜산 화합물에 대해서는, 전술한 바와 같다.The bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent and sulfamic acid compound are as described above.
본 실시형태에 따른 살균제로서는, 역침투막을 보다 열화시키지 않기 위해서, 브로민과, 설팜산 화합물을 함유하는 것(브로민과 설팜산 화합물의 혼합물을 함유하는 것), 예를 들면, 브로민과 설팜산 화합물과 알칼리와 물의 혼합물, 또는 브로민과 설팜산 화합물의 반응 생성물을 함유하는 것, 예를 들면, 브로민과 설팜산 화합물의 반응 생성물과, 알칼리와, 물의 혼합물이 바람직하다.As the bactericide according to the present embodiment, bromine and a compound containing a sulfamic acid compound (containing a mixture of a bromine and a sulfamic acid compound), for example, bromine and A mixture of a sulfamic acid compound and an alkali and water or a reaction product of a bromine and a sulfamic acid compound, for example, a reaction product of a bromine and a sulfamic acid compound, and an alkali and water are preferable.
본 실시형태에 따른 살균제 중, 브로민계 산화제와 설팜산 화합물을 포함하는 살균제, 특히 브로민과 설팜산 화합물을 포함하는 살균제는, 염소계 산화제와 설팜산 화합물을 포함하는 살균제(클로로설팜산 등)와 비교하면, 산화력이 높고, 슬라임 억제력, 슬라임 박리력이 현저하게 높은데도 불구하고, 동일하게 산화력이 높은 차아염소산과 같은 현저한 막열화를 거의 야기하는 일이 없다. 통상의 사용 농도에서는, 막열화에의 영향은 실질적으로 무시할 수 있다. 이 때문에, 살균제로서는 최적이다.Among the bactericides according to the present embodiment, the bactericides containing a bromine-based oxidizing agent and a sulfamic acid compound, especially the bactericides containing bromine and a sulfamic acid compound, can be prepared by mixing a bactericide (such as chlorosulfamic acid) containing a chlorine-based oxidizing agent and a sulfamic acid compound Compared with this, remarkable film deterioration such as hypochlorous acid having a high oxidizing power is hardly caused even though the oxidizing power is high, the slime deterring force and the slime peeling force are remarkably high. At the normal use concentration, the influence on the film deterioration can be substantially ignored. Therefore, it is the most suitable as a bactericide.
본 실시형태에 따른 살균제는, 차아염소산과는 달리, 역침투막을 거의 투과하지 않으므로, 처리수 수질에의 영향이 거의 없다. 또한, 차아염소산 등과 같이 현장에서 농도를 측정할 수 있으므로, 보다 정확한 농도 관리가 가능하다.Unlike hypochlorous acid, the bactericide according to the present embodiment does not substantially permeate the reverse osmosis membrane and has little influence on the quality of treated water. In addition, since concentration can be measured in the field such as hypochlorous acid, more accurate concentration control is possible.
살균제의 pH는, 예를 들면, 13.0 초과이며, 13.2 초과인 것이 보다 바람직하다. 살균제의 pH가 13.0 이하이면 살균제 중의 유효 할로겐이 불안정해질 경우가 있다.The pH of the bactericide is, for example, more than 13.0, more preferably more than 13.2. When the pH of the bactericide is 13.0 or less, the effective halogen in the bactericide may become unstable.
살균제 중의 브로민산 농도는, 5㎎/㎏ 미만인 것이 바람직하다. 살균제 중의 브로민산 농도가 5㎎/㎏ 이상이면, RO 투과수의 브로민산 이온의 농도가 높아질 경우가 있다.The concentration of the Bromic acid in the bactericide is preferably less than 5 mg / kg. If the concentration of bromic acid in the bactericide is 5 mg / kg or more, the concentration of bromate ion in the RO permeate water may be increased.
<살균제의 제조 방법>≪ Preparation method of bactericide &
본 실시형태에 따른 살균제는, 브로민계 산화제 또는 염소계 산화제와 설팜산 화합물을 혼합하는 것에 의해 얻어지고, 알칼리를 더 혼합해도 된다.The bactericide according to the present embodiment is obtained by mixing a bromine-based oxidizing agent or a chlorine-based oxidizing agent with a sulfamic acid compound, and further mixed with an alkali.
