JP2018069124A - Water treatment apparatus and method using reverse osmosis membrane - Google Patents
Water treatment apparatus and method using reverse osmosis membrane Download PDFInfo
- Publication number
- JP2018069124A JP2018069124A JP2016208943A JP2016208943A JP2018069124A JP 2018069124 A JP2018069124 A JP 2018069124A JP 2016208943 A JP2016208943 A JP 2016208943A JP 2016208943 A JP2016208943 A JP 2016208943A JP 2018069124 A JP2018069124 A JP 2018069124A
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- Prior art keywords
- ammonia
- water
- reverse osmosis
- osmosis membrane
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 292
- 239000012528 membrane Substances 0.000 title claims abstract description 212
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 58
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 420
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 209
- 239000007800 oxidant agent Substances 0.000 claims abstract description 113
- -1 sulfamic acid compound Chemical class 0.000 claims abstract description 91
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 74
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 72
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000460 chlorine Substances 0.000 claims abstract description 69
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 69
- 230000001590 oxidative effect Effects 0.000 claims abstract description 64
- 238000000354 decomposition reaction Methods 0.000 claims description 21
- 230000007935 neutral effect Effects 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 7
- 239000003899 bactericide agent Substances 0.000 abstract description 53
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 38
- 238000010586 diagram Methods 0.000 abstract description 5
- 239000003206 sterilizing agent Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 74
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 58
- 239000000645 desinfectant Substances 0.000 description 37
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000007795 chemical reaction product Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000002834 transmittance Methods 0.000 description 15
- 239000003513 alkali Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 12
- 230000000694 effects Effects 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
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000012466 permeate Substances 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 230000002070 germicidal effect Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 229940077239 chlorous acid Drugs 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 102100030621 Carboxypeptidase A4 Human genes 0.000 description 1
- 102100026794 Carboxypeptidase A5 Human genes 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 101000910789 Homo sapiens Carboxypeptidase A5 Proteins 0.000 description 1
- 108091006676 Monovalent cation:proton antiporter-3 Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- WOHVONCNVLIHKY-UHFFFAOYSA-L [Ba+2].[O-]Cl=O.[O-]Cl=O Chemical compound [Ba+2].[O-]Cl=O.[O-]Cl=O WOHVONCNVLIHKY-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating 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
- 239000012670 alkaline solution Substances 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000012267 brine Substances 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
- 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
- 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
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BAQKWXACUNEBOT-UHFFFAOYSA-N dibutylsulfamic acid Chemical compound CCCCN(S(O)(=O)=O)CCCC BAQKWXACUNEBOT-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 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
- 238000005370 electroosmosis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IOISAJSHULNACL-UHFFFAOYSA-N ethyl(methyl)sulfamic acid Chemical compound CCN(C)S(O)(=O)=O IOISAJSHULNACL-UHFFFAOYSA-N 0.000 description 1
- SIVVHUQWDOGLJN-UHFFFAOYSA-N ethylsulfamic acid Chemical group CCNS(O)(=O)=O SIVVHUQWDOGLJN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000005339 levitation Methods 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 group CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 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
- 125000000962 organic group Chemical group 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000001139 pH measurement Methods 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- JWQSOOZHYMZRBT-UHFFFAOYSA-N propan-2-ylsulfamic acid Chemical group CC(C)NS(O)(=O)=O JWQSOOZHYMZRBT-UHFFFAOYSA-N 0.000 description 1
- HLIBNTOXKQCYMV-UHFFFAOYSA-N propylsulfamic acid Chemical group CCCNS(O)(=O)=O HLIBNTOXKQCYMV-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge 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
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- 239000008400 supply water Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
【課題】アンモニアを含有する被処理水を逆浸透膜で処理する水処理装置および方法において、塩素系酸化剤または臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤の逆浸透膜の透過を抑制する水処理装置および方法を提供する。【解決手段】アンモニアを含有する被処理水中のアンモニアを低減するアンモニア低減装置１０と、アンモニアを低減したアンモニア低減水中に臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤を存在させた殺菌剤含有水を、逆浸透膜処理する逆浸透膜処理装置１４と、を備える水処理装置１である。【選択図】図１PROBLEM TO BE SOLVED: To suppress permeation of a bactericide containing a chlorine-based oxidant or a bromine-based oxidant and a sulfamic acid compound in a reverse osmosis membrane in a water treatment apparatus and method for treating water to be treated containing ammonia with a reverse osmosis membrane. Provide water treatment equipment and methods to be used. SOLUTION: There is an ammonia reducing device 10 for reducing ammonia in water to be treated containing ammonia, and a bactericidal agent containing a bromine-based oxidizing agent or a chlorine-based oxidizing agent and a sulfamic acid compound in the ammonia-reduced ammonia-reduced water. It is a water treatment apparatus 1 including a reverse osmosis membrane treatment apparatus 14 that performs a reverse osmosis membrane treatment with the sterilizing agent-containing water. [Selection diagram] Fig. 1
Description
本発明は、逆浸透膜を用いる水処理装置および水処理方法に関する。 The present invention relates to a water treatment apparatus and a water treatment method using a reverse osmosis membrane.
逆浸透膜（ＲＯ膜）を用いる水処理方法において、バイオファウリング対策として各種の殺菌剤（スライム抑制剤）が使用されることが一般的である。次亜塩素酸等の塩素系酸化剤は代表的な殺菌剤であり、系内の殺菌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 a water treatment method using a reverse osmosis membrane (RO membrane), various bactericides (slime inhibitors) are generally used as a measure against biofouling. Chlorine oxidizers such as hypochlorous acid are typical fungicides and are usually added to the front of the reverse osmosis membrane for the purpose of sterilization in the system. Chlorine oxidizers are likely to degrade reverse osmosis membranes, so in general, chlorinated oxidants are reduced and decomposed immediately before reverse osmosis membranes, or chlorine oxidants flow into reverse osmosis membranes intermittently. It is operated by letting.
また、殺菌剤（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 bactericidal agent (slime inhibitor), a method in which a combined chlorine agent comprising a chlorine-based oxidant and a sulfamic acid compound is present in the treated water of the reverse osmosis membrane (see Patent Document 1), a bromine-based oxidant, or A method of adding a mixture of a reaction product of a bromine compound and a chlorine-based oxidant and a sulfamic acid compound or a reaction product to water to be treated is known (see Patent Document 2).
塩素系酸化剤または臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤は、殺菌能力が高いうえにポリアミド系の逆浸透膜を酸化劣化させにくく、逆浸透膜での阻止率も高く、後段の処理水（透過水）質に影響が少ないため有効である。 Bactericides containing chlorine-based or bromine-based oxidants and sulfamic acid compounds have a high bactericidal ability, are resistant to oxidative degradation of polyamide-based reverse osmosis membranes, and have a high rejection rate in reverse osmosis membranes. Effective because it has little effect on the quality of treated water (permeated water).
しかし、被処理水がアンモニア（アンモニウムイオン）を含む場合、塩素系酸化剤または臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤の一部が逆浸透膜を透過してしまうことがわかった。殺菌剤が逆浸透膜を透過すると、処理水質の悪化や後段設備の劣化を招くため、透過の抑制が望まれている。 However, it has been found that when the water to be treated contains ammonia (ammonium ions), a part of the bactericidal agent containing a chlorine-based oxidizing agent or a bromine-based oxidizing agent and a sulfamic acid compound permeates the reverse osmosis membrane. When the disinfectant permeates the reverse osmosis membrane, the quality of the treated water is deteriorated and the downstream equipment is deteriorated. Therefore, suppression of permeation is desired.
本発明の目的は、アンモニアを含有する被処理水を逆浸透膜で処理する水処理システムおよび方法において、塩素系酸化剤または臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤の逆浸透膜の透過を抑制する水処理装置および方法を提供することにある。 An object of the present invention is a water treatment system and method for treating water to be treated containing ammonia with a reverse osmosis membrane, in a reverse osmosis membrane of a bactericide containing a chlorine-based oxidant or bromine-based oxidant and a sulfamic acid compound. It is providing the water treatment apparatus and method which suppress permeation | transmission.
