JP6837301B2 - Reverse osmosis membrane treatment method and reverse osmosis membrane treatment system - Google Patents
Reverse osmosis membrane treatment method and reverse osmosis membrane treatment system Download PDFInfo
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- JP6837301B2 JP6837301B2 JP2016145247A JP2016145247A JP6837301B2 JP 6837301 B2 JP6837301 B2 JP 6837301B2 JP 2016145247 A JP2016145247 A JP 2016145247A JP 2016145247 A JP2016145247 A JP 2016145247A JP 6837301 B2 JP6837301 B2 JP 6837301B2
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- 239000012528 membrane Substances 0.000 title claims description 157
- 238000001223 reverse osmosis Methods 0.000 title claims description 144
- 238000000034 method Methods 0.000 title claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 188
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 86
- 239000000460 chlorine Substances 0.000 claims description 86
- 229910052801 chlorine Inorganic materials 0.000 claims description 86
- -1 sulfamic acid compound Chemical class 0.000 claims description 66
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 59
- 229910052794 bromium Inorganic materials 0.000 claims description 58
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 51
- 239000007800 oxidant agent Substances 0.000 claims description 41
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 35
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 description 27
- 230000001590 oxidative effect Effects 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- 239000007795 chemical reaction product Substances 0.000 description 15
- 230000006866 deterioration Effects 0.000 description 13
- 241000894006 Bacteria Species 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 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 11
- 150000003839 salts Chemical class 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 10
- 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 8
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
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- 230000000903 blocking effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 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
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 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
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 2
- 150000001648 bromium Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 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
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 229920006254 polymer film Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- FECFIIXKXJBOSU-UHFFFAOYSA-N butylsulfamic acid Chemical group CCCCNS(O)(=O)=O FECFIIXKXJBOSU-UHFFFAOYSA-N 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
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 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
- BAQKWXACUNEBOT-UHFFFAOYSA-N dibutylsulfamic acid Chemical compound CCCCN(S(O)(=O)=O)CCCC BAQKWXACUNEBOT-UHFFFAOYSA-N 0.000 description 1
- YGNOYUCUPMACDT-UHFFFAOYSA-N dimethylsulfamic acid Chemical compound CN(C)S(O)(=O)=O YGNOYUCUPMACDT-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XRVWREPFYXZOPK-UHFFFAOYSA-N dipropylsulfamic acid Chemical compound CCCN(S(O)(=O)=O)CCC XRVWREPFYXZOPK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 238000009472 formulation Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000000691 measurement method Methods 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
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- AMULHDKUJWPBKU-UHFFFAOYSA-L nickel(2+);dichlorite Chemical compound [Ni+2].[O-]Cl=O.[O-]Cl=O AMULHDKUJWPBKU-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 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
- 239000000376 reactant Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide 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
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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Description
本発明は、逆浸透膜処理方法および逆浸透膜処理システムに関する。 The present invention relates to a reverse osmosis membrane treatment method and a reverse osmosis membrane treatment system.
逆浸透膜（ＲＯ膜）を用いる逆浸透膜処理方法において、各種のスライム抑制剤（殺菌剤）が使用される。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逆浸透膜の前段に添加される。塩素系酸化剤は逆浸透膜を劣化させる可能性が高いため、一般的には逆浸透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逆浸透膜に流入させることで運用されている。 In the reverse osmosis membrane treatment method using a reverse osmosis membrane (RO membrane), various slime inhibitors (bactericides) are used. Chlorine-based oxidizing agents such as hypochlorous acid are typical slime inhibitors, and are usually added to the pre-stage of the reverse osmosis membrane for the purpose of suppressing slime in the system. Since chlorine-based oxidants have a high possibility of deteriorating the reverse osmosis membrane, generally, the chlorine-based oxidizer is reduced and decomposed immediately before the reverse osmosis membrane, or the chlorine-based oxidant intermittently flows into the reverse osmosis membrane. It is operated by letting it.
また、スライム抑制剤として塩素系酸化剤とスルファミン酸化合物とからなる結合塩素剤を逆浸透膜の被処理水中に存在させる方法（特許文献１参照）や、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混合物もしくは反応生成物を被処理水に添加する方法（特許文献２参照）が知られている。 Further, as a slime inhibitor, a method of allowing a bound chlorine agent composed of a chlorine-based oxidant and a sulfamic acid compound to exist in the water to be treated of the back-penetration film (see Patent Document 1), a bromine-based oxidant, or a bromine compound and chlorine. A method of adding a mixture of a reaction product with a system oxidizing agent and a sulfamic acid compound or a reaction product to water to be treated (see Patent Document 2) is known.
特許文献１の結合塩素剤は、スライム抑制効果が十分ではない。特許文献２では、被処理水中の有効ハロゲン濃度（有効塩素換算濃度）が０．０１〜１００ｍｇ／Ｌが好ましいと記載されているものの、詳細な検討はなされていない。 The combined chlorine agent of Patent Document 1 does not have a sufficient slime suppressing effect. Although Patent Document 2 describes that the effective halogen concentration (effective chlorine equivalent concentration) in the water to be treated is preferably 0.01 to 100 mg / L, detailed studies have not been made.
特許文献３には、逆浸透膜処理において、好ましくは濃縮水の酸化剤濃度が２ｐｐｍ以下、より好ましくは０．０５ｐｐｍ以下となるように、被処理水を逆浸透膜ユニットによって膜分離することが記載されている。しかし、逆浸透膜処理においてスライム抑制を確実に実施するためには、酸化剤の濃度を管理するのでは不十分であった。 According to Patent Document 3, in the reverse osmosis membrane treatment, the water to be treated is membrane-separated by a reverse osmosis membrane unit so that the oxidant concentration of the concentrated water is preferably 2 ppm or less, more preferably 0.05 ppm or less. Have been described. However, it was not sufficient to control the concentration of the oxidizing agent in order to reliably suppress slime in the reverse osmosis membrane treatment.
特許文献４には、被処理水中に次亜塩素酸ナトリウム等の酸化性の物質が含まれる場合や、被処理水のＯＲＰ（酸化還元電位）が高い場合、逆浸透膜が劣化することが記載されている。 Patent Document 4 describes that the reverse osmosis membrane deteriorates when the water to be treated contains an oxidizing substance such as sodium hypochlorite or when the ORP (oxidation-reduction potential) of the water to be treated is high. Has been done.
本発明の目的は、逆浸透膜のスライム抑制効果を有し、かつ逆浸透膜の酸化劣化を抑制する逆浸透膜処理方法および逆浸透膜処理システムを提供することにある。 An object of the present invention is to provide a reverse osmosis membrane treatment method and a reverse osmosis membrane treatment system which have a slime suppressing effect of a reverse osmosis membrane and suppress oxidative deterioration of the reverse osmosis membrane.
本発明は、逆浸透膜に被処理水を通水して処理水および濃縮水を得る逆浸透膜処理方法であって、前記濃縮水の全塩素濃度を測定し、前記濃縮水中の全塩素濃度が０．１ｍｇ／Ｌ以上５．０ｍｇ／Ｌ以下の範囲となるように、前記被処理水に臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を存在させる、逆浸透膜処理方法である。 The present invention is a reverse osmosis membrane treatment method in which water to be treated is passed through a reverse osmosis membrane to obtain treated water and concentrated water. The total chlorine concentration of the concentrated water is measured, and the total chlorine concentration of the concentrated water is measured. A stabilized hypobromic acid composition containing a bromine-based oxidizing agent and a sulfamic acid compound is present in the water to be treated so that the concentration is in the range of 0.1 mg / L or more and 5.0 mg / L or less. This is a reverse osmosis membrane treatment method.