브로민과, 설팜산 화합물을 포함하는 안정화 차아브로민산 조성물을 함유하는 살균제의 제조 방법으로서는, 물, 알칼리 및 설팜산 화합물을 포함하는 혼합액에 브로민을 불활성 가스 분위기 하에서 첨가해서 반응시키는 공정, 또는 물, 알칼리 및 설팜산 화합물을 포함하는 혼합액에 브로민을 불활성 가스 분위기 하에서 첨가하는 공정을 포함하는 것이 바람직하다. 불활성 가스 분위기 하에서 첨가해서 반응시키거나, 또는 불활성 가스 분위기 하에서 첨가하는 것에 의해, 살균제 중의 브로민산 이온 농도가 낮아지고, RO 투과수 중의 브로민산 이온 농도가 낮아진다.Examples of a method for producing a sterilizing agent containing a stabilized hypobromic acid composition containing bromine and a sulfamic acid compound include a step of adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound under an inert gas atmosphere, or And a step of adding bromine to the mixed solution containing water, an alkali and a sulfamic acid compound under an inert gas atmosphere. When the reaction is carried out in the presence of an inert gas atmosphere or under an inert gas atmosphere, the bromic acid ion concentration in the bactericide is lowered and the bromic acid ion concentration in the RO permeated water is lowered.
이용되는 불활성 가스로서는 한정되지 않지만, 제조 등의 면으로부터 질소 및 아르곤 중 적어도 하나가 바람직하고, 특히 제조 비용 등의 면으로부터 질소가 바람직하다.The inert gas to be used is not limited, but at least one of nitrogen and argon is preferable from the standpoint of production and the like, and nitrogen is preferable from the viewpoint of manufacturing cost and the like.
브로민의 첨가 시의 반응기 내의 산소 농도는 6% 이하가 바람직하지만, 4% 이하가 보다 바람직하고, 2% 이하가 더욱 바람직하며, 1% 이하가 특히 바람직하다. 브로민의 반응 시의 반응기 내의 산소 농도가 6%를 초과하면, 반응계 내의 브로민산의 생성량이 증가될 경우가 있다.The concentration of oxygen in the reactor during the addition of bromine is preferably 6% or less, more preferably 4% or less, still more preferably 2% or less, and particularly preferably 1% or less. When the oxygen concentration in the reactor during the reaction of bromine exceeds 6%, the amount of bromic acid produced in the reaction system sometimes increases.
브로민의 첨가율은, 실리카의 저지율 향상제 전체의 양에 대하여 25중량% 이하인 것이 바람직하고, 1중량% 이상 20중량% 이하인 것이 보다 바람직하다. 브로민의 첨가율이 실리카의 저지율 향상제 전체의 양에 대하여 25중량%를 초과하면, 반응계 내의 브로민산의 생성량이 증가될 경우가 있다. 1중량% 미만이면, 살균력이 뒤떨어질 경우가 있다.The addition amount of bromine is preferably 25% by weight or less, more preferably 1% by weight or more and 20% by weight or less with respect to the total amount of the silica inhibiting agent. When the addition amount of bromine exceeds 25 wt% with respect to the total amount of the silica inhibiting agent, the amount of the produced bromic acid in the reaction system sometimes increases. If it is less than 1% by weight, the sterilizing power may be poor.
브로민 첨가 시의 반응 온도는, 0℃ 이상 25℃ 이하의 범위로 제어하는 것이 바람직하지만, 제조 비용 등의 면으로부터, 0℃ 이상 15℃ 이하의 범위로 제어하는 것이 보다 바람직하다. 브로민 첨가 시의 반응 온도가 25℃를 초과하면, 반응계 내의 브로민산의 생성량이 증가될 경우가 있고, 0℃ 미만이면, 동결될 경우가 있다.The reaction temperature at the time of bromine addition is preferably controlled within the range of 0 占 폚 to 25 占 폚, but from the viewpoint of production cost and the like, it is more preferable to control the reaction temperature within the range of 0 占 폚 to 15 占 폚. When the reaction temperature at the time of bromine addition exceeds 25 DEG C, the amount of the produced bromic acid in the reaction system sometimes increases. When the reaction temperature is lower than 0 DEG C, the reaction may be frozen.