本発明は、アンモニアを含有する被処理水中のアンモニアを低減するアンモニア低減手段と、前記アンモニア低減手段によりアンモニアを低減したアンモニア低減水中に臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤を存在させた殺菌剤含有水を、逆浸透膜処理する逆浸透膜処理手段と、を備える水処理装置である。 The present invention includes an ammonia reducing means for reducing ammonia in water to be treated containing ammonia, and a bromine-based oxidizing agent or a chlorine-based oxidizing agent and a sulfamic acid compound in the ammonia-reducing water in which ammonia is reduced by the ammonia reducing means. A reverse osmosis membrane treatment means for treating a sterilizer-containing water containing a bactericide with a reverse osmosis membrane, a water treatment device.
前記水処理装置において、前記アンモニア低減水のアンモニア濃度が、５ｍｇ／Ｌ以下であることが好ましい。 In the water treatment device, the ammonia concentration of the ammonia-reduced water is preferably 5 mg / L or less.
前記水処理装置において、前記アンモニア低減手段として、アンモニアストリッピング処理装置を備えることが好ましい。 The water treatment apparatus preferably includes an ammonia stripping treatment apparatus as the ammonia reducing means.
前記水処理装置において、前記アンモニア低減手段として、酸化剤によるアンモニア分解処理手段を備えることが好ましい。 The water treatment apparatus preferably includes an ammonia decomposition treatment means using an oxidizing agent as the ammonia reduction means.
前記水処理装置において、前記逆浸透膜処理手段が、逆浸透膜として中性膜またはカチオン荷電膜を備えることが好ましい。 In the water treatment apparatus, it is preferable that the reverse osmosis membrane treatment means includes a neutral membrane or a cation charged membrane as a reverse osmosis membrane.
また、本発明は、アンモニアを含有する被処理水中のアンモニアを低減するアンモニア低減工程と、前記アンモニア低減工程によりアンモニアを低減したアンモニア低減水中に臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤を存在させた殺菌剤含有水を、逆浸透膜処理する逆浸透膜処理工程と、を含む水処理方法である。 The present invention also provides an ammonia reduction step for reducing ammonia in water to be treated containing ammonia, and a bromine-based oxidant or a chlorine-based oxidant and a sulfamic acid compound in the ammonia-reduced water in which ammonia is reduced by the ammonia reduction step. And a reverse osmosis membrane treatment step for treating the sterilizer-containing water containing the sterilizer containing water with a reverse osmosis membrane.
前記水処理方法において、前記アンモニア低減水のアンモニア濃度が、５ｍｇ／Ｌ以下であることが好ましい。 In the water treatment method, the ammonia concentration of the ammonia-reduced water is preferably 5 mg / L or less.
前記水処理方法において、前記アンモニア低減工程において、アンモニアストリッピング処理を行うことが好ましい。 In the water treatment method, it is preferable to perform ammonia stripping treatment in the ammonia reduction step.
前記水処理方法において、前記アンモニア低減工程において、酸化剤によるアンモニア分解処理を行うことが好ましい。 In the water treatment method, it is preferable to perform an ammonia decomposition treatment with an oxidizing agent in the ammonia reduction step.
前記水処理方法において、前記逆浸透膜処理工程において、逆浸透膜として中性膜またはカチオン荷電膜を用いることが好ましい。 In the water treatment method, it is preferable to use a neutral membrane or a cation charged membrane as the reverse osmosis membrane in the reverse osmosis membrane treatment step.
本発明では、アンモニアを含有する被処理水を逆浸透膜で処理する水処理装置および方法において、塩素系酸化剤または臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤の逆浸透膜の透過を抑制することができる。 In the present invention, in a water treatment apparatus and method for treating water to be treated containing ammonia with a reverse osmosis membrane, permeation of a bactericide containing a chlorine-based oxidant or bromine-based oxidant and a sulfamic acid compound through the reverse osmosis membrane is performed. Can be suppressed.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.
＜逆浸透膜を用いる水処理装置および水処理方法＞
本発明の実施形態に係る水処理装置の一例の概略を図１に示し、その構成について説明する。
<Water treatment apparatus and water treatment method using reverse osmosis membrane>
An example of a water treatment apparatus according to an embodiment of the present invention is schematically shown in FIG.
図１に示す水処理装置１は、アンモニアを含有する被処理水中のアンモニアを低減するアンモニア低減手段として、アンモニア低減装置１０と、逆浸透膜処理手段として、逆浸透膜処理装置１４とを備える。水処理装置１は、アンモニア低減水を貯留するためのアンモニア低減水槽１２を備えてもよい。 A water treatment apparatus 1 shown in FIG. 1 includes an ammonia reduction apparatus 10 as an ammonia reduction means for reducing ammonia in water to be treated containing ammonia, and a reverse osmosis membrane treatment apparatus 14 as a reverse osmosis membrane treatment means. The water treatment apparatus 1 may include an ammonia reduced water tank 12 for storing ammonia reduced water.
水処理装置１において、アンモニア低減装置１０の入口には、被処理水配管１６が接続されている。アンモニア低減装置１０の出口と、アンモニア低減水槽１２の入口とは、アンモニア低減水配管１８により接続されている。アンモニア低減水槽１２の出口と、逆浸透膜処理装置１４の入口とは、殺菌剤含有水配管２０により接続されている。逆浸透膜処理装置１４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。アンモニア低減水槽１２には、殺菌剤添加配管２６が接続されている。 In the water treatment apparatus 1, a water pipe 16 to be treated is connected to the inlet of the ammonia reduction apparatus 10. The outlet of the ammonia reducing device 10 and the inlet of the ammonia reducing water tank 12 are connected by an ammonia reducing water pipe 18. The outlet of the ammonia reducing water tank 12 and the inlet of the reverse osmosis membrane treatment device 14 are connected by a bactericide-containing water pipe 20. A permeated water pipe 22 is connected to the permeated water outlet of the reverse osmosis membrane treatment apparatus 14, and a concentrated water pipe 24 is connected to the concentrated water outlet. A bactericidal agent addition pipe 26 is connected to the ammonia reducing water tank 12.
本実施形態に係る水処理方法および水処理装置１の動作について説明する。 The operation of the water treatment method and the water treatment apparatus 1 according to this embodiment will be described.
水処理装置１において、アンモニア（アンモニウムイオン）を含有する被処理水は、被処理水配管１６を通してアンモニア低減装置１０に供給され、アンモニア低減装置１０において、アンモニアが低減される（アンモニア低減工程）。 In the water treatment device 1, the water to be treated containing ammonia (ammonium ions) is supplied to the ammonia reducing device 10 through the water to be treated piping 16, and the ammonia is reduced in the ammonia reducing device 10 (ammonia reduction step).
アンモニア低減装置１０によりアンモニアが低減されたアンモニア低減水は、アンモニア低減水配管１８を通して、必要に応じてアンモニア低減水槽１２に送液され、貯留される。アンモニア低減水槽１２において、アンモニア低減水中に臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤が添加され、殺菌剤を存在させる（殺菌剤添加工程）。殺菌剤は、アンモニア低減水配管１８において添加されてもよいし、殺菌剤含有水配管２０において添加されてもよい。 The ammonia-reduced water whose ammonia has been reduced by the ammonia reducing device 10 is sent to and stored in the ammonia-reduced water tank 12 through the ammonia-reduced water pipe 18 as necessary. In the ammonia-reduced water tank 12, a bactericidal agent containing a bromine-based oxidant or a chlorine-based oxidant and a sulfamic acid compound is added to the ammonia-reduced water, and the bactericide is present (bactericide addition step). The bactericidal agent may be added in the ammonia-reducing water pipe 18 or may be added in the bactericidal agent-containing water pipe 20.
