JP6630562B2 - Slime suppression method for separation membrane - Google Patents
Slime suppression method for separation membrane Download PDFInfo
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- JP6630562B2 JP6630562B2 JP2015247043A JP2015247043A JP6630562B2 JP 6630562 B2 JP6630562 B2 JP 6630562B2 JP 2015247043 A JP2015247043 A JP 2015247043A JP 2015247043 A JP2015247043 A JP 2015247043A JP 6630562 B2 JP6630562 B2 JP 6630562B2
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- JP
- Japan
- Prior art keywords
- membrane
- bromine
- separation membrane
- water
- trihalomethane
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims description 211
- 238000000926 separation method Methods 0.000 title claims description 132
- 238000000034 method Methods 0.000 title claims description 65
- 230000001629 suppression Effects 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 158
- -1 bromine compound Chemical class 0.000 claims description 100
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 93
- 239000000203 mixture Substances 0.000 claims description 89
- 229910052794 bromium Inorganic materials 0.000 claims description 88
- 239000007800 oxidant agent Substances 0.000 claims description 68
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 64
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 62
- 239000000460 chlorine Substances 0.000 claims description 62
- 229910052801 chlorine Inorganic materials 0.000 claims description 62
- 239000002243 precursor Substances 0.000 claims description 40
- 238000001223 reverse osmosis Methods 0.000 claims description 36
- 239000007795 chemical reaction product Substances 0.000 claims description 33
- 230000001590 oxidative effect Effects 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 229920002647 polyamide Polymers 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000001728 nano-filtration Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229920006254 polymer film Polymers 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims 3
- 238000005374 membrane filtration Methods 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000003112 inhibitor Substances 0.000 description 25
- 229910052736 halogen Inorganic materials 0.000 description 21
- 150000002367 halogens Chemical group 0.000 description 21
- 230000000694 effects Effects 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 14
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 11
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000005708 Sodium hypochlorite Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004021 humic acid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 6
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920005597 polymer membrane Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- GATVIKZLVQHOMN-UHFFFAOYSA-N Chlorodibromomethane Chemical compound ClC(Br)Br GATVIKZLVQHOMN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas 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
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229950005228 bromoform Drugs 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 3
- 229940005991 chloric acid Drugs 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 3
- 235000020681 well water Nutrition 0.000 description 3
- 239000002349 well water Substances 0.000 description 3
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- FMWLUWPQPKEARP-UHFFFAOYSA-N bromodichloromethane Chemical compound ClC(Cl)Br FMWLUWPQPKEARP-UHFFFAOYSA-N 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229940095100 fulvic acid Drugs 0.000 description 2
- 239000002509 fulvic acid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 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
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 241000282994 Cervidae Species 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- WOHVONCNVLIHKY-UHFFFAOYSA-L [Ba+2].[O-]Cl=O.[O-]Cl=O Chemical compound [Ba+2].[O-]Cl=O.[O-]Cl=O WOHVONCNVLIHKY-UHFFFAOYSA-L 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- VWPXUKSDWYXLKV-UHFFFAOYSA-N bromosulfamic acid Chemical compound OS(=O)(=O)NBr VWPXUKSDWYXLKV-UHFFFAOYSA-N 0.000 description 1
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 0.000 description 1
- FECFIIXKXJBOSU-UHFFFAOYSA-N butylsulfamic acid Chemical group CCCCNS(O)(=O)=O FECFIIXKXJBOSU-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- BAQKWXACUNEBOT-UHFFFAOYSA-N dibutylsulfamic acid Chemical compound CCCCN(S(O)(=O)=O)CCCC BAQKWXACUNEBOT-UHFFFAOYSA-N 0.000 description 1
- YGNOYUCUPMACDT-UHFFFAOYSA-N dimethylsulfamic acid Chemical compound CN(C)S(O)(=O)=O YGNOYUCUPMACDT-UHFFFAOYSA-N 0.000 description 1
- XRVWREPFYXZOPK-UHFFFAOYSA-N dipropylsulfamic acid Chemical compound CCCN(S(O)(=O)=O)CCC XRVWREPFYXZOPK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IOISAJSHULNACL-UHFFFAOYSA-N ethyl(methyl)sulfamic acid Chemical compound CCN(C)S(O)(=O)=O IOISAJSHULNACL-UHFFFAOYSA-N 0.000 description 1
- SIVVHUQWDOGLJN-UHFFFAOYSA-N ethylsulfamic acid Chemical compound CCNS(O)(=O)=O SIVVHUQWDOGLJN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- YZVQGLCYZLGIAM-UHFFFAOYSA-N methyl(propyl)sulfamic acid Chemical compound CCCN(C)S(O)(=O)=O YZVQGLCYZLGIAM-UHFFFAOYSA-N 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical compound CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 244000005700 microbiome Species 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 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
- 230000002265 prevention Effects 0.000 description 1
- JWQSOOZHYMZRBT-UHFFFAOYSA-N propan-2-ylsulfamic acid Chemical group CC(C)NS(O)(=O)=O JWQSOOZHYMZRBT-UHFFFAOYSA-N 0.000 description 1
- HLIBNTOXKQCYMV-UHFFFAOYSA-N propylsulfamic acid Chemical compound CCCNS(O)(=O)=O HLIBNTOXKQCYMV-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical group OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
本発明は、逆浸透膜（ＲＯ膜）等の分離膜のスライム抑制方法に関する。 The present invention relates to a method for suppressing slime of a separation membrane such as a reverse osmosis membrane (RO membrane).
逆浸透膜（ＲＯ膜）等の分離膜のスライム抑制方法としては、各種のスライム抑制剤を使用する方法が知られている。次亜塩素酸等の塩素系酸化剤は代表的なスライム抑制剤であり、系内のスライム抑制目的で通常は分離膜の前段に添加される。塩素系酸化剤は分離膜を劣化させる可能性が高いため、一般的には分離膜の直前で塩素系酸化剤を還元分解するか、間欠的に塩素系酸化剤を分離膜に流入させることで運用されている（特許文献１参照）。 As a slime suppressing method for a separation membrane such as a reverse osmosis membrane (RO membrane), a method using various slime suppressing agents is known. A chlorine-based oxidizing agent such as hypochlorous acid is a typical slime inhibitor, and is usually added before the separation membrane for the purpose of suppressing slime in the system. Chlorine-based oxidizing agents are likely to degrade the separation membrane, so in general, the chlorine-based oxidizing agent is reduced or decomposed immediately before the separation membrane or intermittently flows into the separation membrane. It is in operation (see Patent Document 1).
塩素系酸化剤は、水中にフミン質等のトリハロメタン前駆物質が存在する場合、それらと反応し、クロロホルム等のトリハロメタンを生成することが知られている。ここで、これらの塩素系酸化剤によって生成されるトリハロメタンは、分離膜で排除され難く、分離膜の透過水中へ漏洩しやすいという問題があることが、本発明者らの検討により明らかとなった。 It is known that a chlorine-based oxidizing agent reacts with a trihalomethane precursor such as a humic substance in water to produce a trihalomethane such as chloroform when present in water. Here, the study by the present inventors has revealed that trihalomethane generated by these chlorine-based oxidizing agents is difficult to be eliminated by the separation membrane, and has a problem of easily leaking into permeated water of the separation membrane. .
本発明の目的は、トリハロメタン前駆物質を含有する給水または洗浄水を用いる膜分離装置において、十分なスライム抑制効果を有しながら、透過水中のトリハロメタン含有量を低減することが可能な分離膜のスライム抑制方法を提供することにある。 An object of the present invention is to provide a slime of a separation membrane capable of reducing the trihalomethane content in permeated water while having a sufficient slime suppressing effect in a membrane separation device using feed water or washing water containing a trihalomethane precursor. It is to provide a control method.
本発明は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、を存在させ、前記給水または洗浄水のトリハロメタン前駆物質の濃度が、トリハロメタン生成能として０．０１ｍｇ／Ｌ以上であり、前記分離膜は、ポリアミド系高分子膜である逆浸透膜またはナノろ過膜である分離膜のスライム抑制方法である。 The present invention contains a trihalomethane precursor, in water supply or washing water to a membrane separation device provided with a separation membrane, a bromine-based oxidant, or a reactant of a bromine compound and a chlorine-based oxidant, a sulfamic acid compound, Wherein the concentration of the trihalomethane precursor in the feed water or the washing water is 0.01 mg / L or more as a trihalomethane generating ability, and the separation membrane is a reverse osmosis membrane or a nanofiltration membrane which is a polyamide-based polymer membrane. a slime method for suppressing Oh Ru separation membrane.
本発明は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物を存在させ、前記給水または洗浄水のトリハロメタン前駆物質の濃度が、トリハロメタン生成能として０．０１ｍｇ／Ｌ以上であり、前記分離膜は、ポリアミド系高分子膜である逆浸透膜またはナノろ過膜である分離膜のスライム抑制方法である。 The present invention contains a trihalomethane precursor, in water supply or washing water to a membrane separation device provided with a separation membrane, a bromine-based oxidant, or a reactant of a bromine compound and a chlorine-based oxidant, a sulfamic acid compound, Wherein the concentration of the trihalomethane precursor in the feed water or the washing water is 0.01 mg / L or more as a trihalomethane-producing ability, and the separation membrane is a reverse osmosis membrane or a polyamide polymer membrane. nanofiltration is slime method for suppressing excessive film der Ru separation membrane.
本発明は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、臭素とスルファミン酸化合物の混合物、または、臭素とスルファミン酸化合物との反応生成物を存在させ、前記給水または洗浄水のトリハロメタン前駆物質の濃度が、トリハロメタン生成能として０．０１ｍｇ／Ｌ以上であり、前記分離膜は、ポリアミド系高分子膜である逆浸透膜またはナノろ過膜である分離膜のスライム抑制方法である。 The present invention contains a trihalomethane precursor, a mixture of bromine and a sulfamic acid compound, or a reaction product of a bromine and a sulfamic acid compound, in water or washing water supplied to a membrane separation device provided with a separation membrane , the concentration of trihalomethane precursors of the water or wash water, and a 0.01 mg / L or more as trihalomethane formation potential, the separation membrane, reverse osmosis membrane or a nanofiltration membrane der Ru separation membrane is a polyamide-based polymer membrane Is a method for suppressing slime.
前記分離膜のスライム抑制方法において、前記臭素とスルファミン酸化合物との反応生成物が、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加して反応させる工程を含む方法により得られたものであることが好ましい。 In the slime suppressing method for the separation membrane, the reaction product of the bromine and the sulfamic acid compound includes a step of reacting by adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound under an inert gas atmosphere. It is preferably obtained by the method.