실시예Example
이하, 실시예 및 비교예를 들어, 본 발명을 보다 구체적으로 상세히 설명하지만, 본 발명은, 이하의 실시예로 한정되는 것은 아니다.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.
[안정화 차아브로민산 조성물(조성물 1)의 조제][Preparation of stabilized hypobromic acid composition (composition 1)] [
질소분위기 하에서, 액체 브로민: 16.9중량%(wt%), 설팜산: 10.7중량%, 수산화나트륨: 12.9중량%, 수산화칼륨: 3.94중량%, 물: 잔분을 혼합해서, 안정화 차아브로민산 조성물(조성물 1)을 조제했다. 안정화 차아브로민산 조성물의 pH는 14, 전체 염소 농도는 7.5중량%였다. 안정화 차아브로민산 조성물의 상세한 조제 방법은 이하와 같다.Under the nitrogen atmosphere, the stabilized hypobromic acid composition (composition) was prepared by mixing liquid remnants of bromine: 16.9 wt%, sulfamic acid: 10.7 wt%, sodium hydroxide: 12.9 wt%, potassium hydroxide: 3.94 wt% Composition 1) was prepared. The pH of the stabilized hypobromous acid composition was 14 and the total chlorine concentration was 7.5% by weight. A detailed preparation method of the stabilized hypobromous acid composition is as follows.
반응 용기 내의 산소 농도가 1%로 유지되도록, 질소 가스의 유량을 질량 유량 제어기에 의해 제어하면서 연속 주입으로 봉입한 2ℓ의 4구 플라스크에 1436g의 물, 361g의 수산화나트륨을 첨가하여 혼합하고, 이어서 300g의 설팜산을 첨가해서 혼합한 후, 반응액의 온도가 0 내지 15℃가 되도록 냉각을 유지하면서, 473g의 액체 브로민을 첨가하고, 또한 48% 수산화칼륨 용액 230g을 첨가하고, 조성물 전체의 양에 대한 중량비로 설팜산 10.7%, 브로민 16.9%, 브로민의 당량에 대한 설팜산의 당량비가 1.04인, 목적하는 안정화 차아브로민산 조성물을 얻었다. 얻어진 용액의 pH는, 유리 전극법으로 측정한 바, 14였다. 얻어진 용액의 브로민 함유율은, 브로민을 요오드화칼륨에 의해 요오드로 전환 후, 티오황산나트륨을 이용해서 산화 환원 적정하는 방법에 의해 측정한 바 16.9%이며, 이론 함유율(16.9%)의 100.0%였다. 또한, 브로민 반응 시의 반응 용기 내의 산소 농도는, 주식회사 지코 제품인 "산소 모니터 JKO-02 LJDII"를 이용해서 측정했다. 또, 브로민산 농도는 5㎎/㎏ 미만이었다.1436 g of water and 361 g of sodium hydroxide were added and mixed to a 2 L four-necked flask sealed with continuous injection while the flow rate of nitrogen gas was controlled by a mass flow controller so that the oxygen concentration in the reaction vessel was maintained at 1% After adding 300 g of sulfamic acid and mixing, 473 g of liquid bromine was added while maintaining the temperature of the reaction solution at 0 to 15 캜, and 230 g of a 48% potassium hydroxide solution was added, The desired stabilized hypobromous acid composition was obtained, in which the sulfamoic acid content was 10.7%, bromine content was 16.9%, and the equivalent ratio of sulfamic acid to the equivalent amount of bromine was 1.04. The pH of the obtained solution was 14 as measured by a glass electrode method. The bromine content of the obtained solution was 16.9% as determined by a method of converting bromine to iodine by potassium iodide and then performing redox titration using sodium thiosulfate. The bromine content was 100.0% of the theoretical content (16.9%). The oxygen concentration in the reaction vessel at the time of the bromine reaction was measured using "Oxygen Monitor JKO-02 LJDII" manufactured by Zico Co., Ltd. Also, the concentration of bromic acid was less than 5 mg / kg.