殺菌剤を存在させた殺菌剤含有水は、殺菌剤含有水配管２０を通して、逆浸透膜処理装置１４に供給され、逆浸透膜処理装置１４において、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、処理水として透過水配管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。 The bactericide-containing water containing the bactericide is supplied to the reverse osmosis membrane treatment device 14 through the bactericide-containing water pipe 20, and the reverse osmosis membrane treatment device 14 performs the reverse osmosis membrane treatment (reverse osmosis membrane treatment). Process). The permeated water obtained by the reverse osmosis membrane treatment is discharged as treated water through the permeated water pipe 22, and the concentrated water is discharged through the concentrated water pipe 24.
本発明者らは検討を重ねた結果、臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤の透過率が被処理水中のアンモニアの濃度に応じて上昇することを発見した。そこで、逆浸透膜処理の前処理として、被処理水中のアンモニア濃度を低減することによって、塩素系酸化剤または臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤の逆浸透膜の透過を抑制することができる。特に、アンモニア低減水中のアンモニア濃度が５ｍｇ／Ｌ以下では、アンモニア低減による殺菌剤透過率の低減効果が有効であった。 As a result of repeated studies, the present inventors have found that the transmittance of a bactericide containing a bromine-based oxidant or a chlorine-based oxidant and a sulfamic acid compound increases according to the concentration of ammonia in the water to be treated. Therefore, as a pretreatment for the reverse osmosis membrane treatment, by reducing the ammonia concentration in the water to be treated, the permeation of the reverse osmosis membrane of the bactericide containing chlorine-based oxidant or bromine-based oxidant and sulfamic acid compound is suppressed. be able to. In particular, when the ammonia concentration in the ammonia-reduced water is 5 mg / L or less, the effect of reducing the germicide permeability by reducing ammonia was effective.
アンモニア低減装置１０としては、被処理水中のアンモニア（アンモニウムイオン）の量を低減することができるものであればよく、特に制限はない。アンモニア低減装置１０としては、例えば、アンモニアストリッピング処理を行うアンモニアストリッピング処理装置、酸化剤によるアンモニア分解処理を行うアンモニア分解処理装置、逆浸透膜による前処理等が挙げられる。これらのうち、スライムリスクの増加がほとんどないこと、酸化剤として後段に使用する殺菌剤と同じ薬品を使用することで使用する薬品の種類が増えないこと等の点から、アンモニアストリッピング処理を行うアンモニアストリッピング処理装置、酸化剤によるアンモニア分解処理を行うアンモニア分解処理装置が好ましい。 The ammonia reducing device 10 is not particularly limited as long as it can reduce the amount of ammonia (ammonium ions) in the water to be treated. Examples of the ammonia reduction device 10 include an ammonia stripping treatment device that performs ammonia stripping treatment, an ammonia decomposition treatment device that performs ammonia decomposition treatment using an oxidizing agent, and a pretreatment using a reverse osmosis membrane. Among these, ammonia stripping treatment is performed because there is almost no increase in slime risk and the use of the same chemical as the sterilizing agent used in the subsequent stage as an oxidizing agent does not increase the type of chemical used. An ammonia stripping treatment apparatus and an ammonia decomposition treatment apparatus for performing ammonia decomposition treatment with an oxidizing agent are preferable.
アンモニアストリッピング処理は、アンモニア含有水にアルカリ溶液を添加、加温後、充填物を充填した放散塔に通し、蒸気および空気に接触させることで、アンモニア含有水中のアンモニアをガス側に移動させる処理方法である。 Ammonia stripping treatment is a treatment to move ammonia in ammonia-containing water to the gas side by adding an alkaline solution to ammonia-containing water, heating it, passing it through a diffusion tower filled with packing, and bringing it into contact with steam and air. Is the method.
アンモニアストリッピング処理装置は、例えば、蒸留塔の内部に多孔板や充填物等が設置されたものであり、アンモニア含有水が蒸留塔の上部から流入し、蒸気が下部から吹き込まれ、アンモニア含有水と蒸気とが接触されることにより、アンモニア含有水中の遊離アンモニアが蒸気側に追い出される。追い出されたアンモニアガスは、さらに分解処理されてもよい。このアンモニアガス分解処理としては、例えば、触媒を充填した触媒反応塔を通して無害な窒素に分解する方法、硫酸と反応させて硫酸アンモニウムにする方法等があり、アンモニア水として回収再利用することも可能である。 The ammonia stripping treatment apparatus is, for example, a device in which a perforated plate, a packing, or the like is installed inside a distillation column, in which ammonia-containing water flows from the top of the distillation column, steam is blown from the bottom, and ammonia-containing water Is brought into contact with the steam, so that free ammonia in the ammonia-containing water is expelled to the steam side. The purged ammonia gas may be further decomposed. This ammonia gas decomposition treatment includes, for example, a method of decomposing into harmless nitrogen through a catalyst reaction tower packed with a catalyst, a method of reacting with sulfuric acid to make ammonium sulfate, etc., which can be recovered and reused as ammonia water. is there.
アンモニアストリッピング処理におけるｐＨは、１０以上であることが好ましく、１０．５以上であることがより好ましく、１０．５〜１２の範囲がさらに好ましい。アンモニアストリッピング処理におけるｐＨが１０未満であると、遊離アンモニア（ＮＨ３）の分率が低くなり、アンモニアの除去効率が低下する場合がある。アンモニアストリッピング処理におけるｐＨが１２を超えると、アンモニアストリッピング処理での蒸留塔内部の多孔板や充填物の劣化の可能性があることや、アルカリ薬品のコストが高くなるといった問題が生じる場合がある。 The pH in the ammonia stripping treatment is preferably 10 or more, more preferably 10.5 or more, and further preferably in the range of 10.5 to 12. When the pH in the ammonia stripping treatment is less than 10, the fraction of free ammonia (NH 3 ) is lowered, and the ammonia removal efficiency may be lowered. If the pH in the ammonia stripping treatment exceeds 12, there may be a problem that the porous plate and the packing inside the distillation column in the ammonia stripping treatment may be deteriorated or the cost of the alkali chemicals is increased. is there.
アンモニアストリッピング処理は温度が高いほど効率的になるため、蒸気によって水温を４０℃〜１００℃の範囲、好ましくは８０℃〜１００℃の範囲に上昇させることが好ましい。 Since the ammonia stripping treatment becomes more efficient as the temperature increases, it is preferable to raise the water temperature to a range of 40 ° C. to 100 ° C., preferably 80 ° C. to 100 ° C. by steam.
酸化剤によるアンモニア分解処理に用いられる酸化剤としては、塩素系酸化剤、臭素系酸化剤や、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、塩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塩素酸組成物等が挙げられ、安定化次亜臭素酸組成物、安定化次亜塩素酸組成物が好ましい。塩素系酸化剤、臭素系酸化剤、安定化次亜臭素酸組成物、安定化次亜塩素酸組成物としては、後述する塩素系酸化剤、臭素系酸化剤、安定化次亜臭素酸組成物、安定化次亜塩素酸組成物と同様のものが挙げられる。アンモニア分解処理に用いられる酸化剤としては、アンモニア低減工程の後段においてアンモニア低減水中に存在させる殺菌剤と同じものであることが好ましい。アンモニア低減水中に存在させる殺菌剤と同じものを使用し、アンモニア分解に必要な量より多い量の酸化剤を用いれば、アンモニア分解処理で残存した酸化剤を後段の逆浸透膜処理装置における殺菌剤としても作用させることができる。 The oxidizing agent used for the ammonia decomposition treatment with the oxidizing agent includes a chlorine-based oxidizing agent, a bromine-based oxidizing agent, a stabilized hypobromite composition containing a bromine-based oxidizing agent and a sulfamic acid compound, a chlorine-based oxidizing agent, Examples thereof include a stabilized hypochlorous acid composition containing a sulfamic acid compound, and a stabilized hypochlorous acid composition and a stabilized hypochlorous acid composition are preferred. Chlorine oxidizer, bromine oxidizer, stabilized hypobromite composition, and stabilized hypochlorous acid composition include chlorine oxidizer, bromine oxidizer, and stabilized hypobromite composition described later. The same thing as a stabilized hypochlorous acid composition is mentioned. The oxidizing agent used for the ammonia decomposition treatment is preferably the same as the sterilizing agent that is present in the ammonia-reduced water after the ammonia reduction step. If the same disinfectant that is present in the ammonia-reduced water is used, and if an amount of oxidant greater than that required for ammonia decomposition is used, the oxidant remaining in the ammonia decomposition process is removed from the reverse osmosis membrane treatment device in the subsequent stage. Can also be used.