前記分離膜のスライム抑制方法において、前記トリハロメタン前駆物質がフミン質を含むことが好ましい。 In the method for controlling slime of a separation membrane, it is preferable that the trihalomethane precursor includes humic substances.
本発明では、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、臭素系酸化剤、もしくは臭素化合物と塩素系酸化剤との反応物を存在させることにより；臭素系酸化剤、もしくは臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物とを存在させることにより；臭素系酸化剤、もしくは臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物を存在させることにより；臭素とスルファミン酸化合物の混合物を存在させることにより；または、臭素とスルファミン酸化合物との反応生成物を存在させることにより、十分なスライム抑制効果を有しながら、透過水中のトリハロメタン含有量を低減することが可能となる。 In the present invention, a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent is present in water or washing water containing a trihalomethane precursor and provided to a membrane separation device provided with a separation membrane; A bromine-based oxidant, or a reaction product of a bromine compound and a chlorine-based oxidant, and a sulfamate compound; and a sulfamate compound; And the presence of a mixture of bromine and a sulfamic acid compound; or the presence of a reaction product of bromine and a sulfamic acid compound, thereby having a sufficient slime suppression effect. Meanwhile, the trihalomethane content in the permeated water can be reduced.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 An embodiment of the present invention will be described below. The present embodiment is an example for implementing the present invention, and the present invention is not limited to the present embodiment.
＜分離膜のスライム抑制方法＞
本発明の実施形態に係る分離膜のスライム抑制方法は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、スライム抑制剤として「臭素系酸化剤」を存在させる方法、または次亜臭素酸等の「臭素化合物と塩素系酸化剤との反応物」を存在させる方法である。
<Method of controlling slime of separation membrane>
The method for suppressing slime of a separation membrane according to an embodiment of the present invention includes a trihalomethane precursor, wherein “bromine-based oxidizing agent” is present as a slime inhibitor in water supplied to a membrane separation device provided with a separation membrane or in washing water. Or a method in which a "reactant of a bromine compound and a chlorine-based oxidizing agent" such as hypobromous acid is present.
本発明の実施形態に係る分離膜のスライム抑制方法は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、スライム抑制剤として「臭素系酸化剤」と「スルファミン酸化合物」とを存在させる方法、または「臭素化合物と塩素系酸化剤との反応物」と「スルファミン酸化合物」とを存在させる方法である。これにより、給水または洗浄水中で、次亜臭素酸安定化組成物が生成すると考えられる。 The method for controlling slime of a separation membrane according to an embodiment of the present invention comprises a method for controlling a slime of a bromine-based oxidizing agent and a sulphamine in a feed water or a washing water containing a trihalomethane precursor to a membrane separation device provided with a separation membrane. An acid compound "or a" reaction product of a bromine compound and a chlorine-based oxidizing agent "and a" sulfamic acid compound ". Thereby, it is considered that the hypobromite stabilized composition is formed in the feed water or the wash water.
また、本発明の実施形態に係る分離膜のスライム抑制方法は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、スライム抑制剤として「臭素系酸化剤とスルファミン酸化合物との反応生成物」である次亜臭素酸安定化組成物を存在させる方法、または「臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物」である次亜臭素酸安定化組成物を存在させる方法である。 In addition, the method for controlling slime of a separation membrane according to the embodiment of the present invention includes the steps of: containing a trihalomethane precursor; supplying water or washing water to a membrane separation device provided with a separation membrane; A method of causing a hypobromite-stabilized composition, which is a reaction product of an acid compound, or a reaction product of a reaction product of a bromine compound and a chlorine-based oxidizing agent with a sulfamic acid compound. This is a method in which a hypobromite stabilized composition is present.
具体的には本発明の実施形態に係る分離膜のスライム抑制方法は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、例えば、「臭素」、「塩化臭素」、「次亜臭素酸」または「臭化ナトリウムと次亜塩素酸との反応物」を存在させる方法である。 Specifically, the method for suppressing slime of a separation membrane according to the embodiment of the present invention includes a process for containing a trihalomethane precursor, in a feed water or a washing water to a membrane separation device provided with a separation membrane, for example, “bromine”, “bromine chloride”. "," Hypobromous acid "or" reacted product of sodium bromide and hypochlorous acid ".
本発明の実施形態に係る分離膜のスライム抑制方法は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、例えば、「臭素」、「塩化臭素」、「次亜臭素酸」または「臭化ナトリウムと次亜塩素酸との反応物」と、「スルファミン酸化合物」と、を存在させる方法である。 The method for suppressing slime of a separation membrane according to an embodiment of the present invention includes a method for containing a trihalomethane precursor and supplying or washing water to a membrane separation apparatus having a separation membrane, for example, “bromine”, “bromine chloride”, “ This is a method in which a "bromous acid" or a "reacted product of sodium bromide and hypochlorous acid" and a "sulfamic acid compound" are present.
また、本発明の実施形態に係る分離膜のスライム抑制方法は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、例えば、「臭素とスルファミン酸化合物との反応生成物」、「塩化臭素とスルファミン酸化合物との反応生成物」、または「臭化ナトリウムと次亜塩素酸との反応物と、スルファミン酸化合物と、の反応生成物」である次亜臭素酸安定化組成物を存在させる方法である。なお、「臭素とスルファミン酸化合物との反応生成物」として、どのような化合物が生じているかは明らかではないが、次亜臭素酸安定化化合物である「ブロモスルファミン酸」が生成していると考えられる。 In addition, the method for suppressing slime of a separation membrane according to the embodiment of the present invention includes a method of containing a trihalomethane precursor, in supplying or washing water to a membrane separation device provided with a separation membrane, for example, the reaction of bromine and a sulfamic acid compound. Hypobromous acid, which is a product, a reaction product of bromine chloride and a sulfamic acid compound, or a reaction product of a reaction product of sodium bromide and hypochlorous acid with a sulfamic acid compound This is a method in which a stabilizing composition is present. Although it is not clear what kind of compound is generated as `` reaction product of bromine and sulfamic acid compound '', it is assumed that `` bromosulfamic acid '' which is a hypobromite stabilized compound is generated. Conceivable.
これらの方法により、トリハロメタン前駆物質を含有する給水または洗浄水を用いる膜分離装置における分離膜のスライム発生を抑制しつつ、透過水中のトリハロメタン含有量を低減することができる。また、分離膜の性能をほとんど劣化させることなく、微生物による膜汚染を確実に抑制することができる。本実施形態に係る分離膜のスライム抑制方法により、高いスライム抑制効果を有しながら、膜性能、後段水質への影響を最小限に抑えたスライム抑制処理が可能となる。 According to these methods, it is possible to reduce the trihalomethane content in the permeated water while suppressing the generation of slime on the separation membrane in a membrane separation apparatus using feed water or washing water containing a trihalomethane precursor. In addition, membrane contamination by microorganisms can be reliably suppressed without substantially deteriorating the performance of the separation membrane. The slime suppression method of the separation membrane according to the present embodiment enables a slime suppression treatment that has a high slime suppression effect and minimizes the influence on membrane performance and downstream water quality.
臭素系酸化剤および次亜臭素酸安定化組成物も塩素系酸化剤と同様に、トリハロメタン前駆物質と反応し、トリハロメタンを生成するが、臭素系酸化剤および次亜臭素酸安定化組成物によって生成されるトリハロメタンはブロモホルム等の臭素系トリハロメタンが主であり、塩素系酸化剤により生成されるクロロホルム等の塩素系トリハロメタンよりも分離膜で排除され易く、分離膜の透過水中のトリハロメタンが大幅に低減されると考えられる。臭素系トリハロメタンの分離膜での排除率が高い理由としては、詳細は不明であるが、臭素系トリハロメタンが塩素系トリハロメタンと比較して、相対的に分子量が大きいこと等が推測される。 Bromine-based oxidizing agents and hypobromite-stabilized compositions also react with trihalomethane precursors to produce trihalomethanes, similar to chlorine-based oxidizing agents, but are produced by brominated oxidizing agents and hypobromite-stabilized compositions. Trihalomethanes are mainly brominated trihalomethanes such as bromoform, and are more easily removed by a separation membrane than chlorine-based trihalomethanes such as chloroform generated by a chlorine-based oxidizing agent. It is thought that. The reason why the rejection ratio of brominated trihalomethane on the separation membrane is high is unknown, but it is presumed that brominated trihalomethane has a relatively large molecular weight as compared with chlorine-based trihalomethane.
このように、本実施形態に係る分離膜のスライム抑制方法は、次亜塩素酸等の塩素系酸化剤と同等以上のスライム抑制効果を発揮するにも関わらず、塩素系酸化剤と比較すると、生成する臭素系トリハロメタンの分離膜での排除率が著しく高いため、分離膜の透過水中のトリハロメタンを大幅に低減できる。このため、本実施形態に係る分離膜のスライム抑制方法で用いられるスライム抑制剤は分離膜用スライム抑制剤としては好適である。 Thus, the slime suppression method of the separation membrane according to the present embodiment, despite exhibiting a slime suppression effect equal to or more than a chlorine-based oxidizing agent such as hypochlorous acid, compared with a chlorine-based oxidizing agent, Since the rejection rate of the generated brominated trihalomethane at the separation membrane is extremely high, trihalomethane in the permeated water of the separation membrane can be significantly reduced. For this reason, the slime inhibitor used in the method for controlling slime of a separation membrane according to the present embodiment is suitable as a slime inhibitor for a separation membrane.
本実施形態に係る分離膜のスライム抑制方法のうち、「臭素系酸化剤」と「スルファミン酸化合物」とを存在させる方法、「臭素化合物と塩素系酸化剤との反応物」と「スルファミン酸化合物」とを存在させる方法、「臭素系酸化剤とスルファミン酸化合物との反応生成物」を存在させる方法、または「臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物」を存在させる方法は、分離膜への劣化影響が著しく低く、分離膜に直接流入させてスライム抑制をすることができる。このため、これらのスライム抑制方法で用いられるスライム抑制剤は分離膜用スライム抑制剤としてはより好適である。 Among the slime suppression methods for the separation membrane according to the present embodiment, a method in which a “bromine-based oxidizing agent” and a “sulfamic acid compound” are present, a “reactant of a bromine compound and a chlorine-based oxidizing agent” and a “sulfamic acid compound” ), A method of causing a `` reaction product of a brominated oxidizing agent and a sulfamic acid compound '', or a method of forming a `` reaction product of a brominated compound and a chlorine oxidizing agent with a sulfamic acid compound '' In the method in which the “product” is present, the deterioration effect on the separation membrane is extremely low, and the slime can be suppressed by directly flowing into the separation membrane. For this reason, the slime suppressants used in these slime control methods are more suitable as slime suppressants for separation membranes.