또, pH의 측정은 이하의 조건에서 행하였다. The pH was measured under the following conditions.
전극 타입: 유리 전극식Electrode type: Glass electrode type
pH측정계: 토아DKK사(DKK-TOA CORPORATION) 제품인, IOL-30형태pH meter: IOL-30 form, product of DKK-TOA CORPORATION
전극의 교정: 칸토카가쿠(關東化學)사 제품인 중성 인산염 pH(6.86) 표준액(제2종), 칸토카가쿠사 제품인 붕산염 pH(9.18) 표준액(제2종)의 2점 교정으로 행하였다Calibration of the electrode: Two-point calibration of neutral pH (6.86) standard solution (second grade) manufactured by Kanto Chemical Co., Ltd. and standard solution (second grade) of borate salt pH 9.18 manufactured by Kanto Kagaku Co., Ltd.
측정 온도: 25℃Measuring temperature: 25 ° C
측정값: 측정액에 전극을 침지시키고, 안정 후의 값을 측정값으로 해서 3회 측정의 평균치Measured value: The electrode was immersed in the measuring solution, and the value obtained after the stabilization was used as the measured value. The average value
[안정화 차아염소산 조성물(조성물 2)의 조제][Preparation of stabilized hypochlorous acid composition (Composition 2)] [
12% 차아염소산 나트륨 수용액: 50중량%, 설팜산: 12중량%, 수산화나트륨: 8중량%, 물: 잔분을 혼합하여, 안정화 차아염소산 조성물(조성물2)을 조제했다. 조성물 2의 pH는 13.7, 전체 염소 농도는 6.2중량%였다.A stabilized hypochlorous acid composition (Composition 2) was prepared by mixing 12% sodium hypochlorite aqueous solution: 50% by weight, sulfamic acid: 12% by weight, sodium hydroxide: 8% by weight, and water:
[역침투막의 제타 전위의 측정][Measurement of zeta potential of reverse osmosis membrane]
역침투막의 제타 전위는, 오츠카덴시(大塚電子)주식회사 제품, 제타 전위·입경 측정 시스템 ELSZ 시리즈를 이용해서, 구하였다. 역침투막의 제타 전위는, 측정한 전기 침투 플롯으로부터, 하기 모리·오카모토(森·岡本)의 식 및 스몰루호프스키(Smoluchowski)의 식으로부터 계산했다.The zeta potential of the reverse osmosis membrane was obtained using a zeta potential / particle size measurement system ELSZ series manufactured by Otsuka Electronics Co., Ltd. The zeta potential of the reverse osmosis membrane was calculated from the electro-penetration plots measured from the equation of Himori, Okamoto, and the formula of Smoluchowski.
(모리·오카모토의 식)(Expression of Mori, Okamoto)
Uobs(z) = AU0(z/b)2+ΔU0(z/b)+ (1-A)U0+Up U obs (z) = AU 0 (z / b) 2 + ΔU 0 (z / b) + (1-A)
여기에서,From here,
z: 셀 중심위치부터의 거리z: distance from the cell center position
Uobs(z): 셀 중의 ｚ위치에 있어서의 겉보기의 이동도U obs (z): the apparent mobility at the z-position in the cell
A: 1/[(2/3) - (0.420166/K)]A: 1 / [(2/3) - (0.420166 / K)]
K = a/b: 2a와 2b는 셀 단면의 가로와 세로의 길이, a>bK = a / b: 2a and 2b are the lengths of the cross section of the cell cross section, and a> b
Up: 입자의 참 이동도U p : True mobility of particles
U0: 셀의 상부면, 하부면에 있어서의 평균 이동도U 0 : Average mobility on the upper and lower surfaces of the cell
ΔU0: 셀의 상부면, 하부면에 있어서의 이동도의 차ΔU 0 : Difference in mobility on the upper and lower surfaces of the cell
(스몰루호프스키의 식)(Expression of Small Rhoffsky)
ζ = 4πηU/εζ = 4πηU / ε
여기에서,From here,
U: 전기이동도U: Electricity mobility
ε: 용매의 유전율ε: permittivity of solvent
η: 용매의 점도η: viscosity of solvent