本発明は、逆浸透膜に被処理水を通水して処理水および濃縮水を得る逆浸透膜処理方法であって、前記濃縮水の全塩素濃度を測定し、前記濃縮水中の全塩素濃度が０．１ｍｇ／Ｌ以上５．０ｍｇ／Ｌ以下の範囲となるように、前記被処理水に臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を存在させる、逆浸透膜処理方法である。 The present invention is a reverse osmosis membrane treatment method in which water to be treated is passed through a reverse osmosis membrane to obtain treated water and concentrated water. The total chlorine concentration of the concentrated water is measured, and the total chlorine concentration of the concentrated water is measured. A reverse osmosis membrane in which a stabilized hypobromic acid composition containing bromine and a sulfamic acid compound is present in the water to be treated so that the concentration is in the range of 0.1 mg / L or more and 5.0 mg / L or less. It is a processing method.
本発明は、逆浸透膜に被処理水を通水して処理水および濃縮水を得る逆浸透膜処理システムであって、逆浸透膜を有する逆浸透膜処理装置と；前記濃縮水中の全塩素濃度が０．１ｍｇ／Ｌ以上５．０ｍｇ／Ｌ以下の範囲となるように、前記被処理水に臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を添加する添加手段と；前記濃縮水の全塩素濃度を測定する全塩素濃度測定手段と；を備える、逆浸透膜処理システムである。 The present invention is a reverse osmosis membrane treatment system for obtaining treated water and concentrated water by passing water to be treated through the reverse osmosis membrane, and a reverse osmosis membrane treatment apparatus having a reverse osmosis membrane; total chlorine in the concentrated water. A stabilized hypobromic acid composition containing a bromine-based oxidizing agent and a sulfamic acid compound is added to the water to be treated so that the concentration is in the range of 0.1 mg / L or more and 5.0 mg / L or less. and adding means; and the total chlorine concentration measuring means for measuring the total chlorine concentration before Symbol concentrate; comprises a reverse osmosis membrane treatment system.
本発明は、逆浸透膜に被処理水を通水して処理水および濃縮水を得る逆浸透膜処理システムであって、逆浸透膜を有する逆浸透膜処理装置と；前記濃縮水中の全塩素濃度が０．１ｍｇ／Ｌ以上５．０ｍｇ／Ｌ以下の範囲となるように、前記被処理水に臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を添加する添加手段と；前記濃縮水の全塩素濃度を測定する全塩素濃度測定手段と；を備える、逆浸透膜処理システムである。 The present invention is a reverse osmosis membrane treatment system for obtaining treated water and concentrated water by passing water to be treated through the reverse osmosis membrane, and a reverse osmosis membrane treatment apparatus having a reverse osmosis membrane; total chlorine in the concentrated water. As an addition means for adding a stabilized hypobromic acid composition containing bromine and a sulfamic acid compound to the water to be treated so that the concentration is in the range of 0.1 mg / L or more and 5.0 mg / L or less. ; and the total chlorine concentration measuring means for measuring the total chlorine concentration before Symbol concentrate; comprises a reverse osmosis membrane treatment system.
本発明では、逆浸透膜に被処理水を通水して処理水および濃縮水を得る逆浸透膜処理において、逆浸透膜のスライム抑制効果を有し、かつ逆浸透膜の酸化劣化を抑制することができる。 In the present invention, in the reverse osmosis membrane treatment in which the water to be treated is passed through the reverse osmosis membrane to obtain treated water and concentrated water, the reverse osmosis membrane has a slime-suppressing effect and suppresses oxidative deterioration of the reverse osmosis membrane. be able to.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 Embodiments of the present invention will be described below. The present embodiment is an example of carrying out the present invention, and the present invention is not limited to the present embodiment.
本発明の実施形態に係る逆浸透膜処理システムの一例の概略を図１に示し、その構成について説明する。 An outline of an example of a reverse osmosis membrane treatment system according to an embodiment of the present invention is shown in FIG. 1, and its configuration will be described.
逆浸透膜処理システム１は、逆浸透膜を有する逆浸透膜処理装置１２を備える。逆浸透膜処理システム１は、被処理水を貯留する被処理水槽１０を備えてもよい。
The reverse osmosis membrane treatment system 1 includes a reverse osmosis
図１の逆浸透膜処理システム１において、被処理水槽１０の入口には被処理水配管１８が接続され、被処理水槽１０の出口と逆浸透膜処理装置１２の入口とは、ポンプ１４を介して被処理水供給配管２０により接続されている。逆浸透膜処理装置１２の透過水出口には透過水配管２２が接続され、濃縮水出口には濃縮水配管２４が接続されている。濃縮水配管２４には、全塩素濃度測定手段として、全塩素濃度測定装置１６が接続されている。被処理水槽１０には、スライム抑制剤である安定化次亜臭素酸組成物を添加する添加手段として、添加配管２６が接続されている。
In the reverse osmosis membrane treatment system 1 of FIG. 1, a
本実施形態に係る逆浸透膜処理方法および逆浸透膜処理システム１の動作について説明する。 The reverse osmosis membrane treatment method and the operation of the reverse osmosis membrane treatment system 1 according to the present embodiment will be described.
被処理水は、被処理水配管１８を通して必要に応じて被処理水槽１０に貯留される。被処理水槽１０において被処理水に安定化次亜臭素酸組成物が添加配管２６を通して添加された後、被処理水は、ポンプ１４により被処理水供給配管２０を通して、逆浸透膜処理装置１２に供給される。逆浸透膜処理装置１２において被処理水の逆浸透膜処理が行われる（逆浸透膜処理工程）。逆浸透膜処理で得られた透過水は、透過水配管２２を通して排出され、濃縮水は、濃縮水配管２４を通して排出される。濃縮水配管２４において、全塩素濃度測定装置１６により、濃縮水の全塩素濃度が測定される（全塩素濃度測定工程）。なお、安定化次亜臭素酸組成物は、被処理水供給配管２０におけるポンプ１４の吸込側、吐出側において被処理水に添加されてもよい。
The water to be treated is stored in the
濃縮水は、図２の逆浸透膜処理システム３に示すように、濃縮水循環配管２８により、逆浸透膜処理装置１２の前段側、例えば被処理水槽１０に循環されてもよい。図２の逆浸透膜処理システム３では、全塩素濃度測定手段として、全塩素濃度測定装置１６が濃縮水循環配管２８に接続されている。図２の逆浸透膜処理システム３の場合、全塩素濃度測定装置１６は、通常は濃縮水循環配管２８に接続されているが、濃縮水の全塩素濃度と、安定化次亜臭素酸組成物添加後の被処理水の全塩素濃度とがほぼ同じである場合には、被処理水供給配管２０に接続されていてもよい。
As shown in the reverse osmosis membrane treatment system 3 of FIG. 2, the concentrated water may be circulated by the concentrated
本実施形態に係る逆浸透膜処理方法では、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水に臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を存在させる。「臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物」は、「臭素系酸化剤」と「スルファミン酸化合物」との混合物を含む安定化次亜臭素酸組成物であってもよいし、「臭素系酸化剤とスルファミン酸化合物との反応生成物」を含む安定化次亜臭素酸組成物であってもよい。 In the reverse osmosis membrane treatment method according to the present embodiment, a bromine-based oxidizing agent and a sulfamic acid compound are added to the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L. A stabilized hypobromous acid composition containing is present. The "stabilized hypobromous acid composition containing a bromine-based oxidant and a sulfamic acid compound" is a stabilized hypobromous acid composition containing a mixture of a "bromine-based oxidant" and a "sulfamic acid compound". It may be a stabilized hypobromous acid composition containing "a reaction product of a bromine-based oxidizing agent and a sulfamic acid compound".