本実施形態に係る分離膜のスライム抑制方法のうち、「臭素系酸化剤」、または「臭素化合物と塩素系酸化剤との反応物」が、臭素である場合、塩素系酸化剤が存在しないため、分離膜での排除率の低い塩素系トリハロメタンの生成量も低くなり、分離膜用スライム抑制剤としてはさらに好適である。塩素系酸化剤を含む場合は、塩素酸の生成が懸念される。 In the method for suppressing slime of a separation membrane according to the present embodiment, the "bromine-based oxidizing agent" or the "reactant of a bromine compound and a chlorine-based oxidizing agent" is bromine, because the chlorine-based oxidizing agent does not exist. In addition, the amount of chlorinated trihalomethane having a low rejection rate in the separation membrane is reduced, which is more suitable as a slime inhibitor for separation membranes. When a chlorine-based oxidizing agent is contained, chloric acid may be generated.
トリハロメタンは、メタンの３つの水素原子がハロゲンで置換されたものを指すが、例えば、クロロホルム、ブロモジクロロメタン、ジブロモクロロメタンおよびブロモホルム等が挙げられる。トリハロメタン前駆物質は、トリハロメタンの前駆体となる物質であればよく特に制限はないが、例えば、１，３−ジケトン構造を有する化合物、１，３−ジヒドロキシベンゼン構造を有する化合物等が挙げられる。トリハロメタン前駆物質の具体例としては、例えば、フミン酸やフルボ酸を含むフミン質等が挙げられる。ここで、フミン質（腐植物質）は、植物の葉や茎等の部分が腐植してできた有機成分であり、フミン質の中で酸により沈殿する分画をフミン酸、沈殿しない分画をフルボ酸と呼ぶ。 Trihalomethane refers to one in which three hydrogen atoms of methane are substituted with halogen, and examples thereof include chloroform, bromodichloromethane, dibromochloromethane, and bromoform. The trihalomethane precursor is not particularly limited as long as it is a substance that becomes a precursor of trihalomethane, and examples thereof include a compound having a 1,3-diketone structure and a compound having a 1,3-dihydroxybenzene structure. Specific examples of the trihalomethane precursor include, for example, humic substances including humic acid and fulvic acid. Here, humic substances (humic substances) are organic components formed by humification of leaves and stems of plants. Called fulvic acid.
トリハロメタン前駆物質は、トリハロメタン生成能（ＴＨＭＦＰ）（ｍｇ／Ｌ）として、「特定水道利水障害防止のための水道水源域の水質の保全に関する特別法」に基づいた測定方法で測定することができる。具体的には、試料をｐＨ７．０、温度２０℃、反応時間２４時間、２４時間後の遊離残留塩素濃度が１〜２ｍｇ／Ｌとなるように次亜塩素酸ナトリウムを添加した条件で、生成したトリハロメタン生成量をパージ・トラップ−ガスクロマトグラフ−質量分析計による一斉分析法で測定して、求める方法である。また、トリハロメタン前駆物質は、ＴＯＣ計等でも測定することができる。 The trihalomethane precursor can be measured as a trihalomethane generating ability (THMFP) (mg / L) by a measurement method based on the “Special Law on Conservation of Water Quality in Tap Water Source Areas for Prevention of Specific Water Use Failure”. Specifically, the sample was produced under the condition of adding sodium hypochlorite so that the sample had a pH of 7.0, a temperature of 20 ° C., a reaction time of 24 hours, and a free residual chlorine concentration of 24 mg / L after 24 hours. In this method, the amount of trihalomethane produced is measured and measured by simultaneous analysis using a purge trap-gas chromatograph-mass spectrometer. The trihalomethane precursor can also be measured by a TOC meter or the like.
トリハロメタン前駆物質がトリハロメタン生成能（ＴＨＭＦＰ）（ｍｇ／Ｌ）として、０．００１ｍｇ／Ｌ以上存在するとトリハロメタンが生成し易いため、膜分離装置への給水または洗浄水のトリハロメタン生成能が０．００１ｍｇ／Ｌ以上、好ましくは０．０１ｍｇ／Ｌ以上、より好ましくは０．０２ｍｇ／Ｌ以上であると、本実施形態に係る分離膜のスライム抑制方法がより効果を発揮する。膜分離装置への給水または洗浄水のトリハロメタン生成能の上限には特に制限はないが、例えば、１ｍｇ／Ｌ以下である。 When the trihalomethane precursor is present in an amount of 0.001 mg / L or more as a trihalomethane-forming ability (THMFP) (mg / L), trihalomethane is easily generated. When the amount is L or more, preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, the method for suppressing slime of a separation membrane according to the present embodiment exhibits more effects. The upper limit of the trihalomethane-producing ability of the water supplied to the membrane separation device or the washing water is not particularly limited, but is, for example, 1 mg / L or less.
また、トリハロメタン前駆物質がＴＯＣとして０．５ｍｇ／Ｌ以上存在するとトリハロメタンが生成し易いため、膜分離装置への給水または洗浄水のＴＯＣが０．５ｍｇ／Ｌ以上、好ましくは５．０ｍｇ／Ｌ以上、より好ましくは１０．０ｍｇ／Ｌ以上であると、本実施形態に係る分離膜のスライム抑制方法がより効果を発揮する。膜分離装置への給水または洗浄水のＴＯＣの上限には特に制限はないが、例えば、５００ｍｇ／Ｌ以下である。なお、後述の実施例で測定した場合、トリハロメタン生成能０．０１ｍｇ／Ｌは、ＴＯＣ５．０ｍｇ／Ｌに相当する。 Further, if the trihalomethane precursor is present in an amount of 0.5 mg / L or more as the TOC, trihalomethane is easily generated, so that the TOC of the water supplied to the membrane separation device or the washing water is 0.5 mg / L or more, preferably 5.0 mg / L or more. If it is 10.0 mg / L or more, the method for suppressing slime of a separation membrane according to the present embodiment exhibits more effects. The upper limit of the TOC of the water supplied to the membrane separation device or the washing water is not particularly limited, but is, for example, 500 mg / L or less. In addition, when measured by the below-mentioned Example, the trihalomethane formation ability 0.01 mg / L is equivalent to 5.0 mg / L of TOC.
特にトリハロメタン前駆物質がフミン酸を含む場合は、フミン酸として０．８９ｍｇ／Ｌ以上存在するとトリハロメタンが生成し易いため、膜分離装置への給水または洗浄水のフミン酸が０．８９ｍｇ／Ｌ以上、好ましくは８．９ｍｇ／Ｌ以上、より好ましくは８９０ｍｇ／Ｌ以上であると、本実施形態に係る分離膜のスライム抑制方法がより効果を発揮する。膜分離装置への給水または洗浄水のフミン酸の上限には特に制限はないが、例えば、１８０ｍｇ／Ｌ以下である。なお、後述の実施例で測定した場合、トリハロメタン生成能０．０１ｍｇ／Ｌは、フミン酸８．９ｍｇ／Ｌに相当する。 In particular, when the trihalomethane precursor contains humic acid, the presence of 0.89 mg / L or more of humic acid easily generates trihalomethane, so that the humic acid supplied to the membrane separation device or the washing water is 0.89 mg / L or more. When the amount is preferably 8.9 mg / L or more, more preferably 890 mg / L or more, the method for suppressing slime of a separation membrane according to the present embodiment exhibits more effects. The upper limit of the humic acid in the water supplied to the membrane separation device or the washing water is not particularly limited, but is, for example, 180 mg / L or less. In addition, when measured by the below-mentioned Example, the trihalomethane formation ability 0.01 mg / L is equivalent to humic acid 8.9 mg / L.
本実施形態に係る分離膜のスライム抑制方法では、例えば、トリハロメタン前駆物質を含有する給水または洗浄水を用いる膜分離装置への給水または洗浄水中に、「臭素系酸化剤」または「臭素化合物と塩素系酸化剤との反応物」を薬注ポンプ等により注入すればよい。「臭素化合物」と「塩素系酸化剤」は別々に水系に添加してもよく、または、原液同士で混合させてから水系に添加してもよい。 In the method for suppressing slime of a separation membrane according to the present embodiment, for example, a "bromine-based oxidizing agent" or a "bromine compound and chlorine" is supplied to a membrane separation device using feedwater or washwater containing a trihalomethane precursor. What is necessary is just to inject the "reactant with the system oxidizing agent" using a chemical injection pump or the like. The “bromine compound” and the “chlorine-based oxidizing agent” may be separately added to the aqueous system, or the stock solutions may be mixed and then added to the aqueous system.
例えば、トリハロメタン前駆物質を含有する給水または洗浄水を用いる膜分離装置への給水または洗浄水中に、「臭素系酸化剤」または「臭素化合物と塩素系酸化剤との反応物」と、「スルファミン酸化合物」とを薬注ポンプ等により注入してもよい。「臭素系酸化剤」または「臭素化合物と塩素系酸化剤との反応物」と、「スルファミン酸化合物」とは別々に水系に添加してもよく、または、原液同士で混合させてから水系に添加してもよい。 For example, in a feed water or a wash water to a membrane separation device using a feed water or a wash water containing a trihalomethane precursor, a “bromine-based oxidant” or a “reactant of a bromine compound and a chlorine-based oxidant” and a “sulfamic acid” The compound may be injected by a chemical injection pump or the like. The "bromine-based oxidant" or "reactant of a bromine compound and a chlorine-based oxidant" and the "sulfamic acid compound" may be separately added to an aqueous system, or mixed with stock solutions and then added to an aqueous system. It may be added.
また、例えば、トリハロメタン前駆物質を含有する給水または洗浄水を用いる膜分離装置への給水または洗浄水中に、「臭素系酸化剤とスルファミン酸化合物との反応生成物」、または「臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物」を薬注ポンプ等により注入してもよい。 Further, for example, in the feed water or wash water to a membrane separation device using feed water or wash water containing a trihalomethane precursor, a “reaction product of a bromine-based oxidizing agent and a sulfamic acid compound”, or “a bromine compound and a chlorine-based The reaction product of the reaction product with the oxidizing agent and the sulfamic acid compound ”may be injected by a chemical injection pump or the like.
膜分離装置への給水または洗浄水中に添加された上述のスライム抑制剤は、分離膜の直前で還元剤等により分解されてもよい。 The slime inhibitor added to the water supplied to the membrane separation device or the washing water may be decomposed by a reducing agent or the like immediately before the separation membrane.