측정액으로서 10mM NaCl 수용액(pH 약 5.4)을 사용했다. 이 수용액과 시료의 쌍을 각 시료에 대해서 2조 준비하여, 한쪽은 pH를 산성(pH 2, 3, 4, 5, 6, 7)으로, 다른 쪽은 pH를 알카리성(pH 8, 9)으로 조정해서, 각 pH에 있어서의 제타 전위를 측정했다. 용매의 물성값은 25℃에 있어서의 순수의 값(굴절률: 1.3328, 점도: 0.8878, 유전율: 78.3)을 사용했다.A 10 mM NaCl aqueous solution (pH of about 5.4) was used as a measuring solution. Two pairs of the aqueous solution and the sample were prepared for each sample, and the pH was acidic (
<실시예 1 및 비교예 1>≪ Example 1 and Comparative Example 1 >
[시험 조건 및 시험 방법][Test conditions and test method]
평막시험에서 살균제의 투과수 농도를 측정했다. 평막 셀은, 닛토덴코사 제품인 멤브렌마스터 C70-F 플로우식 평막 테스트 셀을 이용했다. 평막에는, 닛토덴코사 제품인 역침투막(음이온 하전막 "ES20"(폴리아마이드계 음이온 하전막))을 이용하였다. 평막은 원형으로, 직경이 75㎜인 것을 이용하였다. 흐름을 도 1에 나타낸다.In the flat membrane test, the permeate concentration of the bactericide was measured. As the flat membrane cell, a Membrane Master C70-F flow flat membrane test cell manufactured by Nitto Denko Co., Ltd. was used. For the flat membrane, a reverse osmosis membrane (anion underlayer "ES20" (polyamide-based anion underlayer)) manufactured by Nitto Denko Co., Ltd. was used. The flat membrane was circular and had a diameter of 75 mm. The flow is shown in Fig.
시험수(피처리수)는, 초순수에 살균제를 첨가하고, pH가 7.0이 되도록 염산 또는 수산화나트륨을 이용해서 조제한 것을 사용했다. 살균제의 농도는 전체 염소 농도로 약 6㎎/ℓ로 했다. 수온은 25±1℃가 되도록 냉각기를 이용해서 조절했다. 역침투막의 조작압은 0.75㎫로 했다. 역침투막에의 공급수는 5ℓ/분으로 통수시켰다. 3시간 정도의 통수 후, 피처리수 및 투과수의 살균제 농도(전체 염소 농도)를 측정했다. 전체 염소 농도는, HACH사의 다항목 수질분석계 DR/4000을 이용해서, 전체 염소측정법(DPD(다이에틸-p-페닐렌다이아민)법)에 의해 측정한 값(㎎/ℓ, Cl2로서)이다.The test water (for-treatment water) was prepared by adding a sterilizing agent to ultrapure water and using hydrochloric acid or sodium hydroxide so as to have a pH of 7.0. The concentration of the bactericide was about 6 mg / l as the total chlorine concentration. The water temperature was adjusted to 25 ± 1 ℃ using a cooler. The operation pressure of the reverse osmosis membrane was 0.75 MPa. The feed rate to the reverse osmosis membrane was 5 liters / minute. After passing water for about 3 hours, the bactericide concentration (total chlorine concentration) of the for-treatment water and the permeated water was measured. The total chlorine concentration was measured (as mg / l, Cl 2 ) by the total chlorine measurement method (DPD (diethyl-p-phenylenediamine) method) by using a multi-item water quality analyzer DR / to be.
(실시예 1)(Example 1)
실시예 1로서, 피처리수에 암모니아 농도가 1㎎/ℓ이 되도록 염화암모니아를 첨가하고, 그때의 각 살균제의 피처리수 농도 및 투과수 농도를 측정하고, 투과율을 구했다. 결과를 표 1에 나타낸다.As Example 1, ammonia chloride was added to the water to be treated so as to have an ammonia concentration of 1 mg / L, the concentration of the water to be treated and the concentration of permeated water of each sterilizing agent at that time was measured, and the permeability was obtained. The results are shown in Table 1.