アンモニア分解処理において用いられる酸化剤の量は、被処理水中のアンモニア性窒素（ＮＨ４−Ｎ）のモル濃度に対する、有効塩素濃度換算の有効ハロゲンのモル濃度の比が、１．６以上であることが好ましく、２．０以上であることがより好ましい。この比が大きくなればなるほど、アンモニアの低減効果が高くなる。被処理水中のアンモニア性窒素のモル濃度に対する、有効塩素濃度換算の有効ハロゲンのモル濃度の比が、２．０以上であることにより、アンモニア分解処理で残存した酸化剤を後段の逆浸透膜処理装置における殺菌剤としても作用させることができる。このモル濃度の比の上限は、例えば１００以下である。 The amount of the oxidizing agent used in the ammonia decomposition treatment is such that the ratio of the effective halogen molar concentration in terms of effective chlorine concentration to the molar concentration of ammoniacal nitrogen (NH 4 -N) in the water to be treated is 1.6 or more. It is preferable that it is 2.0 or more. The greater this ratio, the higher the ammonia reduction effect. The ratio of the molar concentration of effective halogen in terms of effective chlorine concentration to the molar concentration of ammoniacal nitrogen in the water to be treated is 2.0 or more, so that the oxidant remaining in the ammonia decomposition treatment is treated with a reverse osmosis membrane in the subsequent stage. It can also act as a disinfectant in the device. The upper limit of this molar concentration ratio is, for example, 100 or less.
酸化剤によるアンモニア分解処理におけるｐＨは、例えば、３〜１０の範囲であり、４〜９の範囲であることが好ましい。アンモニア分解処理におけるｐＨが３未満であると、アンモニア性窒素の分解効果が低下する場合があり、１０を超えると、後段の逆浸透膜の阻止率向上のためｐＨを中性に調整する必要が生じる場合がある。 The pH in the ammonia decomposition treatment with the oxidizing agent is, for example, in the range of 3 to 10, and preferably in the range of 4 to 9. If the pH in ammonia decomposition treatment is less than 3, the decomposition effect of ammoniacal nitrogen may be reduced. If it exceeds 10, it is necessary to adjust the pH to neutral in order to improve the rejection of the reverse osmosis membrane in the latter stage. May occur.
酸化剤によるアンモニア分解処理における温度は、例えば、０℃〜１００℃の範囲であり、０℃〜４０℃の範囲であることが好ましい。アンモニア分解処理における温度が０℃未満であると、処理水が凍結する場合があり、１００℃を超えると、酸化剤もしくはアンモニアが揮発してアンモニア分解効率が低下する場合がある。 The temperature in the ammonia decomposition treatment with the oxidizing agent is, for example, in the range of 0 ° C to 100 ° C, and preferably in the range of 0 ° C to 40 ° C. If the temperature in the ammonia decomposition treatment is less than 0 ° C., the treated water may freeze, and if it exceeds 100 ° C., the oxidizing agent or ammonia may volatilize and ammonia decomposition efficiency may be reduced.
アンモニア低減工程における被処理水中のアンモニアの濃度は、例えば、０．１ｍｇ／Ｌ〜５００ｍｇ／Ｌの範囲であり、０．１ｍｇ／Ｌ〜３０ｍｇ／Ｌの範囲であることが好ましい。 The concentration of ammonia in the water to be treated in the ammonia reduction step is, for example, in the range of 0.1 mg / L to 500 mg / L, and preferably in the range of 0.1 mg / L to 30 mg / L.
本発明の実施形態に係る逆浸透膜を用いる水処理装置および方法では、アンモニア低減装置１０によりアンモニアが低減されたアンモニア低減水中に、臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤を存在させる。「臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤」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殺菌剤であってもよいし、「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を含有する殺菌剤であってもよい。「塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤」は、「塩素系酸化剤」と「スルファミン酸化合物」との混合物を含む安定化次亜塩素酸組成物を含有する殺菌剤であってもよいし、「塩素系酸化剤とスルファミン酸化合物との反応生成物」を含む安定化次亜塩素酸組成物を含有する殺菌剤であってもよい。 In the water treatment apparatus and method using the reverse osmosis membrane according to the embodiment of the present invention, the ammonia-reduced water in which ammonia is reduced by the ammonia reducing apparatus 10 contains a bromine-based oxidant or a chlorine-based oxidant and a sulfamic acid compound. There is a disinfectant present. “A disinfectant containing a bromine-based oxidant and a sulfamic acid compound” is a disinfectant containing a stabilized hypobromite composition containing a mixture of a “bromine-based oxidant” and a “sulfamic acid compound”. Alternatively, it may be a disinfectant containing a stabilized hypobromite composition containing “reaction product of bromine-based oxidant and sulfamic acid compound”. “A disinfectant containing a chlorine-based oxidant and a sulfamic acid compound” is a disinfectant containing a stabilized hypochlorous acid composition including a mixture of a “chlorine-based oxidant” and a “sulfamic acid compound”. Alternatively, it may be a bactericide containing a stabilized hypochlorous acid composition containing a “reaction product of a chlorinated oxidant and a sulfamic acid compound”.
すなわち、本発明の実施形態に係る逆浸透膜を用いる水処理装置および方法では、アンモニア低減水中に、「臭素系酸化剤」と「スルファミン酸化合物」との混合物、または「塩素系酸化剤」と「スルファミン酸化合物」との混合物を存在させる。これにより、アンモニア低減水中で、安定化次亜臭素酸組成物または安定化次亜塩素酸組成物が生成すると考えられる。 That is, in the water treatment apparatus and method using the reverse osmosis membrane according to the embodiment of the present invention, a mixture of “bromine-based oxidant” and “sulfamic acid compound” or “chlorine-based oxidant” in ammonia-reduced water. A mixture with a “sulfamic acid compound” is present. Thereby, it is thought that the stabilized hypobromite composition or the stabilized hypochlorous acid composition produces | generates in ammonia reduction water.
また、本発明の実施形態に係る逆浸透膜を用いる水処理装置および方法では、アンモニア低減水中に、「臭素系酸化剤とスルファミン酸化合物との反応生成物」である安定化次亜臭素酸組成物、または「塩素系酸化剤とスルファミン酸化合物との反応生成物」である安定化次亜塩素酸組成物を存在させる。 In the water treatment apparatus and method using the reverse osmosis membrane according to the embodiment of the present invention, the stabilized hypobromite composition which is a “reaction product of bromine-based oxidant and sulfamic acid compound” in ammonia-reduced water. Or a stabilized hypochlorous acid composition that is a “reaction product of a chlorinated oxidant and a sulfamic acid compound”.
具体的には本発明の実施形態に係る逆浸透膜を用いる水処理装置および方法では、アンモニア低減水中に、「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。または、アンモニア低減水中に、「次亜塩素酸」と、「スルファミン酸化合物」との混合物を存在させる。 Specifically, in the water treatment apparatus and method using the reverse osmosis membrane according to the embodiment of the present invention, “bromine”, “bromine chloride”, “hypobromite” or “sodium bromide and sodium bromide” are added in ammonia-reduced water. A mixture of “reactant with chlorous acid” and “sulfamic acid compound” is present. Alternatively, a mixture of “hypochlorous acid” and “sulfamic acid compound” is present in the ammonia-reduced water.