「臭素系酸化剤」または「臭素化合物と塩素系酸化剤との反応物」の当量に対する「スルファミン酸化合物」の当量の比は、１以上であることが好ましく、１以上２以下の範囲であることがより好ましい。「臭素系酸化剤」または「臭素化合物と塩素系酸化剤との反応物」の当量に対する「スルファミン酸化合物」の当量の比が１未満であると、膜を劣化させる可能性があり、２を超えると、製造コストが増加する場合がある。 The ratio of the equivalent of the “sulfamic acid compound” to the equivalent of the “bromine oxidant” or the “reactant of the bromine compound and the chlorine oxidant” is preferably 1 or more, and more preferably 1 or more and 2 or less. Is more preferable. When the ratio of the equivalent of the “sulfamic acid compound” to the equivalent of the “bromine oxidant” or the “reactant of the bromine compound and the chlorine oxidant” is less than 1, the film may be deteriorated. If it exceeds, the manufacturing cost may increase.
分離膜に接触する有効ハロゲン濃度は有効塩素濃度換算で、０．０１〜１００ｍｇ／Ｌであることが好ましい。０．０１ｍｇ／Ｌ未満であると、十分なスライム抑制効果を得ることができない場合があり、１００ｍｇ／Ｌより多いと、分離膜の劣化、配管等の腐食を引き起こす可能性がある。 The effective halogen concentration in contact with the separation membrane is preferably 0.01 to 100 mg / L in terms of effective chlorine concentration. If it is less than 0.01 mg / L, it may not be possible to obtain a sufficient slime suppressing effect, and if it is more than 100 mg / L, deterioration of the separation membrane and corrosion of piping and the like may be caused.
臭素系酸化剤としては、臭素（液体臭素）、塩化臭素、臭素酸、臭素酸塩、次亜臭素酸等が挙げられる。 Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, bromate, bromate, hypobromite and the like.
これらのうち、臭素を用いた「臭素とスルファミン酸化合物（臭素とスルファミン酸化合物の混合物）」または「臭素とスルファミン酸化合物との反応生成物」の製剤は、「次亜塩素酸と臭素化合物とスルファミン酸」の製剤および「塩化臭素とスルファミン酸」の製剤等に比べて、トリハロメタンの生成量自体が少なく、逆浸透膜（ＲＯ膜）等をより劣化させず、逆浸透膜（ＲＯ膜）透過水等の膜透過水への有効ハロゲンのリーク量がより少ないため、逆浸透膜（ＲＯ膜）等の分離膜用スライム抑制剤としてはより好ましい。 Of these, the formulation of "bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound)" or "reaction product of bromine and sulfamic acid compound" using bromine is described as "hypochlorous acid and bromine compound and Compared to the “sulfamic acid” preparation and the “bromine chloride and sulfamic acid” preparations, the amount of trihalomethane generated itself is smaller, the reverse osmosis membrane (RO membrane) and the like are not further deteriorated, and the reverse osmosis membrane (RO membrane) permeates. Since the amount of effective halogen leaking into water permeated through a membrane such as water is smaller, it is more preferable as a slime inhibitor for a separation membrane such as a reverse osmosis membrane (RO membrane).
すなわち、本発明の実施形態に係る分離膜のスライム抑制方法は、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、臭素と、スルファミン酸化合物とを存在させる（臭素とスルファミン酸化合物の混合物を存在させる）ことが好ましい。また、トリハロメタン前駆物質を含有する、分離膜を備える膜分離装置への給水または洗浄水中に、臭素とスルファミン酸化合物との反応生成物を存在させることが好ましい。 That is, in the method for suppressing slime of a separation membrane according to the embodiment of the present invention, bromine and a sulfamic acid compound are present in water or washing water containing a trihalomethane precursor and supplied to a membrane separation apparatus having a separation membrane ( Preferably, a mixture of bromine and a sulfamic acid compound is present). Further, it is preferable that a reaction product of bromine and a sulfamic acid compound is present in water supplied to a membrane separation device having a separation membrane and a washing water containing a trihalomethane precursor.
臭素化合物としては、臭化ナトリウム、臭化カリウム、臭化リチウム、臭化アンモニウム及び臭化水素酸等が挙げられる。これらのうち、製剤コスト等の点から、臭化ナトリウムが好ましい。 Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide, and hydrobromic acid. Of these, sodium bromide is preferred from the viewpoints of formulation cost and the like.
塩素系酸化剤としては、例えば、塩素ガス、二酸化塩素、次亜塩素酸またはその塩、亜塩素酸またはその塩、塩素酸またはその塩、過塩素酸またはその塩、塩素化イソシアヌル酸またはその塩等が挙げられる。これらのうち、塩としては、例えば、次亜塩素酸ナトリウム、次亜塩素酸カリウム等の次亜塩素酸アルカリ金属塩、次亜塩素酸カルシウム、次亜塩素酸バリウム等の次亜塩素酸アルカリ土類金属塩、亜塩素酸ナトリウム、亜塩素酸カリウム等の亜塩素酸アルカリ金属塩、亜塩素酸バリウム等の亜塩素酸アルカリ土類金属塩、亜塩素酸ニッケル等の他の亜塩素酸金属塩、塩素酸アンモニウム、塩素酸ナトリウム、塩素酸カリウム等の塩素酸アルカリ金属塩、塩素酸カルシウム、塩素酸バリウム等の塩素酸アルカリ土類金属塩等が挙げられる。これらの塩素系酸化剤は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。塩素系酸化剤としては、取り扱い性等の点から、次亜塩素酸ナトリウムを用いるのが好ましい。 Examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorite or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, chlorinated isocyanuric acid or a salt thereof. And the like. Among these, examples of the salt include alkali metal hypochlorites such as sodium hypochlorite and potassium hypochlorite, and alkaline earth hypochlorite such as calcium hypochlorite and barium hypochlorite. Metal salts, alkali metal chlorites such as sodium chlorite and potassium chlorite, alkaline earth metal chlorites such as barium chlorite, and other metal chlorites such as nickel chlorite And alkali earth chlorates such as ammonium chlorate, sodium chlorate and potassium chlorate, and alkaline earth chlorates such as calcium chlorate and barium chlorate. One of these chlorine-based oxidizing agents may be used alone, or two or more thereof may be used in combination. As the chlorine-based oxidizing agent, sodium hypochlorite is preferably used from the viewpoint of handleability and the like.
スルファミン酸化合物は、以下の一般式（１）で示される化合物である。
Ｒ２ＮＳＯ３Ｈ （１）
（式中、Ｒは独立して水素原子または炭素数１〜８のアルキル基である。）
The sulfamic acid compound is a compound represented by the following general formula (1).
R 2 NSO 3 H (1)
(In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
スルファミン酸化合物としては、例えば、２個のＲ基の両方が水素原子であるスルファミン酸（アミド硫酸）の他に、Ｎ−メチルスルファミン酸、Ｎ−エチルスルファミン酸、Ｎ−プロピルスルファミン酸、Ｎ−イソプロピルスルファミン酸、Ｎ−ブチルスルファミン酸等の２個のＲ基の一方が水素原子であり、他方が炭素数１〜８のアルキル基であるスルファミン酸化合物、Ｎ，Ｎ−ジメチルスルファミン酸、Ｎ，Ｎ−ジエチルスルファミン酸、Ｎ，Ｎ−ジプロピルスルファミン酸、Ｎ，Ｎ−ジブチルスルファミン酸、Ｎ−メチル−Ｎ−エチルスルファミン酸、Ｎ−メチル−Ｎ−プロピルスルファミン酸等の２個のＲ基の両方が炭素数１〜８のアルキル基であるスルファミン酸化合物、Ｎ−フェニルスルファミン酸等の２個のＲ基の一方が水素原子であり、他方が炭素数６〜１０のアリール基であるスルファミン酸化合物、またはこれらの塩等が挙げられる。スルファミン酸塩としては、例えば、ナトリウム塩、カリウム塩等のアルカリ金属塩、カルシウム塩、ストロンチウム塩、バリウム塩等のアルカリ土類金属塩、マンガン塩、銅塩、亜鉛塩、鉄塩、コバルト塩、ニッケル塩等の他の金属塩、アンモニウム塩およびグアニジン塩等が挙げられる。スルファミン酸化合物およびこれらの塩は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。スルファミン酸化合物としては、環境負荷等の点から、スルファミン酸（アミド硫酸）を用いるのが好ましい。 As the sulfamic acid compound, for example, in addition to sulfamic acid (amidosulfate) in which both R groups are both hydrogen atoms, N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N- One of two R groups such as isopropylsulfamic acid and N-butylsulfamic acid is a hydrogen atom, and the other is an alkyl group having 1 to 8 carbon atoms; a sulfamic acid compound; N, N-dimethylsulfamic acid; Two R groups such as N-diethylsulfamic acid, N, N-dipropylsulfamic acid, N, N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid and N-methyl-N-propylsulfamic acid; One of two R groups such as a sulfamic acid compound in which both are an alkyl group having 1 to 8 carbon atoms and N-phenylsulfamic acid is An atom, the other is sulfamic acid compound or a salt thereof, such as an aryl group having 6 to 10 carbon atoms. As the sulfamate, for example, sodium salts, alkali metal salts such as potassium salts, calcium salts, strontium salts, alkaline earth metal salts such as barium salts, manganese salts, copper salts, zinc salts, iron salts, cobalt salts, Other metal salts such as nickel salts, ammonium salts, guanidine salts and the like. One of these sulfamic acid compounds and salts thereof may be used alone, or two or more thereof may be used in combination. As the sulfamic acid compound, it is preferable to use sulfamic acid (amidosulfuric acid) from the viewpoint of environmental load and the like.
本実施形態に係る分離膜のスライム抑制方法において、さらにアルカリを存在させてもよい。アルカリとしては、水酸化ナトリウム、水酸化カリウム等の水酸化アルカリ等が挙げられる。低温時の製品安定性等の点から、水酸化ナトリウムと水酸化カリウムとを併用してもよい。また、アルカリは、固形でなく、水溶液として用いてもよい。 In the method for suppressing slime of a separation 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 from the viewpoint of product stability at low temperatures. The alkali may be used as an aqueous solution instead of a solid.