すなわち、本実施形態に係る逆浸透膜処理方法は、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水に、「臭素系酸化剤」と「スルファミン酸化合物」との混合物を存在させる方法である。これにより、被処理水中で、安定化次亜臭素酸組成物が生成すると考えられる。 That is, in the reverse osmosis membrane treatment method according to the present embodiment, "bromine-based oxidant" is added to the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L. A method of allowing a mixture with a "sulfamic acid compound" to be present. It is considered that this produces a stabilized hypobromous acid composition in the water to be treated.
また、本実施形態に係る逆浸透膜処理方法は、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水に、「臭素系酸化剤とスルファミン酸化合物との反応生成物」である安定化次亜臭素酸組成物を存在させる方法である。 Further, in the reverse osmosis membrane treatment method according to the present embodiment, "bromium-based oxidant and sulfamine" are added to the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L. This is a method for allowing a stabilized hypobromous acid composition to be present, which is a "reaction product with an acid compound".
具体的には本実施形態に係る逆浸透膜処理方法は、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水に、例えば、「臭素」、「塩化臭素」、「次亜臭素酸」または「臭化ナトリウムと次亜塩素酸との反応物」と、「スルファミン酸化合物」との混合物を存在させる方法である。 Specifically, the reverse osmosis membrane treatment method according to the present embodiment uses, for example, "bromine" in the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L. , "Bromide chloride", "hypobromous acid" or "reactant of sodium bromide and hypochlorous acid" and a mixture of "sulfamic acid compound".
また、本実施形態に係る逆浸透膜処理方法は、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水に、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」である安定化次亜臭素酸組成物を存在させる方法である。 Further, in the back-penetration membrane treatment method according to the present embodiment, for example, "bromium and sulfamic acid" are added to the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L. "Reaction product with compound", "Reaction product with bromine chloride and sulfamic acid compound", or "Reaction product with sodium bromide and hypochlorous acid and sulfamic acid compound". A method in which a stabilized hypobromous acid composition is present.
これらの方法により、逆浸透膜のスライム抑制効果を有し、かつ逆浸透膜の酸化劣化を抑制することができ、逆浸透膜のスライム抑制効果を長期的に維持することができる。本発明者らは、逆浸透膜の長期的なスライム抑制効果を有し、かつ逆浸透膜の酸化劣化を抑制するために、被処理水中ではなく濃縮水中の安定化次亜臭素酸組成物を適切な濃度に維持することが重要であることを見出した。本実施形態では、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように維持するが、０．１ｍｇ／Ｌ以上５ｍｇ／Ｌ未満の範囲となるように維持することが好ましく、０．１ｍｇ／Ｌ以上０．５ｍｇ／Ｌ未満の範囲となるように維持することがより好ましく、０．１ｍｇ／Ｌ以上０．２ｍｇ／Ｌ未満の範囲となるように維持することがさらに好ましい。濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ未満の場合、スライムが十分に抑制できず、１０ｍｇ／Ｌ以上であると逆浸透膜を劣化させるおそれがある。被処理水中の全塩素濃度が０．０５ｍｇ／Ｌ以上であっても、被処理水および逆浸透膜の汚染度等によっては逆浸透膜の濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ未満となり、スライムが抑制できない場合があるため、被処理水の全塩素濃度管理だけでは不十分である。 By these methods, the slime suppressing effect of the reverse osmosis membrane can be obtained, the oxidative deterioration of the reverse osmosis membrane can be suppressed, and the slime suppressing effect of the reverse osmosis membrane can be maintained for a long period of time. In order to have a long-term slime-suppressing effect on the reverse osmosis membrane and to suppress oxidative deterioration of the reverse osmosis membrane, the present inventors have prepared a stabilized hypobromous acid composition in concentrated water instead of the water to be treated. We have found that it is important to maintain an appropriate concentration. In the present embodiment, the total chlorine concentration in the concentrated water is maintained in the range of 0.05 mg / L or more and less than 10 mg / L, but is maintained in the range of 0.1 mg / L or more and less than 5 mg / L. It is preferable to maintain it in the range of 0.1 mg / L or more and less than 0.5 mg / L, and it is more preferable to maintain it in the range of 0.1 mg / L or more and less than 0.2 mg / L. Is even more preferable. If the total chlorine concentration in the concentrated water is less than 0.05 mg / L, slime cannot be sufficiently suppressed, and if it is 10 mg / L or more, the reverse osmosis membrane may be deteriorated. Even if the total chlorine concentration in the water to be treated is 0.05 mg / L or more, the total chlorine concentration in the concentrated water of the reverse osmosis membrane may be less than 0.05 mg / L depending on the degree of contamination of the water to be treated and the reverse osmosis membrane. Since slime may not be suppressed, it is not enough to control the total chlorine concentration of the water to be treated.
このように、本実施形態に係る逆浸透膜処理方法において、安定化次亜臭素酸組成物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、逆浸透膜への劣化影響が低い。このため、本実施形態に係る逆浸透膜処理方法で用いられる安定化次亜臭素酸組成物は、スライム抑制剤としては好適である。 As described above, in the reverse osmosis membrane treatment method according to the present embodiment, the stabilized hypobromous acid composition exerts a slime suppressing effect equal to or higher than that of a chlorine-based oxidizing agent such as hypochlorous acid. Compared with chlorine-based oxidants, the effect of deterioration on the reverse osmosis membrane is low. Therefore, the stabilized hypobromous acid composition used in the reverse osmosis membrane treatment method according to the present embodiment is suitable as a slime inhibitor.
本実施形態に係る逆浸透膜処理方法において、「臭素系酸化剤」が臭素である場合、塩素系酸化剤が存在しないため、逆浸透膜への劣化影響が著しく低く、逆浸透膜の長期的なスライム抑制効果を有する。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 reverse osmosis membrane treatment method according to the present embodiment, when the "bromine-based oxidant" is bromine, the effect of deterioration on the reverse osmosis membrane is extremely low because there is no chlorine-based oxidant, and the reverse osmosis membrane is long-term. Has a slime-suppressing effect. When a chlorine-based oxidizing agent is contained, there is concern about the formation of chloric acid.
本実施形態に係る逆浸透膜処理方法では、例えば、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水に、「臭素系酸化剤」と「スルファミン酸化合物」とを薬注ポンプ等により注入してもよい。「臭素系酸化剤」と「スルファミン酸化合物」とは別々に被処理水に添加してもよく、または、原液同士で混合させてから被処理水に添加してもよい。 In the reverse osmosis membrane treatment method according to the present embodiment, for example, the water to be treated is referred to as a "bromine-based oxidant" so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L. The "sulfamic acid compound" may be injected by a chemical injection pump or the like. The "bromine-based oxidizing agent" and the "sulfamic acid compound" may be added to the water to be treated separately, or the stock solutions may be mixed with each other and then added to the water to be treated.