また、本発明の実施形態に係る逆浸透膜を用いる水処理装置および方法では、アンモニア低減水中に、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」、「次亜臭素酸とスルファミン酸化合物との反応生成物」、または「臭化ナトリウムと次亜塩素酸との反応物と、スルファミン酸化合物と、の反応生成物」である安定化次亜臭素酸組成物を存在させる。または、アンモニア低減水中に、「次亜塩素酸とスルファミン酸化合物との反応生成物」である安定化次亜塩素酸組成物を存在させる。 Further, in the water treatment apparatus and method using the reverse osmosis membrane according to the embodiment of the present invention, for example, “reaction product of bromine and sulfamic acid compound”, “bromine chloride and sulfamic acid compound” in ammonia-reduced water. Stabilization that is "reaction product", "reaction product of hypobromite and sulfamic acid compound", or "reaction product of reaction product of sodium bromide and hypochlorous acid and sulfamic acid compound" A chemical hypobromite composition is present. Alternatively, a stabilized hypochlorous acid composition that is a “reaction product of hypochlorous acid and a sulfamic acid compound” is present in the ammonia-reduced water.
本実施形態に係る逆浸透膜を用いる水処理装置および方法において、安定化次亜臭素酸組成物または安定化次亜塩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ため、逆浸透膜でのファウリングを抑制しながら、逆浸透膜の酸化劣化を抑制できる。このため、本実施形態に係る逆浸透膜を用いる水処理装置および方法で用いられる安定化次亜臭素酸組成物または安定化次亜塩素酸組成物は、アンモニアを含有する被処理水を逆浸透膜で処理する水処理装置および方法で用いるスライム抑制剤としては好適である。 In the water treatment apparatus and method using a reverse osmosis membrane according to the present embodiment, the stabilized hypobromite composition or the stabilized hypochlorous acid composition is a slime equal to or greater than a chlorine-based oxidizing agent such as hypochlorous acid. Despite exerting its inhibitory effect, it has less influence on reverse osmosis membranes compared to chlorinated oxidants, so it can suppress oxidative degradation of reverse osmosis membranes while suppressing fouling in reverse osmosis membranes. . For this reason, the stabilized hypobromite composition or the stabilized hypochlorous acid composition used in the water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment performs reverse osmosis on the treated water containing ammonia. It is suitable as a slime inhibitor used in a water treatment apparatus and method for treating with a membrane.
本実施形態に係る逆浸透膜を用いる水処理装置および方法のうち、「臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤」の場合、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より低い。塩素系酸化剤を含む場合は、塩素酸の生成が懸念される。 Among the water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment, in the case of “a bactericide containing a bromine-based oxidant and a sulfamic acid compound”, there is no chlorine-based oxidant, Deterioration effect is lower. When a chlorinated oxidant is included, there is a concern about the production of chloric acid.
本実施形態に係る逆浸透膜を用いる水処理装置および方法のうち、「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い。 In the water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment, when the “bromine-based oxidant” is bromine, there is no chlorine-based oxidant, so the deterioration effect on the reverse osmosis membrane is extremely low. .
本実施形態に係る逆浸透膜を用いる水処理装置および方法では、例えば、アンモニア低減水中に、「臭素系酸化剤」または「塩素系酸化剤」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」または「塩素系酸化剤」と「スルファミン酸化合物」とは別々にアンモニア低減水に添加してもよく、または、原液同士で混合させてからアンモニア低減水に添加してもよい。 In the water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment, for example, in the ammonia-reduced water, “bromine-based oxidant” or “chlorine-based oxidant” and “sulfamic acid compound” are fed by a chemical pump or the like. It may be injected. The “bromine-based oxidant” or “chlorine-based oxidant” and the “sulfamic acid compound” may be added separately to the ammonia-reduced water, or may be mixed with each other and then added to the ammonia-reduced water. Good.
また、例えば、アンモニア低減水中に、「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「塩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。 In addition, for example, “reaction product of bromine-based oxidant and sulfamic acid compound” or “reaction product of chlorine-based oxidant and sulfamic acid compound” may be injected into ammonia-reduced water using a chemical injection pump or the like. Good.
本実施形態に係る逆浸透膜を用いる水処理装置および方法において、「臭素系酸化剤」または「塩素系酸化剤」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」または「塩素系酸化剤」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 water treatment apparatus and method using a reverse osmosis membrane according to this embodiment, the ratio of the equivalent of the “sulfamic acid compound” to the equivalent of the “bromine-based oxidant” or “chlorine-based oxidant” is 1 or more. Preferably, it is in the range of 1 or more and 2 or less. If the ratio of the equivalent amount of “sulfamic acid compound” to the equivalent amount of “bromine-based oxidant” or “chlorine-based oxidant” is less than 1, there is a possibility of deteriorating the film. There is a case.
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 the amount is less than 0.01 mg / L, a sufficient slime-inhibiting effect may not be obtained. If the amount is more than 100 mg / L, the reverse osmosis membrane may be deteriorated and the piping may be corroded.
本実施形態に係る逆浸透膜を用いる水処理装置および方法において、アンモニア低減水中のアンモニウムイオン濃度が、５ｍｇ／Ｌ以下であることが好ましく、１ｍｇ／Ｌ以下であることがより好ましい。アンモニア低減水中のアンモニウムイオン濃度が５ｍｇ／Ｌを超えると、殺菌剤が逆浸透膜を透過しやすくなる。 In the water treatment apparatus and method using the reverse osmosis membrane according to this embodiment, the ammonium ion concentration in the ammonia-reduced water is preferably 5 mg / L or less, and more preferably 1 mg / L or less. When the ammonium ion concentration in the ammonia-reduced water exceeds 5 mg / L, the bactericidal agent easily passes through the reverse osmosis membrane.
アンモニア低減水中の全塩素濃度に対するアンモニアの濃度の比（アンモニア濃度（ｍｇ／Ｌ）／殺菌剤濃度（全塩素濃度：ｍｇ／Ｌ））は、例えば、０．０１〜５０の範囲である。アンモニア低減水中の全塩素濃度に対するアンモニアの濃度の比が０．０１未満であると、殺菌剤が十分に逆浸透膜で阻止されるため、それ以上のアンモニア低減の効果がない場合があり、５０を超えると、アンモニア濃度を低減しても殺菌剤透過率が十分に高く、透過率の低減効果が見られなくなる場合がある。 The ratio of the concentration of ammonia to the total chlorine concentration in the ammonia-reduced water (ammonia concentration (mg / L) / disinfectant concentration (total chlorine concentration: mg / L)) is, for example, in the range of 0.01 to 50. If the ratio of the concentration of ammonia to the total chlorine concentration in the ammonia-reduced water is less than 0.01, the bactericidal agent is sufficiently blocked by the reverse osmosis membrane, so there may be no further ammonia reduction effect. If the concentration exceeds 1, the disinfectant permeability is sufficiently high even if the ammonia concentration is reduced, and the effect of reducing the transmittance may not be observed.
臭素系酸化剤としては、臭素（液体臭素）、塩化臭素、臭素酸、臭素酸塩、次亜臭素酸等が挙げられる。次亜臭素酸は、臭化ナトリウム等の臭化物と次亜塩素酸等の塩素系酸化剤とを反応させて生成させたものであってもよい。 Examples of bromine-based oxidizing agents include bromine (liquid bromine), bromine chloride, bromic acid, bromate, and hypobromite. Hypobromous acid may be produced by reacting a bromide such as sodium bromide with a chlorine-based oxidizing agent such as hypochlorous acid.
これらのうち、臭素を用いた「臭素とスルファミン酸化合物（臭素とスルファミン酸化合物の混合物）」または「臭素とスルファミン酸化合物との反応生成物」の製剤は、「次亜塩素酸と臭素化合物とスルファミン酸」の製剤および「塩化臭素とスルファミン酸」の製剤等に比べて、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、逆浸透膜用殺菌剤としてはより好ましい。 Among these, the preparation of “bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound)” or “reaction product of bromine and sulfamic acid compound” using bromine is composed of “hypochlorous acid and bromine compound and Compared with the preparation of “sulfamic acid” and the preparation of “bromine chloride and sulfamic acid”, etc., since there is less by-product of bromic acid and the reverse osmosis membrane is not further deteriorated, it is more preferable as a fungicide for reverse osmosis membrane.