分離膜としては、逆浸透膜（ＲＯ膜）、ナノろ過膜（ＮＦ膜）、精密ろ過膜（ＭＦ膜）、限外ろ過膜（ＵＦ膜）等が挙げられる。これらのうち、特に逆浸透膜（ＲＯ膜）に、本発明の実施形態に係る分離膜のスライム抑制方法を好適に適用することができる。また、逆浸透膜として昨今主流であるポリアミド系高分子膜に本発明の実施形態に係る分離膜のスライム抑制方法を好適に適用することができる。ポリアミド系高分子膜は、酸化剤に対する耐性が比較的低く、遊離塩素等をポリアミド系高分子膜に連続的に接触させると、膜性能の著しい低下が起こる。しかしながら、本実施形態に係る分離膜のスライム抑制方法ではポリアミド高分子膜においても、このような著しい膜性能の低下はほとんど起こらない。 Examples of the separation membrane include a reverse osmosis membrane (RO membrane), a nanofiltration membrane (NF membrane), a microfiltration membrane (MF membrane), and an ultrafiltration membrane (UF membrane). Among these, the method for suppressing slime of a separation membrane according to the embodiment of the present invention can be suitably applied to a reverse osmosis membrane (RO membrane). Further, the method for suppressing slime of a separation membrane according to the embodiment of the present invention can be suitably applied to a polyamide-based polymer membrane that is currently mainstream as a reverse osmosis membrane. The polyamide-based polymer film has relatively low resistance to an oxidizing agent, and when free chlorine or the like is continuously brought into contact with the polyamide-based polymer film, the film performance is significantly reduced. However, in the method for suppressing slime of a separation membrane according to the present embodiment, such a remarkable decrease in membrane performance hardly occurs even in a polyamide polymer membrane.
本実施形態に係る分離膜のスライム抑制方法において、膜分離装置が分離膜として逆浸透膜（ＲＯ膜）を備えるＲＯ装置の場合、ＲＯ装置への給水のｐＨが５．５以上であることが好ましく、６．０以上であることがより好ましく、６．５以上であることがさらに好ましい。ＲＯ装置への給水のｐＨが５．５未満であると、透過水量が低下する場合がある。また、ＲＯ装置への給水のｐＨの上限値については、通常の逆浸透膜（ＲＯ膜）の適用上限ｐＨ（例えば、ｐＨ１０）以下であれば特に制限はないが、カルシウム等の硬度成分のスケール析出を考慮すると、ｐＨは例えば９．０以下で運転することが好ましい。本実施形態に係る分離膜のスライム抑制方法を用いる場合、ＲＯ装置への給水のｐＨが５．５以上で運転することにより、逆浸透膜（ＲＯ膜）の劣化、処理水（透過水）の水質悪化を抑制し、十分なスライム抑制効果を発揮しつつ、十分な透過水量の確保も可能となる。 In the method for suppressing slime of a separation membrane according to the present embodiment, when the membrane separation apparatus is an RO apparatus including a reverse osmosis membrane (RO membrane) as a separation membrane, the pH of water supplied to the RO apparatus may be 5.5 or more. Preferably, it is 6.0 or more, more preferably 6.5 or more. If the pH of the water supply to the RO device is less than 5.5, the amount of permeated water may decrease. The upper limit of the pH of water supplied to the RO device is not particularly limited as long as it is equal to or lower than the upper limit pH (for example, pH 10) of a normal reverse osmosis membrane (RO membrane). In consideration of precipitation, it is preferable to operate at a pH of, for example, 9.0 or less. When the method for controlling slime of a separation membrane according to the present embodiment is used, the reverse osmosis membrane (RO membrane) is degraded and the treated water (permeated water) is deteriorated by operating the feedwater to the RO device at a pH of 5.5 or more. Water quality deterioration is suppressed, and a sufficient amount of permeated water can be secured while exhibiting a sufficient slime suppressing effect.
ＲＯ装置において、ＲＯ装置への給水のｐＨ５．５以上でスケールが発生する場合には、スケール抑制のために分散剤を臭素系酸化剤または次亜臭素酸安定化組成物と併用してもよい。分散剤としては、例えば、ポリアクリル酸、ポリマレイン酸、ホスホン酸等が挙げられる。分散剤の給水への添加量は、例えば、ＲＯ濃縮水中の濃度として０．１〜１，０００ｍｇ／Ｌの範囲である。 In the RO apparatus, when scale is generated at a pH of 5.5 or more in the water supplied to the RO apparatus, a dispersant may be used in combination with a brominated oxidizing agent or a hypobromite-stabilizing composition for scale suppression. . Examples of the dispersant include polyacrylic acid, polymaleic acid, and phosphonic acid. The amount of the dispersant added to the feed water is, for example, in the range of 0.1 to 1,000 mg / L as the concentration in the RO concentrated water.
また、分散剤を使用せずにスケールの発生を抑制するためには、例えば、ＲＯ濃縮水中のシリカ濃度を溶解度以下に、カルシウムスケールの指標であるランゲリア指数を０以下になるように、ＲＯ装置の回収率等の運転条件を調整することが挙げられる。 Further, in order to suppress the generation of scale without using a dispersant, for example, the RO apparatus is set so that the silica concentration in the RO concentrated water is equal to or less than the solubility, and the Langeria index which is an index of the calcium scale is equal to or less than 0. Adjusting the operating conditions such as the recovery rate of the wastewater.
ＲＯ装置の用途としては、例えば、海水淡水化、排水回収等が挙げられる。 Applications of the RO device include, for example, seawater desalination, wastewater recovery, and the like.
＜分離膜用スライム抑制剤組成物＞
本実施形態に係る分離膜用スライム抑制剤組成物は、「臭素系酸化剤」または「臭素化合物と塩素系酸化剤との反応物」と、「スルファミン酸化合物」とを含有するものであり、さらにアルカリを含有してもよい。
<Slime inhibitor composition for separation membrane>
The slime inhibitor composition for a separation membrane according to this embodiment contains a `` bromine-based oxidant '' or a `` reactant of a bromine compound and a chlorine-based oxidant '' and a `` sulfamic acid compound '', Furthermore, you may contain alkali.
また、本実施形態に係る分離膜用スライム抑制剤組成物は、「臭素系酸化剤とスルファミン酸化合物との反応生成物」、または「臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物」を含有するものであり、さらにアルカリを含有してもよい。 In addition, the slime inhibitor composition for a separation membrane according to the present embodiment is a "reaction product of a brominated oxidizing agent and a sulfamic acid compound" or "a reaction product of a brominated compound and a chlorine oxidizing agent, and sulfamic acid. And a reaction product with a compound, and may further contain an alkali.
臭素系酸化剤、臭素化合物、塩素系酸化剤およびスルファミン酸化合物については、上述した通りである。 The bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent, and sulfamic acid compound are as described above.
本実施形態に係る分離膜用スライム抑制剤組成物としては、逆浸透膜（ＲＯ膜）等をより劣化させず、ＲＯ透過水等の膜透過水への有効ハロゲンのリーク量がより少ないため、臭素と、スルファミン酸化合物とを含有するもの（臭素とスルファミン酸化合物の混合物を含有するもの）、例えば、臭素とスルファミン酸化合物とアルカリと水との混合物、または、臭素とスルファミン酸化合物との反応生成物を含有するもの、例えば、臭素とスルファミン酸化合物との反応生成物と、アルカリと、水との混合物が好ましい。 The slime inhibitor composition for a separation membrane according to the present embodiment does not deteriorate the reverse osmosis membrane (RO membrane) and the like, and the amount of effective halogen leaked to the membrane permeated water such as the RO permeated water is smaller. One containing bromine and a sulfamic acid compound (containing a mixture of bromine and a sulfamic acid compound), for example, a mixture of bromine, a sulfamic acid compound, an alkali, and water, or a reaction of a bromine with a sulfamic acid compound Those containing a product, for example, a mixture of a reaction product of bromine and a sulfamic acid compound, an alkali, and water are preferable.
本実施形態に係る分離膜用スライム抑制剤組成物は、クロロスルファミン酸等の結合塩素系スライム抑制剤と比較すると、酸化力が高く、スライム抑制力、スライム剥離力が著しく高いにもかかわらず、同じく酸化力の高い次亜塩素酸のような著しい膜劣化をほとんど引き起こすことがない。通常の使用濃度では、膜劣化への影響は実質的に無視することができる。このため、逆浸透膜（ＲＯ膜）等の分離膜用スライム抑制剤としては最適である。 The slime inhibitor composition for a separation membrane according to the present embodiment has a higher oxidizing power, a higher slime suppressing power, and a significantly higher slime peeling power, compared to a chlorinated slime inhibitor such as chlorosulfamic acid. Also, it hardly causes remarkable film deterioration such as hypochlorous acid having high oxidizing power. At normal use concentrations, the effect on film degradation can be substantially ignored. Therefore, it is most suitable as a slime inhibitor for a separation membrane such as a reverse osmosis membrane (RO membrane).
本実施形態に係る分離膜用スライム抑制剤組成物は、次亜塩素酸とは異なり、逆浸透膜（ＲＯ膜）をほとんど透過しないため、処理水水質への影響がほとんどない。また、次亜塩素酸等と同様に現場で濃度を測定することができるため、より正確な濃度管理が可能である。また、本実施形態に係る分離膜用スライム抑制剤組成物は、トリハロメタン前駆物質と反応して臭素系トリハロメタンを生成するが、分離膜で排除され易く、分離膜の透過水中のトリハロメタンが大幅に低減されると考えられる。 Unlike hypochlorous acid, the slime inhibitor composition for a separation membrane according to the present embodiment hardly permeates a reverse osmosis membrane (RO membrane), and thus has little effect on the quality of treated water. Further, since the concentration can be measured on site similarly to hypochlorous acid or the like, more accurate concentration control is possible. Further, the slime inhibitor composition for a separation membrane according to the present embodiment reacts with a trihalomethane precursor to generate a brominated trihalomethane, but is easily removed by the separation membrane, and trihalomethane in permeated water of the separation membrane is significantly reduced. It is thought to be done.
組成物のｐＨは、例えば、１３．０超であり、１３．２超であることがより好ましい。組成物のｐＨが１３．０以下であると組成物中の有効ハロゲンが不安定になる場合がある。 The pH of the composition is, for example, above 13.0, more preferably above 13.2. When the pH of the composition is 13.0 or less, the effective halogen in the composition may become unstable.
分離膜用スライム抑制剤組成物中の臭素酸濃度は、５ｍｇ／ｋｇ未満であることが好ましい。分離膜用スライム抑制剤組成物中の臭素酸濃度が５ｍｇ／ｋｇ以上であると、透過水の臭素酸イオンの濃度が高くなる場合がある。 The concentration of bromate in the slime inhibitor composition for a separation membrane is preferably less than 5 mg / kg. When the concentration of bromate in the slime inhibitor composition for a separation membrane is 5 mg / kg or more, the concentration of bromate ion in permeated water may increase.
＜分離膜用スライム抑制剤組成物の製造方法＞
本実施形態に係る分離膜用スライム抑制剤組成物は、臭素系酸化剤とスルファミン酸化合物とを混合する、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物とを混合することにより得られ、さらにアルカリを混合してもよい。
<Production method of slime inhibitor composition for separation membrane>
The slime inhibitor composition for a separation membrane according to the present embodiment is obtained by mixing a brominated oxidizing agent and a sulfamic acid compound, or mixing a reactant of a bromine compound and a chlorine oxidizing agent with a sulfamic acid compound. And an alkali may be further mixed.