また、例えば、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水に、「臭素系酸化剤とスルファミン酸化合物との反応生成物」を薬注ポンプ等により注入してもよい。 Further, for example, a "reaction product of a bromine-based oxidant and a sulfamic acid compound" is added to the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L. Injection It may be injected by a pump or the like.
全塩素濃度測定手段としては、安定化次亜臭素酸組成物が添加された被処理水または濃縮水の安定化次亜臭素酸組成物の濃度を全塩素濃度として測定することができるものであればよく、特に制限はないが、例えば、ジエチル−ｐ−フェニレンジアミン（ＤＰＤ）比色法、ジエチル−ｐ−フェニレンジアミン（ＤＰＤ）吸光光度法、電流滴定法、ジエチル−ｐ−フェニレンジアミン（ＤＰＤ）滴定法、ヨウ素滴定法、ポーラログラフ法、オルトトリジン法等による測定装置が挙げられる。 As the means for measuring the total chlorine concentration, the concentration of the stabilized hypobromic acid composition in the water to be treated or the concentrated water to which the stabilized hypobromic acid composition is added can be measured as the total chlorine concentration. However, there are no particular restrictions, but for example, diethyl-p-phenylenediamine (DPD) colorimetric method, diethyl-p-phenylenediamine (DPD) absorptiometry, current titration method, diethyl-p-phenylenediamine (DPD). Examples thereof include a measuring device using a titration method, an iodine titration method, a polarograph method, an orthotridin method, or the like.
本実施形態に係る逆浸透膜処理方法において、「臭素系酸化剤」の当量に対する「スルファミン酸化合物」の当量の比は、１以上であることが好ましく、１以上２以下の範囲であることがより好ましい。「臭素系酸化剤」の当量に対する「スルファミン酸化合物」の当量の比が１未満であると、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。 In the reverse osmosis membrane treatment method according to the present embodiment, the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" is preferably 1 or more, and preferably in the range of 1 or more and 2 or less. More preferred. If the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidant" is less than 1, the film may be deteriorated, and if it exceeds 2, the production cost may increase.
逆浸透膜に接触する全塩素濃度は有効塩素濃度換算で、０．０１〜１００ｍｇ／Ｌであることが好ましい。０．０１ｍｇ／Ｌ未満であると、十分な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、逆浸透膜の劣化、配管等の腐食を引き起こす可能性がある。 The total chlorine concentration in contact with the reverse osmosis membrane is preferably 0.01 to 100 mg / L in terms of effective chlorine concentration. If it is less than 0.01 mg / L, a sufficient slime suppressing effect may not be obtained, and if it is more than 100 mg / L, deterioration of the reverse osmosis membrane and corrosion of pipes 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。次亜臭素酸は、臭化ナトリウム等の臭化物と次亜塩素酸等の塩素系酸化剤とを反応させて生成させたものであってもよい。 Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, bromate, bromate, hypobromous acid and the like. Hypobromous acid may be produced by reacting a bromide such as sodium bromide with a chlorine-based oxidizing agent such as hypochlorous acid.
これらのうち、臭素を用いた「臭素とスルファミン酸化合物（臭素とスルファミン酸化合物の混合物）」または「臭素とスルファミン酸化合物との反応生成物」の製剤は、「次亜塩素酸と臭素化合物とスルファミン酸」の製剤および「塩化臭素とスルファミン酸」の製剤等に比べて、臭素酸の副生が少なく、逆浸透膜をより劣化させないため、逆浸透膜用スライム抑制剤としてはより好ましい。 Of these, the preparations of "bromic acid and sulfamic acid compound (mixture of bromic acid and sulfamic acid compound)" or "reaction product of bromic acid and sulfamic acid compound" using bromine are "hypochlorous acid and bromic acid compound". Compared with the preparations of "sulfamic acid" and "bromine chloride and sulfamic acid", the by-product of bromic acid is less and the back-penetrating membrane is not further deteriorated, so that it is more preferable as a slime inhibitor for back-penetrating membranes.
すなわち、本発明の実施形態に係る逆浸透膜処理方法は、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水に、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、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ以上１０ｍｇ／Ｌ未満の範囲となるように、被処理水中に、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 reverse osmosis membrane treatment method according to the embodiment of the present invention, bromine and sulfamic acid are added to the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L. It is preferable that the compound is present (a mixture of bromine and a sulfamic acid compound is present). Further, it is preferable that the reaction product of bromine and the sulfamic acid compound is present in the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.05 mg / L or more and less than 10 mg / L.
臭素化合物としては、臭化ナトリウム、臭化カリウム、臭化リチウム、臭化アンモニウムおよび臭化水素酸等が挙げられる。これらのうち、製剤コスト等の点から、臭化ナトリウムが好ましい。 Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide, hydrobromic acid and the like. Of these, sodium bromide is preferable from the viewpoint of formulation cost and the like.
塩素系酸化剤としては、例えば、塩素ガス、二酸化塩素、次亜塩素酸またはその塩、亜塩素酸またはその塩、塩素酸またはその塩、過塩素酸またはその塩、塩素化イソシアヌル酸またはその塩等が挙げられる。これらのうち、塩としては、例えば、次亜塩素酸ナトリウム、次亜塩素酸カリウム等の次亜塩素酸アルカリ金属塩、次亜塩素酸カルシウム、次亜塩素酸バリウム等の次亜塩素酸アルカリ土類金属塩、亜塩素酸ナトリウム、亜塩素酸カリウム等の亜塩素酸アルカリ金属塩、亜塩素酸バリウム等の亜塩素酸アルカリ土類金属塩、亜塩素酸ニッケル等の他の亜塩素酸金属塩、塩素酸アンモニウム、塩素酸ナトリウム、塩素酸カリウム等の塩素酸アルカリ金属塩、塩素酸カルシウム、塩素酸バリウム等の塩素酸アルカリ土類金属塩等が挙げられる。これらの塩素系酸化剤は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。塩素系酸化剤としては、取り扱い性等の点から、次亜塩素酸ナトリウムを用いるのが好ましい。 Examples of the chlorine-based oxidant include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chloric acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, and chlorinated isocyanuric acid or a salt thereof. And so on. Among these, examples of the salt include an alkali metal hypochlorite salt such as sodium hypochlorite and potassium hypochlorite, and an alkaline soil hypochlorite such as calcium hypochlorite and barium hypochlorite. Metallic salts, alkali metal chlorite salts such as sodium chlorate and potassium chlorate, alkaline earth metal chlorite salts such as barium chlorate, and other metal chlorite salts such as nickel chlorite. , Chlorate alkali metal salts such as ammonium chlorate, sodium chlorate, potassium chlorate, and chlorate alkaline earth metal salts such as calcium chlorate and barium chlorate. These chlorine-based oxidizing agents may be used alone or in combination of two or more. 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。 Examples of the sulfamic acid compound include N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, and N-, in addition to sulfamic acid (amide sulfate) in which both of the two R groups are hydrogen atoms. Sulfamic acid compounds, N, N-dimethylsulfamic acid, N, where one of the 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. Two R groups such as N-diethylsulfamic acid, N, N-dipropylsulfamic acid, N, N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid, etc. Sulfamic acid is a sulfamic acid compound in which both are alkyl groups having 1 to 8 carbon atoms, one of two R groups such as N-phenylsulfamic acid is a hydrogen atom, and the other is an aryl group having 6 to 10 carbon atoms. Examples include compounds and salts thereof. Examples of sulfamates include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, strontium salt and barium salt, manganese salt, copper salt, zinc salt, iron salt and cobalt salt. Other metal salts such as nickel salts, ammonium salts, guanidine salts and the like can be mentioned. The sulfamic acid compound and salts thereof may be used alone or in combination of two or more. As the sulfamic acid compound, it is preferable to use sulfamic acid (amide sulfate) from the viewpoint of environmental load and the like.