すなわち、本発明の実施形態に係る逆浸透膜を用いる水処理装置および方法では、アンモニア低減水中に、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、アンモニア低減水中に、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 water treatment apparatus and method using the reverse osmosis membrane according to the embodiment of the present invention, bromine and a sulfamic acid compound are present in the ammonia-reduced water (a mixture of bromine and sulfamic acid compound is present). preferable. Moreover, it is preferable to make the reaction product of a bromine and a sulfamic acid compound exist in ammonia reduction water.
臭素化合物としては、臭化ナトリウム、臭化カリウム、臭化リチウム、臭化アンモニウムおよび臭化水素酸等が挙げられる。これらのうち、製剤コスト等の点から、臭化ナトリウムが好ましい。 Examples of bromine compounds include sodium bromide, potassium bromide, lithium bromide, ammonium bromide and hydrobromic acid. Of these, sodium bromide is preferable from the viewpoint of formulation cost and the like.
塩素系酸化剤としては、例えば、塩素ガス、二酸化塩素、次亜塩素酸またはその塩、亜塩素酸またはその塩、塩素酸またはその塩、過塩素酸またはその塩、塩素化イソシアヌル酸またはその塩等が挙げられる。これらのうち、塩としては、例えば、次亜塩素酸ナトリウム、次亜塩素酸カリウム等の次亜塩素酸アルカリ金属塩、次亜塩素酸カルシウム、次亜塩素酸バリウム等の次亜塩素酸アルカリ土類金属塩、亜塩素酸ナトリウム、亜塩素酸カリウム等の亜塩素酸アルカリ金属塩、亜塩素酸バリウム等の亜塩素酸アルカリ土類金属塩、亜塩素酸ニッケル等の他の亜塩素酸金属塩、塩素酸アンモニウム、塩素酸ナトリウム、塩素酸カリウム等の塩素酸アルカリ金属塩、塩素酸カルシウム、塩素酸バリウム等の塩素酸アルカリ土類金属塩等が挙げられる。これらの塩素系酸化剤は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。塩素系酸化剤としては、取り扱い性等の点から、次亜塩素酸ナトリウムを用いるのが好ましい。 Examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, chlorinated isocyanuric acid or a salt thereof. Etc. Among these, examples of the salt include alkali metal hypochlorites such as sodium hypochlorite and potassium hypochlorite, alkaline earth hypochlorite such as calcium hypochlorite and barium hypochlorite. Metal salts, alkali metal chlorites such as sodium chlorite and potassium chlorite, alkaline earth metal chlorites such as barium chlorite, and other metal chlorites such as nickel chlorite , Alkali metal chlorates such as ammonium chlorate, sodium chlorate and potassium chlorate, and alkaline earth metal chlorates such as calcium chlorate and barium chlorate. These chlorine-based oxidants may be used alone or in combination of two or more. As the chlorine-based oxidant, sodium hypochlorite is preferably used from the viewpoint of handleability.
スルファミン酸化合物は、以下の一般式（１）で示される化合物である。
Ｒ２ＮＳＯ３Ｈ （１）
（式中、Ｒは独立して水素原子または炭素数１〜８のアルキル基である。）
The sulfamic acid compound is a compound represented by the following general formula (1).
R 2 NSO 3 H (1)
(In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
スルファミン酸化合物としては、例えば、２個のＲ基の両方が水素原子であるスルファミン酸（アミド硫酸）の他に、Ｎ−メチルスルファミン酸、Ｎ−エチルスルファミン酸、Ｎ−プロピルスルファミン酸、Ｎ−イソプロピルスルファミン酸、Ｎ−ブチルスルファミン酸等の２個のＲ基の一方が水素原子であり、他方が炭素数１〜８のアルキル基であるスルファミン酸化合物、Ｎ，Ｎ−ジメチルスルファミン酸、Ｎ，Ｎ−ジエチルスルファミン酸、Ｎ，Ｎ−ジプロピルスルファミン酸、Ｎ，Ｎ−ジブチルスルファミン酸、Ｎ−メチル−Ｎ−エチルスルファミン酸、Ｎ−メチル−Ｎ−プロピルスルファミン酸等の２個のＲ基の両方が炭素数１〜８のアルキル基であるスルファミン酸化合物、Ｎ−フェニルスルファミン酸等の２個のＲ基の一方が水素原子であり、他方が炭素数６〜１０のアリール基であるスルファミン酸化合物、またはこれらの塩等が挙げられる。スルファミン酸塩としては、例えば、ナトリウム塩、カリウム塩等のアルカリ金属塩、カルシウム塩、ストロンチウム塩、バリウム塩等のアルカリ土類金属塩、マンガン塩、銅塩、亜鉛塩、鉄塩、コバルト塩、ニッケル塩等の他の金属塩、アンモニウム塩およびグアニジン塩等が挙げられる。スルファミン酸化合物およびこれらの塩は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。スルファミン酸化合物としては、環境負荷等の点から、スルファミン酸（アミド硫酸）を用いるのが好ましい。 Examples of the sulfamic acid compound include sulfamic acid (amidosulfuric acid) in which both two R groups are hydrogen atoms, N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N- A sulfamic acid compound in which one of two R groups such as isopropylsulfamic acid and N-butylsulfamic acid is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, N, N-dimethylsulfamic acid, N, Two R groups such as N-diethylsulfamic acid, N, N-dipropylsulfamic acid, N, N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid, etc. One of two R groups such as a sulfamic acid compound and N-phenylsulfamic acid, both of which are alkyl groups having 1 to 8 carbon atoms, An atom, the other is sulfamic acid compound or a salt thereof, such as an aryl group having 6 to 10 carbon atoms. Examples of the sulfamate include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, strontium salt and barium salt, manganese salt, copper salt, zinc salt, iron salt, cobalt salt, Other metal salts such as nickel salts, ammonium salts, guanidine salts and the like can be mentioned. The sulfamic acid compounds and salts thereof may be used alone or in combination of two or more. As the sulfamic acid compound, sulfamic acid (amidosulfuric acid) is preferably used from the viewpoint of environmental load.
本実施形態に係る逆浸透膜を用いる水処理装置および方法において、アンモニア低減水中に、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 water treatment apparatus and method using the reverse osmosis membrane according to this embodiment, an alkali may be further present in the ammonia-reduced water. 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. Further, the alkali is not solid and may be used as an aqueous solution.
本実施形態に係る逆浸透膜を用いる水処理装置および方法は、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を用いる水処理装置および方法ではポリアミド系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 water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment can be suitably applied to polyamide polymer membranes that are currently mainstream as reverse osmosis membranes. Polyamide polymer membranes have a relatively low resistance to oxidizing agents, and when free chlorine or the like is continuously brought into contact with the polyamide polymer membrane, the membrane performance is significantly reduced. However, in the water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment, such a remarkable decrease in membrane performance hardly occurs even in the polyamide polymer membrane.
逆浸透膜には、中性膜、アニオン荷電膜、およびカチオン荷電膜がある。本明細書では、後述する実施例に記載したゼータ電位の測定方法により求めた、ｐＨ７．０におけるゼータ電位が−１０ｍＶ以上５ｍＶ未満である膜を中性膜、５ｍＶ以上である膜をカチオン荷電膜、−１０ｍＶ未満である膜をアニオン荷電膜と定義する。中性膜のゼータ電位は、−５ｍＶ以上であれば好ましく、−３．９ｍＶ以上であればより好ましく、−１．３ｍＶ以上であればさらに好ましい。カチオン荷電膜のゼータ電位の上限は特に制限はないが、例えば、２０ｍＶ以下である。 Reverse osmosis membranes include neutral membranes, anion charged membranes, and cation charged membranes. In the present specification, a membrane having a zeta potential at pH 7.0 of −10 mV or more and less than 5 mV determined by the method for measuring a zeta potential described in Examples described later is a neutral membrane, and a membrane having a zeta potential of 5 mV or more is a cation charged membrane. , A membrane of less than −10 mV is defined as an anion charged membrane. The zeta potential of the neutral membrane is preferably −5 mV or more, more preferably −3.9 mV or more, and even more preferably −1.3 mV or more. The upper limit of the zeta potential of the cationic charged membrane is not particularly limited, but is, for example, 20 mV or less.