臭素と、スルファミン酸化合物とを含有する分離膜用スライム抑制剤組成物、または、臭素とスルファミン酸化合物との反応生成物を含有する分離膜用スライム抑制剤組成物の製造方法としては、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加して反応させる工程、または、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加する工程を含むことが好ましい。不活性ガス雰囲気下で添加して反応させる、または、不活性ガス雰囲気下で添加することにより、組成物中の臭素酸イオン濃度が低くなり、ＲＯ透過水等の透過水中の臭素酸イオン濃度が低くなる。 Bromine and a slime inhibitor composition for a separation membrane containing a sulfamic acid compound, or a method for producing a slime inhibitor composition for a separation membrane containing a reaction product of bromine and a sulfamic acid compound, water, A step of adding and reacting bromine to a mixture containing an alkali and a sulfamic acid compound under an inert gas atmosphere, or a step of adding bromine to a mixture containing water, an alkali and a sulfamic acid compound under an inert gas atmosphere It is preferable to include By adding and reacting under an inert gas atmosphere, or by adding under an inert gas atmosphere, the bromate ion concentration in the composition decreases, and the bromate ion concentration in permeated water such as RO permeated water is reduced. Lower.
用いる不活性ガスとしては限定されないが、製造等の面から窒素およびアルゴンのうち少なくとも１つが好ましく、特に製造コスト等の面から窒素が好ましい。 Used but are not limited to inert gas, at least one and preferably one in terms of nitrogen and argon, such as production, nitrogen is particularly preferred from the viewpoint of production cost and the like.
臭素の添加の際の反応器内の酸素濃度は６％以下が好ましいが、４％以下がより好ましく、２％以下がさらに好ましく、１％以下が特に好ましい。臭素の反応の際の反応器内の酸素濃度が６％を超えると、反応系内の臭素酸の生成量が増加する場合がある。 The oxygen concentration in the reactor at the time of adding bromine is preferably 6% or less, more preferably 4% or less, further preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reactor during the reaction of bromine exceeds 6%, the amount of bromic acid generated in the reaction system may increase.
臭素の添加率は、組成物全体の量に対して２５重量％以下であることが好ましく、１重量％以上２０重量％以下であることがより好ましい。臭素の添加率が組成物全体の量に対して２５重量％を超えると、反応系内の臭素酸の生成量が増加する場合がある。１重量％未満であると、殺菌力が劣る場合がある。 The addition ratio of bromine is preferably 25% by weight or less, more preferably 1% by weight or more and 20% by weight or less based on the total amount of the composition. If the bromine addition rate exceeds 25% by weight based on the total amount of the composition, the amount of bromic acid generated in the reaction system may increase. If it is less than 1% by weight, the bactericidal activity may be poor.
臭素添加の際の反応温度は、０℃以上２５℃以下の範囲に制御することが好ましいが、製造コスト等の面から、０℃以上１５℃以下の範囲に制御することがより好ましい。臭素添加の際の反応温度が２５℃を超えると、反応系内の臭素酸の生成量が増加する場合があり、０℃未満であると、凍結する場合がある。 The reaction temperature at the time of adding bromine is preferably controlled in the range of 0 ° C. or more and 25 ° C. or less, but is more preferably controlled in the range of 0 ° C. or more and 15 ° C. or less from the viewpoint of production cost and the like. If the reaction temperature at the time of adding bromine exceeds 25 ° C., the amount of bromic acid produced in the reaction system may increase, and if it is lower than 0 ° C., it may freeze.
以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples.
スライム抑制剤として「臭素系酸化剤とスルファミン酸化合物との反応生成物」である次亜臭素酸安定化組成物を使用した場合（実施例１）、「臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、の反応生成物」である次亜臭素酸安定化組成物を使用した場合（実施例２）、「臭素系酸化剤」を使用した場合（参考例３）と、一般的なスライム抑制剤である次亜塩素酸を使用した場合（比較例１）との透過水中のトリハロメタン濃度、逆浸透膜（ＲＯ膜）性能への影響について比較した。 When a hypobromite stabilized composition which is a "reaction product of a brominated oxidizing agent and a sulfamic acid compound" is used as a slime inhibitor (Example 1), "reaction between a brominated compound and a chlorine oxidizing agent" When a hypobromite stabilizing composition which is a reaction product of a product and a sulfamic acid compound is used (Example 2), when a "brominated oxidizing agent" is used ( Reference Example 3), The effect on the concentration of trihalomethane in the permeated water and the performance on the reverse osmosis membrane (RO membrane) was compared with the case where hypochlorous acid, which is a general slime inhibitor, was used (Comparative Example 1).
［組成物１の調製］
窒素雰囲気下で、液体臭素：１６．９重量％（ｗｔ％）、スルファミン酸：１０．７重量％、水酸化ナトリウム：１２．９重量％、水酸化カリウム：３．９４重量％、水：残分を混合して、組成物１を調製した。組成物１のｐＨは１４、有効ハロゲン濃度（有効塩素換算濃度）は７．５重量％であった。組成物１の詳細な調製方法は以下の通りである。
[Preparation of Composition 1]
Under a nitrogen atmosphere, liquid bromine: 16.9% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.94% by weight, water: residual The components were mixed to prepare Composition 1. The pH of composition 1 was 14, and the effective halogen concentration (concentration in terms of effective chlorine) was 7.5% by weight. The detailed preparation method of the composition 1 is as follows.
反応容器内の酸素濃度が１％に維持されるように、窒素ガスの流量をマスフローコントローラでコントロールしながら連続注入で封入した２Ｌの４つ口フラスコに１４３６ｇの水、３６１ｇの水酸化ナトリウムを加え混合し、次いで３００ｇのスルファミン酸を加え混合した後、反応液の温度が０〜１５℃になるように冷却を維持しながら、４７３ｇの液体臭素を加え、さらに４８％水酸化カリウム溶液２３０ｇを加え、組成物全体の量に対する重量比でスルファミン酸１０．７％、臭素１６．９％、臭素の当量に対するスルファミン酸の当量比が１．０４である、目的の組成物１を得た。生じた溶液のｐＨは、ガラス電極法にて測定したところ、１４であった。生じた溶液の臭素含有率は、臭素をヨウ化カリウムによりヨウ素に転換後、チオ硫酸ナトリウムを用いて酸化還元滴定する方法により測定したところ１６．９％であり、理論含有率（１６．９％）の１００．０％であった。また、臭素反応の際の反応容器内の酸素濃度は、株式会社ジコー製の「酸素モニタＪＫＯ−０２ ＬＪＤＩＩ」を用いて測定した。なお、臭素酸濃度は５ｍｇ／ｋｇ未満であった。 While controlling the flow rate of nitrogen gas with a mass flow controller so that the oxygen concentration in the reaction vessel is maintained at 1%, 1436 g of water and 361 g of sodium hydroxide are added to a 2 L four-necked flask sealed by continuous injection. After mixing and then adding 300 g of sulfamic acid and mixing, 473 g of liquid bromine was added while maintaining the cooling of the reaction solution at 0 to 15 ° C., and 230 g of a 48% potassium hydroxide solution was further added. Thus, a target composition 1 was obtained in which the weight ratio of sulfamic acid to the total amount of the composition was 10.7%, the bromine content was 16.9%, and the equivalent ratio of sulfamic acid to the equivalent weight of bromine was 1.04. The pH of the resulting solution was 14, as measured by the glass electrode method. The bromine content of the resulting solution was 16.9% as measured by a method of converting bromine to iodine with potassium iodide and then performing redox titration with sodium thiosulfate, and the theoretical content was 16.9%. ) Was 100.0%. The oxygen concentration in the reaction vessel during the bromine reaction was measured using "Oxygen Monitor JKO-02 LJDII" manufactured by Jiko Corporation. The bromate concentration was less than 5 mg / kg.
［組成物２の調製］
臭化ナトリウム：１１重量％、１２％次亜塩素酸ナトリウム水溶液：５０重量％、スルファミン酸ナトリウム：１４重量％、水酸化ナトリウム：８重量％、水：残分を混合して、組成物２を調製した。組成物２のｐＨは１４、有効ハロゲン濃度（有効塩素換算濃度）は６重量％であった。組成物２の詳細な調製方法は以下の通りである。
[Preparation of Composition 2]
Sodium bromide: 11% by weight, 12% aqueous solution of sodium hypochlorite: 50% by weight, sodium sulfamate: 14% by weight, sodium hydroxide: 8% by weight, and water: the residue are mixed to obtain composition 2. Prepared. The pH of the composition 2 was 14, and the effective halogen concentration (concentration in terms of effective chlorine) was 6% by weight. The detailed preparation method of the composition 2 is as follows.
反応容器に１７ｇの水を入れ、１１ｇの臭化ナトリウムを加え撹拌して溶解させた後、５０ｇの１２％次亜塩素酸ナトリウム水溶液を加え混合し、次いで１４ｇのスルファミン酸ナトリウムを加え撹拌して溶解させた後、８ｇの水酸化ナトリウムを加え撹拌し溶解させて目的の組成物２を得た。 17 g of water was put in a reaction vessel, 11 g of sodium bromide was added and stirred to dissolve, 50 g of a 12% aqueous sodium hypochlorite solution was added and mixed, and then 14 g of sodium sulfamate was added and stirred. After dissolving, 8 g of sodium hydroxide was added, and the mixture was stirred and dissolved to obtain a desired composition 2.
なお、水道用次亜塩素酸ナトリウム規格（ＪＷＷＡ Ｋ １２０ ２００８）に定められる方法に則り、イオンクロマトグラフ法で測定したところ、組成物中の塩素酸の含有量は、組成物２（１１００ｍｇ／ｋｇ）よりも組成物１の方が少なかった（５０ｍｇ／ｋｇ未満）。 The content of chloric acid in the composition was measured by ion chromatography in accordance with the method defined in the standard for sodium hypochlorite for water supply (JWWA K 120 2008). Composition 1 was less (less than 50 mg / kg).
［組成物３］
９重量％次亜臭素酸ナトリウム水溶液（関東化学、鹿１級）を組成物３として使用した。
[Composition 3]
A 9% by weight aqueous solution of sodium hypobromite (Kanto Chemical, deer grade 1) was used as composition 3.
［組成物４］
１２重量％次亜塩素酸ナトリウム水溶液を組成物４として使用した。
[Composition 4]
A 12% by weight aqueous solution of sodium hypochlorite was used as composition 4.