本実施形態に係る逆浸透膜処理方法において、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 reverse osmosis membrane treatment method 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 temperature. Further, the alkali may be used as an aqueous solution instead of being solid.
本実施形態に係る逆浸透膜処理方法は、逆浸透膜として昨今主流であるポリアミド系高分子膜に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、本実施形態に係る逆浸透膜処理方法ではポリアミド高分子膜においても、このような著しい膜性能の低下はほとんど起こらない。 The reverse osmosis membrane treatment method according to the present embodiment can be suitably applied to a polyamide-based polymer membrane which is the mainstream in recent years as a reverse osmosis membrane. The polyamide-based polymer film has a 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 reverse osmosis membrane treatment method according to the present embodiment, such a significant decrease in membrane performance hardly occurs even in the polyamide polymer membrane.
本実施形態に係る逆浸透膜処理方法において、逆浸透膜を備える逆浸透膜装置へ給水される被処理水の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。被処理水の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、被処理水のｐＨの上限値については、通常の逆浸透膜の適用上限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。本実施形態に係る逆浸透膜処理方法を用いる場合、被処理水のｐＨが５．５以上で運転することにより、逆浸透膜の劣化、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 reverse osmosis membrane treatment method according to the present embodiment, the pH of the water to be treated supplied to the reverse osmosis membrane apparatus provided with the reverse osmosis membrane is preferably 5.5 or more, and more preferably 6.0 or more. It is preferably 6.5 or more, and more preferably 6.5 or more. If the pH of the water to be treated is less than 5.5, the amount of permeated water may decrease. The upper limit of the pH of the water to be treated is not particularly limited as long as it is equal to or lower than the applicable upper limit pH of a normal reverse osmosis membrane (for example, pH 10), but considering the scale precipitation of hardness components such as calcium, the pH is Is preferably operated at, for example, 9.0 or less. When the reverse osmosis membrane treatment method according to the present embodiment is used, by operating the water to be treated at a pH of 5.5 or higher, deterioration of the reverse osmosis membrane and deterioration of the water quality of the treated water (permeated water) can be suppressed sufficiently. It is possible to secure a sufficient amount of permeated water while exerting a slime suppressing effect.
逆浸透膜装置において、被処理水のｐＨ５．５以上でスケールが発生する場合には、スケール抑制のために分散剤を安定化次亜臭素酸組成物と併用してもよい。分散剤としては、例えば、ポリアクリル酸、ポリマレイン酸、ホスホン酸等が挙げられる。分散剤の被処理水への添加量は、例えば、ＲＯ濃縮水中の濃度として０．１〜１，０００ｍｇ／Ｌの範囲である。 In the reverse osmosis membrane device, when scale is generated at pH 5.5 or higher of the water to be treated, a dispersant may be used in combination with a stabilized hypobromous acid composition to suppress scale. Examples of the dispersant include polyacrylic acid, polymaleic acid, phosphonic acid and the like. The amount of the dispersant 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 RO concentrated water.
また、分散剤を使用せずにスケールの発生を抑制するためには、例えば、ＲＯ濃縮水中のシリカ濃度を溶解度以下に、カルシウムスケールの指標であるランゲリア指数を０以下になるように、逆浸透膜装置の回収率等の運転条件を調整することが挙げられる。 Further, in order to suppress the generation of scale without using a dispersant, for example, reverse osmosis is performed so that the silica concentration in RO concentrated water is less than the solubility and the Langeria index, which is an index of the calcium scale, is 0 or less. It is possible to adjust operating conditions such as the recovery rate of the membrane device.
逆浸透膜装置の用途としては、例えば、海水淡水化、排水回収等が挙げられる。 Applications of the reverse osmosis membrane device include, for example, seawater desalination, wastewater recovery, and the like.
＜逆浸透膜用スライム抑制剤＞
本実施形態に係る逆浸透膜用スライム抑制剤は、「臭素系酸化剤」と「スルファミン酸化合物」との混合物を含む安定化次亜臭素酸組成物を含有するものであり、さらにアルカリを含有してもよい。
<Slime inhibitor for reverse osmosis membrane>
The slime inhibitor for reverse osmosis membrane according to the present embodiment contains a stabilized hypobromous acid composition containing a mixture of a "bromine-based oxidizing agent" and a "sulfamic acid compound", and further contains an alkali. You may.
また、本実施形態に係る逆浸透膜用スライム抑制剤は、「臭素系酸化剤とスルファミン酸化合物との反応生成物」を含む安定化次亜臭素酸組成物を含有するものであり、さらにアルカリを含有してもよい。 Further, the slime inhibitor for reverse osmosis membrane according to the present embodiment contains a stabilized hypobromous acid composition containing "a reaction product of a bromine-based oxidizing agent and a sulfamic acid compound", and further contains an alkali. May be contained.
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.
本実施形態に係る逆浸透膜用スライム抑制剤としては、逆浸透膜をより劣化させないため、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 for a back-penetrating membrane according to the present embodiment contains bromine and a sulfamic acid compound (containing a mixture of bromine and a sulfamic acid compound) in order not to further deteriorate the back-penetrating membrane, for example. , A mixture of bromine, sulfamic acid compound, alkali and water, or a reaction product of bromine and sulfamic acid compound, for example, reaction product of bromine and sulfamic acid compound, alkali, water and Mixtures of are preferred.
本実施形態に係る逆浸透膜用スライム抑制剤は、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、逆浸透膜用スライム抑制剤としては最適である。 The slime inhibitor for reverse osmosis membranes according to the present embodiment has higher oxidizing power, slime suppressing power, and slime peeling power as compared with a bound chlorine-based slime inhibitor such as chlorosulfamic acid. It hardly causes remarkable film deterioration like hypochlorous acid, which has high oxidizing power. At normal working concentrations, the effect on film deterioration is virtually negligible. Therefore, it is most suitable as a slime inhibitor for reverse osmosis membranes.
本実施形態に係る逆浸透膜用スライム抑制剤は、次亜塩素酸とは異なり、逆浸透膜をほとんど透過しないため、処理水水質への影響がほとんどない。また、次亜塩素酸等と同様に現場で濃度を測定することができるため、より正確な濃度管理が可能である。 Unlike hypochlorous acid, the slime inhibitor for reverse osmosis membranes according to the present embodiment has almost no effect on the quality of treated water because it hardly permeates the reverse osmosis membrane. In addition, since the concentration can be measured on-site in the same manner as hypochlorous acid and the like, more accurate concentration control is possible.
逆浸透膜用スライム抑制剤の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。逆浸透膜用スライム抑制剤のｐＨが１３．０以下であると逆浸透膜用スライム抑制剤中の有効ハロゲンが不安定になる場合がある。 The pH of the slime inhibitor for reverse osmosis membrane is, for example, more than 13.0, more preferably more than 13.2. If the pH of the reverse osmosis membrane slime inhibitor is 13.0 or less, the effective halogen in the reverse osmosis membrane slime inhibitor may become unstable.