本実施形態に係る逆浸透膜を用いる水処理方法では、逆浸透的として好ましくは中性膜またはカチオン荷電膜を用いることにより、より好ましくは中性膜を用いることにより、アニオン荷電膜を用いた場合に比べて、塩素系酸化剤または臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤の逆浸透膜の透過を抑制することができる。 In the water treatment method using a reverse osmosis membrane according to the present embodiment, an anion charged membrane is preferably used by using a neutral membrane or a cation charged membrane, more preferably a neutral membrane as reverse osmosis. Compared with the case, the permeation | transmission of the reverse osmosis membrane of the disinfectant containing a chlorine-type oxidizing agent or a bromine-type oxidizing agent, and a sulfamic acid compound can be suppressed.
市販の中性膜としては、例えば、ＢＷ３０ＸＦＲ（ダウ・ケミカル社製）、ＬＦＣ３（日東電工株式会社製）、ＴＭＬ２０（東レ株式会社製）、ＯＦＲ６２５（以上、オルガノ株式会社製）等が挙げられる。 Examples of commercially available neutral membranes include BW30XFR (manufactured by Dow Chemical Co.), LFC3 (manufactured by Nitto Denko Corporation), TML20 (manufactured by Toray Industries, Inc.), OFR625 (manufactured by Organo Corporation), and the like.
市販のカチオン荷電膜としては、例えば、ＥＳ１０Ｃ（日東電工株式会社製）等が挙げられる。 Examples of commercially available cationic charged membranes include ES10C (manufactured by Nitto Denko Corporation).
市販のアニオン荷電膜としては、例えば、ＥＳ１５、ＥＳ２０、ＣＰＡ３、ＣＰＡ５（以上、日東電工株式会社製）、ＲＥ−８０４０ＢＬＮ（ウンジン社製）等が挙げられる。 Examples of commercially available anion charged membranes include ES15, ES20, CPA3, CPA5 (manufactured by Nitto Denko Corporation), RE-8040BLN (manufactured by Eunjin Co., Ltd.), and the like.
本実施形態に係る逆浸透膜を用いる水処理装置および方法において、逆浸透膜を備える逆浸透膜処理装置へ給水されるアンモニア低減水の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。アンモニア低減水の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、アンモニア低減水の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を用いる水処理装置および方法を用いる場合、アンモニア低減水の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 water treatment apparatus and method using the reverse osmosis membrane according to this embodiment, the pH of the ammonia-reduced water supplied to the reverse osmosis membrane treatment apparatus including the reverse osmosis membrane is preferably 5.5 or more, and 6.0. More preferably, it is more preferably 6.5 or more. If the pH of the ammonia-reduced water is less than 5.5, the amount of permeated water may decrease. In addition, the upper limit of the pH of the ammonia-reduced water is not particularly limited as long as it is equal to or lower than the application upper limit pH of a normal reverse osmosis membrane (for example, pH 10), but considering pH precipitation of hardness components such as calcium, pH Is preferably operated at, for example, 9.0 or less. When using the water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment, the reverse osmosis membrane is deteriorated and the water quality of the treated water (permeate) is deteriorated by operating the ammonia-reduced water at a pH of 5.5 or higher. It is also possible to secure a sufficient amount of permeated water while suppressing the slime and exhibiting a sufficient slime suppressing effect.
逆浸透膜処理装置において、アンモニア低減水の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上記殺菌剤と併用してもよい。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。分散剤のアンモニア低減水への添加量は、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 treatment apparatus, when scale is generated at pH 5.5 or more of ammonia-reduced water, a dispersant may be used in combination with the above bactericidal agent to suppress scale. Examples of the dispersant include polyacrylic acid, polymaleic acid, and phosphonic acid. The amount of the dispersant added to the ammonia-reduced water is, for example, in the range of 0.1 to 1,000 mg / L as the concentration in the RO concentrated water.
また、分散剤を使用せずにスケールの発生を抑制するためには、例えば、ＲＯ濃縮水中のシリカ濃度を溶解度以下に、カルシウムスケールの指標であるランゲリア指数を０以下になるように、逆浸透膜処理装置の回収率等の運転条件を調整することが挙げられる。 In addition, in order to suppress the occurrence of scale without using a dispersant, for example, reverse osmosis is performed so that the silica concentration in RO concentrated water is less than the solubility and the Langeria index, which is a calcium scale index, is less than 0. Adjusting the operating conditions such as the recovery rate of the membrane processing apparatus can be mentioned.
逆浸透膜処理装置の用途としては、例えば、純水製造、海水淡水化、排水回収等が挙げられる。 Examples of the use of the reverse osmosis membrane treatment apparatus include pure water production, seawater desalination, wastewater recovery, and the like.
本実施形態に係る逆浸透膜を用いる水処理装置および方法は、特に、排水回収への適用、例えば、電子産業排水の回収への適用が考えられる。電子産業排水には低分子有機物が含まれることが多く、排水回収するフローとして、例えば、図２に示すような、生物処理装置５０と膜処理装置５４とを備える生物処理システム５６の後段に、本実施形態に係る逆浸透膜を用いる水処理方法を適用する、アンモニア低減装置１０および逆浸透膜処理装置１４を備える水処理装置１を有するフローが考えられる。 The water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment can be applied particularly to wastewater recovery, for example, recovery of electronic industrial wastewater. Electronic industrial wastewater often contains low-molecular-weight organic matter. As a flow for collecting wastewater, for example, as shown in FIG. 2, a biological treatment system 56 including a biological treatment device 50 and a membrane treatment device 54, The flow which has the water treatment apparatus 1 provided with the ammonia reduction apparatus 10 and the reverse osmosis membrane treatment apparatus 14 to which the water treatment method using the reverse osmosis membrane which concerns on this embodiment is applied can be considered.
図２に示す水処理システム３は、生物処理手段として生物処理装置５０と、生物処理水槽５２と、膜処理手段として膜処理装置５４と、膜処理水槽５８と、上記水処理装置１とを備える。水処理システム３は、第２逆浸透膜処理手段として第２逆浸透膜処理装置６０を備えてもよい。 The water treatment system 3 shown in FIG. 2 includes a biological treatment device 50, a biological treatment water tank 52 as a biological treatment means, a membrane treatment device 54 as a membrane treatment means, a membrane treatment water tank 58, and the water treatment apparatus 1. . The water treatment system 3 may include a second reverse osmosis membrane treatment device 60 as the second reverse osmosis membrane treatment means.
水処理システム３において、原水として例えば電子産業排水が生物処理装置５０に送液され、生物処理装置５０において生物処理が行われる（生物処理工程）。生物処理された生物処理水は、必要に応じて生物処理水槽５２に貯留された後、膜処理装置５４に送液され、膜処理装置５４において除濁膜により膜処理（除濁）が行われる（膜処理工程）。膜処理された膜処理水は、必要に応じて膜処理水槽５８に貯留された後、被処理水として水処理装置１のアンモニア低減装置１０に供給され、アンモニア低減装置１０において、アンモニアが低減される（アンモニア低減工程）。 In the water treatment system 3, for example, electronic industrial wastewater is fed as raw water to the biological treatment device 50, and biological treatment is performed in the biological treatment device 50 (biological treatment step). Biologically treated biologically treated water is stored in the biologically treated water tank 52 as necessary, and then sent to the membrane treatment device 54 where membrane treatment (turbidity) is performed by the turbidity membrane. (Membrane treatment step). The membrane-treated water subjected to membrane treatment is stored in the membrane-treated water tank 58 as necessary, and then supplied to the ammonia reducing device 10 of the water treatment device 1 as treated water. In the ammonia reducing device 10, ammonia is reduced. (Ammonia reduction step).