＜実施例１，２、比較例１、参考例１〜３＞
以下の条件で、逆浸透膜装置の原水に、組成物１〜４をそれぞれ添加して、分離膜給水中と分離膜透過水中の総トリハロメタン濃度、総トリハロメタンの逆浸透膜（ＲＯ膜）での排除率を比較した。原水としては、実施例１，２、参考例３、比較例１では、下記模擬水を、参考例１，２では純水を使用した。
<Examples 1 and 2 , Comparative Example 1, and Reference Examples 1 to 3 >
Under the following conditions, compositions 1 to 4 were respectively added to the raw water of the reverse osmosis membrane apparatus, and the total trihalomethane concentration in the separation membrane feed water and the separation membrane permeated water, and the total trihalomethane in the reverse osmosis membrane (RO membrane) The exclusion rates were compared. As raw water, the following simulated water was used in Examples 1 and 2, Reference Example 3, and Comparative Example 1, and pure water was used in Reference Examples 1 and 2.
（試験条件）
・試験装置：平膜試験装置
・分離膜：日東電工（株）製、ポリアミド系高分子逆浸透膜 ＥＳ１５
・運転圧力：０．７５ＭＰａ
・原水：トリハロメタン生成能が０．０１ｍｇ／Ｌの模擬水（純水にトリハロメタン前駆物質としてフミン酸（和光純薬工業製）８．９ｍｇ／Ｌを添加したもの、ＴＯＣ：５ｍｇ／Ｌ）または純水
・薬剤：組成物１〜４を、有効ハロゲン濃度（有効塩素換算濃度）として３ｍｇ／Ｌとなるように添加
・原水ｐＨ：薬剤添加後に試験水のｐＨが８となるように調整
・試験温度：２５℃
・トリハロメタン生成能測定方法：試料をｐＨ７．０、温度２０℃、反応時間２４時間、２４時間後の遊離残留塩素濃度が１〜２ｍｇ／Ｌとなるように次亜塩素酸ナトリウムを添加した条件で、生成したトリハロメタン生成量をパージ・トラップ−ガスクロマトグラフ−質量分析計による一斉分析法で測定して、求めた。パージ・トラップ装置は「ＴＥＫＭＡＲ製、Ｔｅｋｍａｒ Ｓｔｒａｔｕｍ」、ガスクロマトグラフは「Ａｇｉｌｅｎｔ製、７８９０」、質量分析計は「Ａｇｉｌｅｎｔ製、５９７５Ｃ」を使用した。
・有効ハロゲン濃度の測定方法：残留塩素測定装置（Ｈａｃｈ社製、「ＤＲ−４０００」）を使用してＤＰＤ法により測定）
(Test condition)
・ Testing equipment: Flat membrane testing equipment ・ Separation membrane: Nitto Denko Corporation, polyamide-based polymer reverse osmosis membrane ES15
・ Operating pressure: 0.75MPa
Raw water: Simulated water having a trihalomethane generating ability of 0.01 mg / L (purified water to which humic acid (manufactured by Wako Pure Chemical Industries) 8.9 mg / L is added as a trihalomethane precursor, TOC: 5 mg / L) or pure water Water / drug: Compositions 1 to 4 are added so that the effective halogen concentration (concentration in terms of effective chlorine) becomes 3 mg / L. Raw water pH: adjusted so that the pH of test water becomes 8 after adding the drug. Test temperature : 25 ° C
Trihalomethane-forming ability measurement method: pH 7.0, temperature 20 ° C., reaction time 24 hours, under the condition that sodium hypochlorite was added such that the free residual chlorine concentration after 24 hours was 1-2 mg / L. And the amount of generated trihalomethane was determined by simultaneous analysis using a purge trap-gas chromatograph-mass spectrometer. The purge trap apparatus used was "Tekmar Stratum" manufactured by TEKMAR, the gas chromatograph used was "7890" manufactured by Agilent, and the mass spectrometer used was "5975C manufactured by Agilent".
-Measuring method of effective halogen concentration: Measured by DPD method using residual chlorine measuring device ("DR-4000" manufactured by Hach))
（評価方法）
［ＲＯ給水中とＲＯ透過水中の総トリハロメタン濃度、総トリハロメタンの逆浸透膜（ＲＯ膜）での排除率］
模擬水または純水に、表１に示す通り組成物１〜４を添加し、ｐＨを８に調整したものを、水温２５℃に調整し、ＲＯ装置に循環通水した。４時間後にＲＯ給水中とＲＯ透過水中の総トリハロメタン濃度（ｍｇ／Ｌ）を測定した。ＲＯ給水中とＲＯ透過水中の総トリハロメタン濃度から、総トリハロメタンの逆浸透膜（ＲＯ膜）での排除率（％）を求めた。結果を表１に示す。ここで、総トリハロメタンとは、クロロホルム、ブロモジクロロメタン、ジブロモクロロメタンおよびブロモホルムの４物質のことを指す。
(Evaluation method)
[Total trihalomethane concentration in RO feed water and RO permeated water, rejection rate of total trihalomethane by reverse osmosis membrane (RO membrane)]
Compositions 1 to 4 were added to simulated water or pure water as shown in Table 1 and the pH was adjusted to 8, the water temperature was adjusted to 25 ° C, and the water was circulated through an RO device. Four hours later, the total trihalomethane concentration (mg / L) in the RO feedwater and the RO permeate was measured. From the total trihalomethane concentration in the RO feed water and the RO permeate, the rejection (%) of the total trihalomethane on the reverse osmosis membrane (RO membrane) was determined. Table 1 shows the results. Here, the total trihalomethane refers to four substances of chloroform, bromodichloromethane, dibromochloromethane and bromoform.
総トリハロメタン濃度は、水質基準に関する省令の規定に基づき厚生労働大臣が定める方法（平成１５年厚生労働省告示第２６１号）に則り、パージ・トラップ−ガスクロマトグラフ−質量分析計による一斉分析法で測定した。 The total trihalomethane concentration was measured by a simultaneous analysis method using a purge trap-gas chromatograph-mass spectrometer in accordance with the method specified by the Minister of Health, Labor and Welfare based on the regulations of the Ministry of Health, Labor and Welfare based on the regulations of the Ministry of Health, Labor and Welfare. .
このように、実施例１，２では、比較例１に比べて、十分なスライム抑制効果を有しながら、透過水中のトリハロメタン含有量を低減することができた。なお、原水として純水を用いた参考例１，２の場合は、トリハロメタンはほとんど生成しなかった。 Thus, in Examples 1 and 2 , the trihalomethane content in the permeated water was able to be reduced while having a sufficient slime suppressing effect as compared with Comparative Example 1. In addition, in the case of Reference Examples 1 and 2 using pure water as raw water, trihalomethane was hardly generated.
「逆浸透膜（ＲＯ膜）排除率への影響、透過水への影響、酸化力の比較試験」
臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物とを使用した場合と、一般的なスライム抑制剤である次亜塩素酸、次亜臭素酸を使用した場合の逆浸透膜（ＲＯ膜）排除率への影響、透過水への影響、酸化力、殺菌力について比較した。
"Influence on reverse osmosis membrane (RO membrane) rejection rate, effect on permeated water, comparative test of oxidizing power"
When a bromine-based oxidant, or a reaction product of a bromine compound and a chlorine-based oxidant, and a sulfamic acid compound are used, and when hypochlorite or hypobromite, which is a general slime inhibitor, is used. Were compared for the effect on the reverse osmosis membrane (RO membrane) exclusion rate, the effect on permeated water, the oxidizing power, and the sterilizing power.
以下の条件で、逆浸透膜装置の原水に、組成物１，２，４〜７を添加して、逆浸透膜（ＲＯ膜）の排除率への影響、透過水への影響、酸化力を比較した。 Under the following conditions, the compositions 1, 2, 4 to 7 are added to the raw water of the reverse osmosis membrane apparatus to reduce the effect on the rejection rate of the reverse osmosis membrane (RO membrane), the effect on the permeated water, and the oxidizing power. Compared.
［組成物５］
組成物２の各組成を水中に別々に添加した。
[Composition 5]
Each composition of Composition 2 was added separately in water.
［組成物６］
塩化臭素、スルファミン酸ナトリウム、水酸化ナトリウムを含有する組成物６を使用した。組成物６のｐＨは１４、有効ハロゲン濃度（有効塩素換算濃度）は７重量％であった。
[Composition 6]
Composition 6 containing bromine chloride, sodium sulfamate and sodium hydroxide was used. The pH of the composition 6 was 14, and the effective halogen concentration (concentration in terms of effective chlorine) was 7% by weight.
［組成物７］
臭化ナトリウム：１５重量％、１２％次亜塩素酸ナトリウム水溶液：４２．４重量％、を水中に別々に添加した。
[Composition 7]
Sodium bromide: 15% by weight, 12% aqueous sodium hypochlorite solution: 42.4% by weight were separately added to water.
（試験条件）
・試験装置：平膜試験装置
・分離膜：日東電工（株）製、ポリアミド系高分子逆浸透膜 ＥＳ２０
・運転圧力：０．７５ＭＰａ
・原水：相模原井水（ｐＨ７．２、導電率２４０μＳ／ｃｍ、臭化物イオン濃度１．０ｍｇ／Ｌ未満）
・薬剤：組成物１，２，４〜７を、有効ハロゲン濃度（有効塩素換算濃度）として１０ｍｇ／Ｌとなるように添加
(Test condition)
・ Testing device: Flat membrane testing device ・ Separation membrane: Nitto Denko Corporation, polyamide-based polymer reverse osmosis membrane ES20
・ Operating pressure: 0.75MPa
Raw water: Sagamihara well water (pH 7.2, conductivity 240 μS / cm, bromide ion concentration less than 1.0 mg / L)
-Drug: Compositions 1, 2, 4 to 7 are added so that the effective halogen concentration (concentration in terms of effective chlorine) becomes 10 mg / L.
（評価方法）
・逆浸透膜（ＲＯ膜）の排除率への影響：３０日通水後の導電率排除率（％）
（１００−［透過水導電率／給水導電率］×１００）
・透過水への影響：薬剤添加１時間後の透過水中の有効ハロゲン濃度（有効塩素換算濃度、ｍｇ／Ｌ）を、残留塩素測定装置（Ｈａｃｈ社製、「ＤＲ−４０００」）を使用してＤＰＤ法により測定
・酸化力：１時間後の給水の酸化還元電位（ＯＲＰ）を、酸化還元電位測定装置（東亜ＤＫＫ製、ＲＭ−２０Ｐ型ＯＲＰ計）を使用して測定
(Evaluation method)
・ Effect of reverse osmosis membrane (RO membrane) on rejection rate: conductivity rejection rate after 30 days of water flow (%)
(100- [permeated water conductivity / water supply conductivity] × 100)
-Influence on permeate: The effective halogen concentration (concentration in terms of effective chlorine, mg / L) in the permeate water 1 hour after the addition of the chemical was measured using a residual chlorine measuring device ("DR-4000", manufactured by Hach). Oxidation power: Oxidation-reduction potential (ORP) of feed water after 1 hour is measured using an oxidation-reduction potential measuring device (RM-20P ORP meter manufactured by Toa DKK).