逆浸透膜用スライム抑制剤中の臭素酸濃度は、５ｍｇ／ｋｇ未満であることが好ましい。逆浸透膜用スライム抑制剤中の臭素酸濃度が５ｍｇ／ｋｇ以上であると、ＲＯ透過水の臭素酸イオンの濃度が高くなる場合がある。 The bromic acid concentration in the slime inhibitor for reverse osmosis membranes is preferably less than 5 mg / kg. When the bromate concentration in the slime inhibitor for reverse osmosis membrane is 5 mg / kg or more, the concentration of bromate ion in RO permeated water may increase.
＜逆浸透膜用スライム抑制剤の製造方法＞
本実施形態に係る逆浸透膜用スライム抑制剤は、臭素系酸化剤とスルファミン酸化合物とを混合することにより得られ、さらにアルカリを混合してもよい。
<Manufacturing method of slime inhibitor for reverse osmosis membrane>
The slime inhibitor for reverse osmosis membrane according to the present embodiment can be obtained by mixing a bromine-based oxidizing agent and a sulfamic acid compound, and may be further mixed with an alkali.
臭素と、スルファミン酸化合物とを含む安定化次亜臭素酸組成物を含有する逆浸透膜用スライム抑制剤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、逆浸透膜用スライム抑制剤中の臭素酸イオン濃度が低くなり、ＲＯ透過水中の臭素酸イオン濃度が低くなる。 As a method for producing a slime inhibitor for a back-penetrating membrane containing a stabilized hypobromous acid composition containing bromine and a sulfamic acid compound, bromine is added to an inert gas in a mixed solution containing water, an alkali and a sulfamic acid compound. It is preferable to include a step of adding and reacting in an atmosphere, or a step of adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere. By adding and reacting in an inert gas atmosphere, or by adding in an inert gas atmosphere, the bromate ion concentration in the slime inhibitor for reverse osmosis membrane becomes low, and the bromate ion concentration in RO permeated water becomes low. Will be low.
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 bromine reaction exceeds 6%, the amount of bromic acid produced in the reaction system may increase.
臭素の添加率は、逆浸透膜用スライム抑制剤全体の量に対して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。臭素の添加率が逆浸透膜用スライム抑制剤全体の量に対して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 rate of bromine is preferably 25% by weight or less, and more preferably 1% by weight or more and 20% by weight or less, based on the total amount of the slime inhibitor for reverse osmosis membrane. If the addition rate of bromine exceeds 25% by weight based on the total amount of the slime inhibitor for reverse osmosis membrane, the amount of bromic acid produced in the reaction system may increase. If it is less than 1% by weight, the bactericidal activity may be inferior.
臭素添加の際の反応温度は、０℃以上２５℃以下の範囲に制御することが好ましいが、製造コスト等の面から、０℃以上１５℃以下の範囲に制御することがより好ましい。臭素添加の際の反応温度が２５℃を超えると、反応系内の臭素酸の生成量が増加する場合があり、０℃未満であると、凍結する場合がある。 The reaction temperature at the time of adding bromine is preferably controlled in the range of 0 ° C. or higher and 25 ° C. or lower, but more preferably controlled in the range of 0 ° C. or higher and 15 ° C. or lower from the viewpoint of manufacturing 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 less 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, but the present invention is not limited to the following Examples.
［安定化次亜臭素酸組成物の調製］
窒素雰囲気下で、液体臭素：１６．９重量％（ｗｔ％）、スルファミン酸：１０．７重量％、水酸化ナトリウム：１２．９重量％、水酸化カリウム：３．９４重量％、水：残分を混合して、安定化次亜臭素酸組成物を調製した。安定化次亜臭素酸組成物のｐＨは１４、全塩素濃度は７．５重量％であった。安定化次亜臭素酸組成物の詳細な調製方法は以下の通りである。
[Preparation of stabilized hypobromous acid composition]
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: residue under a nitrogen atmosphere. The minutes were mixed to prepare a stabilized hypobromous acid composition. The pH of the stabilized hypobromous acid composition was 14, and the total chlorine concentration was 7.5% by weight. The detailed preparation method of the stabilized hypobromous acid composition is as follows.
反応容器内の酸素濃度が１％に維持されるように、窒素ガスの流量をマスフローコントローラでコントロールしながら連続注入で封入した２Ｌの４つ口フラスコに１４３６ｇの水、３６１ｇの水酸化ナトリウムを加えて混合し、次いで３００ｇのスルファミン酸を加えて混合した後、反応液の温度が０〜１５℃になるように冷却を維持しながら、４７３ｇの液体臭素を加え、さらに４８％水酸化カリウム溶液２３０ｇを加え、組成物全体の量に対する重量比でスルファミン酸１０．７％、臭素１６．９％、臭素の当量に対するスルファミン酸の当量比が１．０４である、目的の安定化次亜臭素酸組成物を得た。生じた溶液のｐＨは、ガラス電極法にて測定したところ、１４であった。生じた溶液の臭素含有率は、臭素をヨウ化カリウムによりヨウ素に転換後、チオ硫酸ナトリウムを用いて酸化還元滴定する方法により測定したところ１６．９％であり、理論含有率（１６．９％）の１００．０％であった。また、臭素反応の際の反応容器内の酸素濃度は、株式会社ジコー製の「酸素モニタＪＫＯ−０２ ＬＪＤＩＩ」を用いて測定した。なお、臭素酸濃度は５ｍｇ／ｋｇ未満であった。 1436 g of water and 361 g of sodium hydroxide were added to a 2 L 4-port flask sealed by continuous injection while controlling the flow rate of nitrogen gas with a mass flow controller so that the oxygen concentration in the reaction vessel was maintained at 1%. After mixing, 300 g of sulfamic acid was added and mixed, and then 473 g of liquid bromine was added while maintaining cooling so that the temperature of the reaction solution became 0 to 15 ° C., and 230 g of 48% potassium hydroxide solution was further added. The desired stabilized hypobromous acid composition is 10.7% sulfamic acid, 16.9% bromine, and the equivalent ratio of sulfamic acid to the equivalent of bromine is 1.04 as a weight ratio to the total amount of the composition. I got something. 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 redox titrating with sodium thiosulfate, and the theoretical content (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 Co., Ltd. The bromic acid concentration was less than 5 mg / kg.
なお、ｐＨの測定は、以下の条件で行った。
電極タイプ：ガラス電極式
ｐＨ測定計：東亜ディーケーケー社製、ＩＯＬ−３０型
電極の校正：関東化学社製中性リン酸塩ｐＨ（６．８６）標準液（第２種）、同社製ホウ酸塩ｐＨ（９．１８）標準液（第２種）の２点校正で行った
測定温度：２５℃
測定値：測定液に電極を浸漬し、安定後の値を測定値とし、３回測定の平均値
The pH was measured under the following conditions.
Electrode type: Glass electrode type pH meter: DKK-TOA Corporation, IOL-30 type Electrode calibration: Kanto Chemical Co., Inc. Neutral phosphate pH (6.86) standard solution (Type 2), Borate manufactured by Kanto Chemical Co., Inc. Measurement temperature performed by two-point calibration of salt pH (9.18) standard solution (type 2): 25 ° C.
Measured value: The electrode is immersed in the measuring solution, and the value after stabilization is used as the measured value, which is the average value of three measurements.