(비교예 1)(Comparative Example 1)
또한, 비교예 1로서, 피처리수에 염화암모니아를 첨가하지 않았을 경우의 각 살균제의 피처리수 농도 및 투과수 농도를 측정하고, 투과율을 구했다. 결과를 표 2에 나타낸다.In addition, as Comparative Example 1, the concentration of the water to be treated and the concentration of the permeated water of each bactericide in the case where ammonia chloride was not added to the water to be treated was measured, and the permeability was determined. The results are shown in Table 2.
[㎎/ℓ]Fungicide concentration
[Mg / l]
[㎎/ℓ]Permeate sanitizer concentration
[Mg / l]
[%]Bactericide permeability
[%]
[㎎/ℓ]Fungicide concentration
[Mg / l]
[㎎/ℓ]Permeate sanitizer concentration
[Mg / l]
[%]Bactericide permeability
[%]
이와 같이, 실시예 1과 같이 피처리수에 암모니아가 존재함으로써, 살균제 투과율이 향상되는 것을 일 수 있다.Thus, as in Example 1, the presence of ammonia in the for-treatment water may improve the bactericide permeability.
<실시예 2>≪ Example 2 >
실시예 2에서는, 평막으로서, 중성막인, LFC3(닛토덴코 주식회사 제품), TML20(토레 주식회사 제품), 음이온 하전막인, OFR-625(오르가노 주식회사 제품), ES15, ES20, CPA5(이상, 닛토덴코 주식회사 제품)를 이용하고, 살균제로서, 안정화 차아브로민산 조성물(조성물 1)을 이용해서, 실시예 1과 마찬가지로 도 1의 흐름으로 하기 조건 및 방법으로 투과수 농도를 측정했다.In Example 2, as the flat membrane, a neutral membrane such as LFC3 (manufactured by Nitto Denko Corporation), TML20 (manufactured by Toray Industries, Inc.), OFR-625 (manufactured by ORGANO CORPORATION) and ES15, ES20, CPA5 (Manufactured by Nitto Denko Co., Ltd.) and a stabilized hypochlorous acid composition (composition 1) was used as a bactericide, the permeated water concentration was measured in the flow of Fig.
시험수(피처리수)는, 초순수에 살균제를 첨가하고, pH가 7.0이 되도록 염산 또는 수산화나트륨을 이용해서 조제한 것을 사용하였다. 살균제의 농도는 전체 염소 농도로 10㎎/ℓ로 하였다. 수온은 25±1℃가 되도록 냉각기를 이용해서 조절했다. 역침투막의 조작압은 0.75㎫로 했다. 역침투막에의 공급수는 5 ℓ/분으로 통수시켰다. 피처리수에 암모니아 농도가 0, 0.1, 0.5, 1,5, 10㎎/ℓ가 되도록 염화암모니아를 첨가하고, 3시간 정도의 통수 후, 각 살균제의 피처리수 농도(전체 염소 농도) 및 투과수 농도(전체 염소 농도)를 측정하고, 투과율을 구했다. 결과를 표 3 및 도 2에 나타낸다.The test water (for-treatment water) was prepared by adding a sterilizing agent to ultrapure water and using hydrochloric acid or sodium hydroxide so as to have a pH of 7.0. The concentration of the bactericide was 10 mg / L as the total chlorine concentration. The water temperature was adjusted to 25 ± 1 ℃ using a cooler. The operation pressure of the reverse osmosis membrane was 0.75 MPa. The feed rate to the reverse osmosis membrane was 5 liters / minute. Ammonium chloride was added to the water to be treated so as to have ammonia concentrations of 0, 0.1, 0.5, 1, 5, and 10 mg / liter. After passing water for 3 hours, the concentration of the water to be treated (total chlorine concentration) The water concentration (total chlorine concentration) was measured, and the transmittance was obtained. The results are shown in Table 3 and FIG.
번호Film type
number
(%)Total chlorine permeability
(%)
이와 같이, 음이온 하전막을 이용한 경우, 중성막을 이용한 경우에 비해서, 살균제의 투과율이 높고, 역침투막의 2차 측에 있어서도 슬라임 오염을 보다 억제할 수 있는 것을 알 수 있었다.As described above, when the anion charged membrane was used, it was found that the permeability of the sterilizing agent was high and the slime contamination could be further suppressed even on the secondary side of the reverse osmosis membrane, as compared with the case of using a neutral membrane.