「殺菌力の比較試験」
以下の条件で、模擬水に組成物１，２，４〜７を添加して、殺菌力を比較した。
`` Comparative test of sterilization power ''
Under the following conditions, the compositions 1, 2, 4 to 7 were added to the simulated water, and the sterilizing power was compared.
（試験条件）
・水：相模原井水に普通ブイヨンを添加し、一般細菌数が１０５ＣＦＵ／ｍｌとなるよう調整した模擬水
・薬剤：組成物１，２，４〜７を、有効ハロゲン濃度（有効塩素換算濃度）として１ｍｇ／Ｌとなるよう添加（有効ハロゲン濃度の測定方法：残留塩素測定装置（Ｈａｃｈ社製、「ＤＲ−４０００」）を使用してＤＰＤ法により測定）
(Test condition)
・ Water: Simulated water prepared by adding ordinary bouillon to Sagamihara well water and adjusting the number of common bacteria to 10 5 CFU / ml ・ Drug: Compositions 1, 2, 4 to 7 were converted to effective halogen concentration (effective chlorine conversion) (Concentration) to be 1 mg / L (measurement method of effective halogen concentration: measured by DPD method using residual chlorine measuring device (DR-4000, manufactured by Hach))
（評価方法）
・薬剤添加後２４時間後の一般細菌数を菌数測定キット（三愛石油製、バイオチェッカーＴＴＣ）を使用して測定
(Evaluation method)
・ Measure the number of general bacteria 24 hours after the addition of the drug using a bacteria count kit (Bio-Checker TTC, manufactured by Sanai Petroleum)
試験結果を表２に示す。 Table 2 shows the test results.
組成物１，２，５，６は、高い逆浸透膜（ＲＯ膜）の排除率を保持し、透過水の有効ハロゲン濃度（有効塩素換算濃度）も低く、酸化力、殺菌力も高かった。組成物１，２，５，６の中では、組成物１が、最も高い逆浸透膜（ＲＯ膜）の排除率を保持し、透過水の有効ハロゲン濃度（有効塩素換算濃度）が最も低かった。 Compositions 1, 2, 5, and 6 retained a high rejection rate of a reverse osmosis membrane (RO membrane), had a low effective halogen concentration (concentration in terms of effective chlorine) of permeated water, and had high oxidizing power and sterilizing power. Among compositions 1, 2, 5, and 6, composition 1 retained the highest rejection rate of the reverse osmosis membrane (RO membrane) and had the lowest effective halogen concentration (concentration in terms of effective chlorine) of the permeated water. .
組成物４は、酸化力、殺菌力は高いものの、逆浸透膜（ＲＯ膜）の排除率が低下し、透過水の有効ハロゲン濃度（有効塩素換算濃度）も高かった。組成物７は、酸化力、殺菌力は高いものの、透過水の有効ハロゲン濃度（有効塩素換算濃度）がやや高かった。 Although composition 4 had high oxidizing power and sterilizing power, the rejection rate of the reverse osmosis membrane (RO membrane) was reduced, and the effective halogen concentration (concentration in terms of effective chlorine) of the permeated water was also high. Although the oxidizing power and the bactericidal power of the composition 7 were high, the effective halogen concentration (concentration in terms of effective chlorine) of the permeated water was slightly higher.
「透過水の臭素酸イオンの濃度の比較実験」
組成物調製時の窒素ガスパージの有無による透過水の臭素酸イオンの濃度を比較した。
"Comparison experiment of bromate ion concentration in permeated water"
The bromate ion concentrations in the permeated water were compared with and without the nitrogen gas purge during the preparation of the composition.
［組成物１’の調製］
組成物１と同様にして、窒素雰囲気下で、液体臭素：１７重量％（ｗｔ％）、スルファミン酸：１０．７重量％、水酸化ナトリウム：１２．９重量％、水酸化カリウム：３．９５重量％、水：残分を混合して、組成物１’を調製した。組成物１’のｐＨは１４、有効ハロゲン濃度（有効塩素換算濃度）は７．５重量％であり、臭素酸濃度は５ｍｇ／ｋｇ未満であった。
[Preparation of composition 1 ']
Similarly to composition 1, under a nitrogen atmosphere, liquid bromine: 17% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.95 Composition 1 'was prepared by mixing the weight%, water: residue. Composition 1 'had a pH of 14, an effective halogen concentration (concentration in terms of effective chlorine) of 7.5% by weight, and a bromate concentration of less than 5 mg / kg.
［組成物８の調製］
窒素パージを行わず、大気下で、液体臭素：１７重量％（ｗｔ％）、スルファミン酸：１０．７重量％、水酸化ナトリウム：１２．９重量％、水酸化カリウム：３．９５重量％、水：残分を混合して、組成物８を調製した。組成物８のｐＨは１４、有効ハロゲン濃度（有効塩素換算濃度）は７．４重量％であり、臭素酸濃度は６３ｍｇ／ｋｇであった。
[Preparation of Composition 8]
Without nitrogen purging, under air, liquid bromine: 17% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.95% by weight, Water: The residue was mixed to prepare Composition 8. Composition 8 had a pH of 14, an effective halogen concentration (concentration in terms of effective chlorine) of 7.4% by weight, and a bromic acid concentration of 63 mg / kg.
（試験条件）
・試験装置：平膜試験装置
・分離膜：日東電工（株）製、ポリアミド系高分子逆浸透膜 ＥＳ２０
・運転圧力：０．７５ＭＰａ
・原水：相模原井水（ｐＨ７．２、導電率２４０μＳ／ｃｍ）
・薬剤：組成物１’，８を、有効ハロゲン濃度（有効塩素換算濃度）として５０ｍｇ／Ｌとなるように添加
(Test condition)
・ Testing device: Flat membrane testing device ・ Separation membrane: Nitto Denko Corporation, polyamide-based polymer reverse osmosis membrane ES20
・ Operating pressure: 0.75MPa
Raw water: Sagamihara well water (pH 7.2, conductivity 240 μS / cm)
-Drugs: Compositions 1 'and 8 are added so that the effective halogen concentration (concentration in terms of effective chlorine) becomes 50 mg / L.
（評価方法）
・透過水の臭素酸イオン濃度を、イオンクロマトグラフ−ポストカラム吸光光度法で測定した。
(Evaluation method)
-The bromate ion concentration of the permeated water was measured by ion chromatography-post column absorption spectrophotometry.
試験結果を表３に示す。 Table 3 shows the test results.
組成物１’では、給水、透過水中の臭素酸イオン濃度は１μｇ／Ｌ未満であった。組成物８では、給水、透過水中の臭素酸イオン濃度は、組成物１’に比べて高かった。 In the composition 1 ', the bromate ion concentration in the feed water and the permeated water was less than 1 µg / L. In composition 8, the bromate ion concentration in the feed water and the permeated water was higher than in composition 1 '.
Claims (5)
臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、
スルファミン酸化合物と、
を存在させ、
前記給水または洗浄水のトリハロメタン前駆物質の濃度が、トリハロメタン生成能として０．０１ｍｇ／Ｌ以上であり、
前記分離膜は、ポリアミド系高分子膜である逆浸透膜またはナノろ過膜であることを特徴とする分離膜のスライム抑制方法。 Containing a trihalomethane precursor, in feed water or washing water to a membrane separation device equipped with a separation membrane,
A bromine-based oxidant, or a reaction product of a bromine compound and a chlorine-based oxidant,
A sulfamic acid compound;
Exist ,
The concentration of the trihalomethane precursor in the feed water or the washing water is 0.01 mg / L or more as a trihalomethane generating ability,
The separation membrane, reverse osmosis membrane or nanofiltration slime inhibiting method of the separation membrane to excessive membrane der wherein Rukoto a polyamide-based polymer film.
臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、
スルファミン酸化合物と、
の反応生成物を存在させ、
前記給水または洗浄水のトリハロメタン前駆物質の濃度が、トリハロメタン生成能として０．０１ｍｇ／Ｌ以上であり、
前記分離膜は、ポリアミド系高分子膜である逆浸透膜またはナノろ過膜であることを特徴とする分離膜のスライム抑制方法。 Containing a trihalomethane precursor, in feed water or washing water to a membrane separation device equipped with a separation membrane,
A bromine-based oxidant, or a reaction product of a bromine compound and a chlorine-based oxidant,
A sulfamic acid compound;
In the presence of the reaction product,
The concentration of the trihalomethane precursor in the feed water or the washing water is 0.01 mg / L or more as a trihalomethane generating ability,
The separation membrane, reverse osmosis membrane or nanofiltration slime inhibiting method of the separation membrane to excessive membrane der wherein Rukoto a polyamide-based polymer film.
臭素とスルファミン酸化合物の混合物、または、臭素とスルファミン酸化合物との反応生成物を存在させ、
前記給水または洗浄水のトリハロメタン前駆物質の濃度が、トリハロメタン生成能として０．０１ｍｇ／Ｌ以上であり、
前記分離膜は、ポリアミド系高分子膜である逆浸透膜またはナノろ過膜であることを特徴とする分離膜のスライム抑制方法。 Containing a trihalomethane precursor, in feed water or washing water to a membrane separation device equipped with a separation membrane,
A mixture of bromine and a sulfamic acid compound, or a reaction product of bromine and a sulfamic acid compound ,
The concentration of the trihalomethane precursor in the feed water or the washing water is 0.01 mg / L or more as a trihalomethane generating ability,
The separation membrane, reverse osmosis membrane or nanofiltration slime inhibiting method of the separation membrane to excessive membrane der wherein Rukoto a polyamide-based polymer film.
前記臭素とスルファミン酸化合物との反応生成物が、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加して反応させる工程を含む方法により得られたものであることを特徴とする分離膜のスライム抑制方法。 A slime suppressing method for a separation membrane according to claim 3 ,
The reaction product of the bromine and the sulfamic acid compound is obtained by a method including a step of adding bromine to a mixed solution containing water, an alkali, and a sulfamic acid compound under an inert gas atmosphere to cause a reaction. A method for suppressing slime of a separation membrane, comprising:
前記トリハロメタン前駆物質が、フミン質を含むことを特徴とする分離膜のスライム抑制方法。 A slime suppression method for a separation membrane according to any one of claims 1 to 4 ,
The method for suppressing slime of a separation membrane, wherein the trihalomethane precursor contains humic substances.
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