＜実施例１〜３、比較例１，２＞
［殺菌力の比較試験］
逆浸透膜用スライム抑制剤として「臭素とスルファミン酸化合物との反応生成物」である安定化次亜臭素酸組成物を使用して、下記の通りに濃縮水中の全塩素濃度で管理した結果を比較した。
<Examples 1 to 3 and Comparative Examples 1 and 2>
[Comparative test of bactericidal power]
Using a stabilized hypobromous acid composition, which is a "reaction product of bromine and a sulfamic acid compound", as a slime inhibitor for reverse osmosis membranes, the results of controlling the total chlorine concentration in concentrated water as shown below are shown. Compared.
（試験条件）
・試験装置：エレメント試験装置
・逆浸透膜：ＬＦ１０（日東電工製）
・運転圧力：０．７５ＭＰａ
・被処理水：相模原井水（ｐＨ７．２、導電率２４０μＳ／ｃｍ）
・薬剤：安定化次亜臭素酸組成物
・試験温度：２５℃
(Test condition)
・ Test equipment: Element test equipment ・ Reverse osmosis membrane: LF10 (manufactured by Nitto Denko)
・ Operating pressure: 0.75 MPa
-Water to be treated: Sagamihara well water (pH 7.2, conductivity 240 μS / cm)
-Drug: Stabilized hypobromous acid composition-Test temperature: 25 ° C
全塩素濃度は、ＨＡＣＨ社の多項目水質分析計ＤＲ／４０００を用いて、全塩素測定法（ＤＰＤ（ジエチル−ｐ−フェニレンジアミン）法）により測定した値（ｍｇ／Ｌ ａｓＣｌ２）である。 The total chlorine concentration is a value (mg / LasCl 2 ) measured by a total chlorine measurement method (DPD (diethyl-p-phenylenediamine) method) using a multi-item water quality analyzer DR / 4000 manufactured by HACH.
菌数（一般細菌数）は、菌数測定キット（三愛石油製、バイオチェッカーＴＴＣ）を使用して測定した。酸化還元電位（ＯＲＰ）は、酸化還元電位測定装置（東亜ＤＫＫ製、ＲＭ−２０Ｐ型ＯＲＰ計）を使用して測定した。 The number of bacteria (general number of bacteria) was measured using a bacterial count measurement kit (manufactured by San-Ai Oil, Biochecker TTC). The redox potential (ORP) was measured using an oxidation-reduction potential measuring device (RM-20P type ORP meter manufactured by Toa DKK).
導電率は、電気伝導率計（東亜ディーケーケー社製、ＡＯＬ−１０）により測定した。導電率阻止率の変化率は、以下の式により計算した。
（０時間後導電率阻止率［％］）÷（１００時間後導電率阻止率［％］）×１００
The conductivity was measured with an electric conductivity meter (AOL-10, manufactured by DKK-TOA CORPORATION). The rate of change in the conductivity blocking rate was calculated by the following formula.
(Conductivity blocking rate after 0 hours [%]) ÷ (Conductivity blocking rate after 100 hours [%]) x 100
評価結果を表１に示す。 The evaluation results are shown in Table 1.
（比較例１）
比較例１は、濃縮水中の全塩素濃度を０．０３ｍｇ／Ｌ以下に維持して通水した例である。２４時間通水後、濃縮水中の菌数はほとんど減少しないことがわかった。また、酸化還元電位（ＯＲＰ）が２００ｍＶ以下のため、１００時間通水後、導電率阻止率がほとんど低下しないことがわかった。
(Comparative Example 1)
Comparative Example 1 is an example in which the total chlorine concentration in the concentrated water was maintained at 0.03 mg / L or less and water was passed. After 24 hours of water flow, it was found that the number of bacteria in the concentrated water hardly decreased. Further, it was found that since the redox potential (ORP) was 200 mV or less, the conductivity blocking rate hardly decreased after 100 hours of water flow.
（比較例２）
比較例２は、濃縮水中の全塩素濃度を１０ｍｇ／Ｌで通水した例である。２４時間通水後、濃縮水中の菌数は減少したが、酸化還元電位（ＯＲＰ）が７００ｍＶを超えたため、膜劣化により１００時間通水後、導電率阻止率が低下したことがわかった。
(Comparative Example 2)
Comparative Example 2 is an example in which the total chlorine concentration in the concentrated water was passed at 10 mg / L. After 24 hours of water flow, the number of bacteria in the concentrated water decreased, but since the redox potential (ORP) exceeded 700 mV, it was found that the conductivity inhibition rate decreased after 100 hours of water flow due to membrane deterioration.
（実施例１〜３）
実施例１〜３は、濃縮水中の全塩素濃度をそれぞれ０．１、１．０、５ｍｇ／Ｌで通水した例である。２４時間通水後、濃縮水中菌数は減少し、ＯＲＰが２００ｍＶを超え、７００ｍＶ以下になったため、１００時間通水後、導電率阻止率がほとんど低下しないことがわかった。
(Examples 1 to 3)
Examples 1 to 3 are examples in which the total chlorine concentration in the concentrated water was 0.1, 1.0, and 5 mg / L, respectively. After 24 hours of water flow, the number of bacteria in the concentrated water decreased, and the ORP exceeded 200 mV and became 700 mV or less. Therefore, it was found that the conductivity blocking rate hardly decreased after 100 hours of water flow.
＜実施例４〜６、比較例３＞
［汚染した膜への効果検証試験］
次に、逆浸透膜用スライム抑制剤として「臭素とスルファミン酸化合物との反応生成物」である安定化次亜臭素酸組成物を使用して、汚染した膜への効果検証を試験した。
<Examples 4 to 6, Comparative Example 3>
[Effect verification test on contaminated membrane]
Next, a stabilized hypobromous acid composition, which is a “reaction product of bromine and a sulfamic acid compound”, was used as a slime inhibitor for reverse osmosis membranes, and verification of its effect on contaminated membranes was tested.
（試験条件）
・試験装置：現場実運用装置
・逆浸透膜：ＲＥ４０４０−ＦＥＮ（東レ製）
・水：工水＋回収水
・薬剤：安定化次亜臭素酸組成物
(Test condition)
・ Test equipment: On-site actual operation equipment ・ Reverse osmosis membrane: RE4040-FEN (manufactured by Toray Industries, Inc.)
・ Water: Reclaimed water + Recovered water ・ Chemicals: Stabilized hypobromous acid composition
全塩素濃度は、実施例１と同様にして測定した。菌数（一般細菌数）は、３Ｍ製、ペトリフィルムＡＣプレートを使用して測定した。 The total chlorine concentration was measured in the same manner as in Example 1. The number of bacteria (general number of bacteria) was measured using a Petrifilm AC plate manufactured by 3M.
評価結果を表２に示す。 The evaluation results are shown in Table 2.
（比較例３）
比較例３は、汚染した逆浸透膜に安定化次亜臭素酸組成物を供給し、通水した例である。被処理水中の全塩素濃度が０．０７ｍｇ／Ｌの場合、汚染した逆浸透膜に通水することにより、濃縮水中の全塩素濃度が０．０４ｍｇ／Ｌとなった。濃縮水中の菌数は３８０ＣＦＵ／ｍＬとなった。被処理水中の全塩素濃度が０．０５ｍｇ／Ｌ以上であっても、濃縮水中の全塩素濃度が０．０５ｍｇ／Ｌ未満となり、スライムが抑制できず、被処理水の全塩素濃度管理だけでは不十分であることがわかる。
(Comparative Example 3)
Comparative Example 3 is an example in which a stabilized hypobromous acid composition was supplied to a contaminated reverse osmosis membrane and water was passed through the membrane. When the total chlorine concentration in the water to be treated was 0.07 mg / L, the total chlorine concentration in the concentrated water became 0.04 mg / L by passing water through the contaminated reverse osmosis membrane. The number of bacteria in the concentrated water was 380 CFU / mL. Even if the total chlorine concentration in the water to be treated is 0.05 mg / L or more, the total chlorine concentration in the concentrated water is less than 0.05 mg / L, slime cannot be suppressed, and only the total chlorine concentration control of the water to be treated is sufficient. It turns out to be inadequate.