이상과 같이, 실시예 1의 방법에 의해, 역침투막의 2차 측에 있어서도 슬라임 오염을 억제하고, 그리고 역침투막의 산화 열화를 억제할 수 있었다.As described above, slime contamination was suppressed even in the secondary side of the reverse osmosis membrane by the method of Example 1, and oxidation deterioration of the reverse osmosis membrane was suppressed.
Claims (6)
암모니아를 함유하는 상기 피처리수 중에, 브로민계 산화제 또는 염소계 산화제와 설팜산 화합물을 포함하는 살균제를 존재시키는 것을 특징으로 하는, 역침투막을 이용하는 수처리 방법.A water treatment method using a reverse osmosis membrane for treating water to be treated with a reverse osmosis membrane,
Characterized in that a bromine-based oxidizing agent or a sterilizing agent containing a chlorine-based oxidizing agent and a sulfamic acid compound is present in the for-treatment water containing ammonia.
암모니아를 함유하는 상기 피처리수 중에, 브로민과 설팜산 화합물을 포함하는 살균제를 존재시키는 것을 특징으로 하는, 역침투막을 이용하는 수처리 방법.A water treatment method using a reverse osmosis membrane for treating water to be treated with a reverse osmosis membrane,
A water treatment method using a reverse osmosis membrane, wherein a disinfectant containing bromine and a sulfamic acid compound is present in the for-treatment water containing ammonia.
상기 피처리수 중의 전체 염소 농도에 대한 상기 암모니아의 농도의 비가 0.01 내지 1의 범위가 되도록 상기 살균제 또는 상기 암모니아의 농도를 조정하는 것을 특징으로 하는, 역침투막을 이용하는 수처리 방법.3. The method according to claim 1 or 2,
Characterized in that the concentration of the bactericide or the ammonia is adjusted such that the ratio of the concentration of ammonia to the total chlorine concentration in the for-treatment water is in the range of 0.01 to 1. 2. The water treatment method according to claim 1,
상기 역침투막이 음이온 하전막인 것을 특징으로 하는, 역침투막을 이용하는 수처리 방법.4. The method according to any one of claims 1 to 3,
Wherein the reverse osmosis membrane is an anion-under-ion membrane.
상기 피처리수가 상기 역침투막을 투과하는 유기물을 0.5㎎/ℓ 이상 포함하는 것을 특징으로 하는, 역침투막을 이용하는 수처리 방법.5. The method according to any one of claims 1 to 4,
Characterized in that the water to be treated contains 0.5 mg / L or more of organic matter permeating through the reverse osmosis membrane.
투과수를 사용점에서 사용하지 않을 때에만 상기 살균제를 첨가해서 상기 피처리수 중에 존재시키는 것을 특징으로 하는, 역침투막을 이용하는 수처리 방법.6. The method according to any one of claims 1 to 5,
Wherein the sterilizing agent is added only when the permeated water is not used at the point of use and is present in the for-treatment water.
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| WO2012132892A1 (en) * | 2011-03-30 | 2012-10-04 | 栗田工業株式会社 | Scale preventing agent for reverse osmosis membrane and scale preventing method |
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| CN104801195A (en) * | 2015-04-30 | 2015-07-29 | 浙江农林大学 | Novel method for cleaning organic pollutants of reverse osmosis membrane and nanofiltration membrane |
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| JP2005185985A (en) * | 2003-12-26 | 2005-07-14 | Toray Ind Inc | Method and apparatus for producing water |
| JP2006263510A (en) | 2005-03-22 | 2006-10-05 | Kurita Water Ind Ltd | Anti-slime agent for membrane separation and membrane separation method |
| JP2015062889A (en) | 2013-08-28 | 2015-04-09 | オルガノ株式会社 | Method for inhibiting slime in separation membrane, slime inhibition agent composition for separation membrane, and method for producing slime inhibition agent composition for separation membrane |
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