（実施例４，５）
実施例４，５は、汚染した逆浸透膜に安定化次亜臭素酸組成物を供給し、通水した例である。被処理水中の全塩素濃度がそれぞれ０．２１、０．２８ｍｇ／Ｌの場合、汚染した逆浸透膜に通水することにより、濃縮水中の全塩素濃度がそれぞれ０．０５、０．１２ｍｇ／Ｌとなった。濃縮水中の菌数はそれぞれ１５１、６８ＣＦＵ／ｍＬとなり、比較例３と比べて濃縮水中の菌数が減少したことがわかった。
(Examples 4 and 5)
Examples 4 and 5 are examples in which the stabilized hypobromous acid composition was supplied to the contaminated reverse osmosis membrane and water was passed through the contaminated reverse osmosis membrane. When the total chlorine concentration in the water to be treated is 0.21 and 0.28 mg / L, respectively, the total chlorine concentration in the concentrated water is 0.05 and 0.12 mg / L, respectively, by passing water through the contaminated reverse osmosis membrane. It became. The numbers of bacteria in the concentrated water were 151 and 68 CFU / mL, respectively, and it was found that the number of bacteria in the concentrated water was reduced as compared with Comparative Example 3.
（実施例６）
実施例６は、汚染していない逆浸透膜に安定化次亜臭素酸組成物を供給し、通水した例である。被処理水中の全塩素濃度が０．２２ｍｇ／Ｌの場合、濃縮水中の全塩素濃度が０．２ｍｇ／Ｌとなった。濃縮水中の菌数は５６ＣＦＵ／ｍＬとなり、比較例３および実施例４〜５と比べて濃縮水中の菌数が減少したことがわかった。
(Example 6)
Example 6 is an example in which a stabilized hypobromous acid composition is supplied to an uncontaminated reverse osmosis membrane and water is passed through the membrane. When the total chlorine concentration in the water to be treated was 0.22 mg / L, the total chlorine concentration in the concentrated water was 0.2 mg / L. The number of bacteria in the concentrated water was 56 CFU / mL, and it was found that the number of bacteria in the concentrated water was reduced as compared with Comparative Example 3 and Examples 4 to 5.
このように、実施例の方法により、逆浸透膜のスライム抑制効果を有し、かつ逆浸透膜の酸化劣化を抑制することができた。実施例の方法により、逆浸透膜のスライム抑制効果を長期的に維持することができる。 As described above, according to the method of the example, it was possible to have the slime suppressing effect of the reverse osmosis membrane and suppress the oxidative deterioration of the reverse osmosis membrane. By the method of the example, the slime suppressing effect of the reverse osmosis membrane can be maintained for a long period of time.
１，３ 逆浸透膜処理システム、１０ 被処理水槽、１２ 逆浸透膜処理装置、１４ ポンプ、１６ 全塩素濃度測定装置、１８ 被処理水配管、２０ 被処理水供給配管、２２ 透過水配管、２４ 濃縮水配管、２６ 添加配管、２８ 濃縮水循環配管。 1,3 Reverse osmosis membrane treatment system, 10 Reverse osmosis membrane treatment equipment, 12 Reverse osmosis membrane treatment equipment, 14 pumps, 16 Total chlorine concentration measuring equipment, 18 Treatment water pipes, 20 Water treatment water supply pipes, 22 Permeated water pipes, 24 Concentrated water piping, 26 additive piping, 28 concentrated water circulation piping.
Claims (4)
前記濃縮水の全塩素濃度を測定し、前記濃縮水中の全塩素濃度が０．１ｍｇ／Ｌ以上５．０ｍｇ／Ｌ以下の範囲となるように、前記被処理水に臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を存在させることを特徴とする逆浸透膜処理方法。 A reverse osmosis membrane treatment method in which treated water is passed through a reverse osmosis membrane to obtain treated water and concentrated water.
The total chlorine concentration of the concentrated water is measured, and a bromine-based oxidizing agent is added to the water to be treated so that the total chlorine concentration of the concentrated water is in the range of 0.1 mg / L or more and 5.0 mg / L or less. A method for treating a reverse osmosis membrane, which comprises the presence of a stabilized hypobromous acid composition containing a sulfamic acid compound.
前記濃縮水の全塩素濃度を測定し、前記濃縮水中の全塩素濃度が０．１ｍｇ／Ｌ以上５．０ｍｇ／Ｌ以下の範囲となるように、前記被処理水に臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を存在させることを特徴とする逆浸透膜処理方法。 A reverse osmosis membrane treatment method in which treated water is passed through a reverse osmosis membrane to obtain treated water and concentrated water.
The total chlorine concentration of the concentrated water is measured, and bromine and a sulfamic acid compound are added to the water to be treated so that the total chlorine concentration of the concentrated water is in the range of 0.1 mg / L or more and 5.0 mg / L or less. A method for treating a reverse osmosis membrane, which comprises the presence of a stabilized hypobromous acid composition containing and.
逆浸透膜を有する逆浸透膜処理装置と；
前記濃縮水中の全塩素濃度が０．１ｍｇ／Ｌ以上５．０ｍｇ／Ｌ以下の範囲となるように、前記被処理水に臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を添加する添加手段と；
前記濃縮水の全塩素濃度を測定する全塩素濃度測定手段と；
を備えることを特徴とする逆浸透膜処理システム。 A reverse osmosis membrane treatment system that obtains treated water and concentrated water by passing water to be treated through the reverse osmosis membrane.
With a reverse osmosis membrane treatment device having a reverse osmosis membrane;
Stabilized hypobromous acid containing a bromine-based oxidizing agent and a sulfamic acid compound in the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.1 mg / L or more and 5.0 mg / L or less. With the addition means for adding the acid composition;
And the total chlorine concentration measuring means for measuring the total chlorine concentration before Symbol concentrate;
A reverse osmosis membrane treatment system characterized by comprising.
逆浸透膜を有する逆浸透膜処理装置と；
前記濃縮水中の全塩素濃度が０．１ｍｇ／Ｌ以上５．０ｍｇ／Ｌ以下の範囲となるように、前記被処理水に臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物を添加する添加手段と；
前記濃縮水の全塩素濃度を測定する全塩素濃度測定手段と；
を備えることを特徴とする逆浸透膜処理システム。 A reverse osmosis membrane treatment system that obtains treated water and concentrated water by passing water to be treated through the reverse osmosis membrane.
With a reverse osmosis membrane treatment device having a reverse osmosis membrane;
A stabilized hypobromous acid composition containing bromine and a sulfamic acid compound in the water to be treated so that the total chlorine concentration in the concentrated water is in the range of 0.1 mg / L or more and 5.0 mg / L or less. With the addition means to add
And the total chlorine concentration measuring means for measuring the total chlorine concentration before Symbol concentrate;
A reverse osmosis membrane treatment system characterized by comprising.
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