アンモニア低減装置１０によりアンモニアが低減されたアンモニア低減水は、必要に応じてアンモニア低減水槽１２に送液され、貯留される。アンモニア低減水槽１２において、アンモニア低減水中に臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤が添加され、殺菌剤を存在させる（殺菌剤添加工程）。殺菌剤は、アンモニア低減水槽１２の前後の配管において添加されてもよい。 The ammonia-reduced water whose ammonia has been reduced by the ammonia reducing device 10 is sent to and stored in the ammonia-reduced water tank 12 as necessary. In the ammonia-reduced water tank 12, a bactericidal agent containing a bromine-based oxidant or a chlorine-based oxidant and a sulfamic acid compound is added to the ammonia-reduced water, and the bactericide is present (bactericide addition step). The disinfectant may be added in the pipes before and after the ammonia reducing water tank 12.
殺菌剤を存在させた殺菌剤含有水は、逆浸透膜処理装置１４に供給され、逆浸透膜処理装置１４において、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、処理水として透過水配管を通して排出され、濃縮水は濃縮水配管を通して排出される。逆浸透膜処理で得られた透過水は系外に排出される。濃縮水は系外に排出されてもよいし、必要に応じて第２逆浸透膜処理装置６０に送液され、第２逆浸透膜処理装置６０においてさらに逆浸透膜処理が行われてもよい（第２逆浸透膜処理工程）。第２逆浸透膜処理で得られた濃縮水は系外に排出される。透過水は系外に排出されてもよいし、必要に応じてアンモニア低減水槽１２に送液され、循環されてもよい。 The bactericide-containing water in which the bactericide is present is supplied to the reverse osmosis membrane treatment device 14, and the reverse osmosis membrane treatment device 14 performs the reverse osmosis membrane treatment (reverse osmosis membrane treatment step). The permeated water obtained by the reverse osmosis membrane treatment is discharged as treated water through the permeated water pipe, and the concentrated water is discharged through the concentrated water pipe. The permeated water obtained by the reverse osmosis membrane treatment is discharged out of the system. The concentrated water may be discharged out of the system, or may be sent to the second reverse osmosis membrane treatment device 60 as necessary, and further the reverse osmosis membrane treatment may be performed in the second reverse osmosis membrane treatment device 60. (Second reverse osmosis membrane treatment step). The concentrated water obtained by the second reverse osmosis membrane treatment is discharged out of the system. The permeated water may be discharged out of the system, or sent to the ammonia-reduced water tank 12 and circulated as necessary.
図２の水処理システム３では、生物処理装置５０、生物処理水槽５２、膜処理装置５４を個別に備える生物処理システム５６を例示したが、これらを１つのユニットにまとめた膜分離活性汚泥装置（ＭＢＲ）を用いてもよい。 In the water treatment system 3 of FIG. 2, the biological treatment system 56 including the biological treatment device 50, the biological treatment water tank 52, and the membrane treatment device 54 is illustrated as an example, but the membrane separation activated sludge device ( MBR) may be used.
図２の水処理システム３では、原水に含まれる低分子有機物等を生物処理によって分解し、除濁膜等を備える膜処理装置５４で生物代謝物等を阻止し、次にアンモニア低減装置１０においてアンモニアが低減され、逆浸透膜処理装置１４で各種イオンおよび残存する有機物等を阻止し、処理水（透過水）を得る。このような排水回収では、排水自体にアンモニアが含まれていたり、生物処理によってアンモニアが発生することが多い。例えば、有機物として水酸化テトラメチルアンモニウムを含む排水を生物処理するとアンモニアが発生しやすい。 In the water treatment system 3 of FIG. 2, low molecular organic substances and the like contained in the raw water are decomposed by biological treatment, and biological metabolites and the like are blocked by a membrane treatment device 54 having a turbidity membrane and the like. Ammonia is reduced and various ions and remaining organic substances are blocked by the reverse osmosis membrane treatment device 14 to obtain treated water (permeated water). In such wastewater recovery, ammonia is often contained in the wastewater itself, or ammonia is often generated by biological treatment. For example, when wastewater containing tetramethylammonium hydroxide as an organic substance is biologically treated, ammonia is likely to be generated.
このとき、生物処理により発生する生物代謝物や、生物処理後も残存する低分子の有機物により、後段の逆浸透膜のバイオファウリングが懸念される。殺菌力が高い次亜塩素酸を用いて対応することが考えられるが、次亜塩素酸は近年主流となっているポリアミド系の逆浸透膜を劣化させることがある。逆浸透膜の前段に活性炭塔や、還元剤の薬注点を設けることも考えられるが、いずれもイニシャルランニングコストの面が問題となる。そこで、水処理システム３では、アンモニア低減装置においてアンモニアを低減し、アンモニア低減水中に臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤を存在させることにより、殺菌能力が高いうえにポリアミド系の逆浸透膜を酸化劣化させにくく、逆浸透膜での阻止率も高く、後段の処理水（透過水）質に影響が少ないため有効である。 At this time, biofouling of the reverse osmosis membrane in the latter stage is a concern due to biological metabolites generated by biological treatment and low molecular weight organic matter remaining after biological treatment. Although it is conceivable to use hypochlorous acid having a high sterilizing power, hypochlorous acid may deteriorate a polyamide-based reverse osmosis membrane which has become the mainstream in recent years. It is conceivable to provide an activated carbon tower or a reducing agent pouring point in front of the reverse osmosis membrane, but both have problems in terms of initial running cost. Therefore, the water treatment system 3 has a high sterilizing ability by reducing ammonia in the ammonia reducing device, and making the ammonia-reduced water contain a sterilizing agent containing a bromine-based oxidizing agent or a chlorine-based oxidizing agent and a sulfamic acid compound. In addition, the polyamide-based reverse osmosis membrane is less susceptible to oxidative degradation, has a high rejection rate at the reverse osmosis membrane, and is effective because it has little influence on the quality of treated water (permeated water) in the subsequent stage.
このように殺菌剤を添加した場合、殺菌剤が処理水側に透過すると、処理水質の悪化が問題となる。そのため、本実施形態に係る逆浸透膜を用いる水処理装置および方法では、逆浸透膜処理の前処理として、被処理水中のアンモニア濃度を低減することによって、透過水に殺菌剤が検出されることはほとんどなく、殺菌剤の逆浸透膜の透過が抑制される。 When the bactericidal agent is added in this way, if the bactericidal agent permeates the treated water side, deterioration of the treated water becomes a problem. Therefore, in the water treatment apparatus and method using the reverse osmosis membrane according to the present embodiment, as a pretreatment for the reverse osmosis membrane treatment, the bactericidal agent is detected in the permeated water by reducing the ammonia concentration in the water to be treated. There is almost no antibacterial agent permeation through the reverse osmosis membrane.
また、このとき、逆浸透膜処理装置１４へ給水されるアンモニア低減水のｐＨ、すなわち逆浸透膜処理装置１４の運転ｐＨを９以下とすることが好ましい。ｐＨ９を超えるアルカリ側では、逆浸透膜の脱塩率が低下する場合、および、殺菌剤の酸化力が低下する場合がある。逆浸透膜処理装置１４へ給水されるアンモニア低減水のｐＨが９以下であれば、ＲＯ透過水の水質がより良好に保たれ、スライム発生がより抑制される。 At this time, the pH of the ammonia-reduced water supplied to the reverse osmosis membrane treatment device 14, that is, the operating pH of the reverse osmosis membrane treatment device 14 is preferably 9 or less. On the alkali side exceeding pH 9, the desalination rate of the reverse osmosis membrane may decrease, and the oxidizing power of the bactericide may decrease. If the pH of the ammonia-reduced water supplied to the reverse osmosis membrane treatment device 14 is 9 or less, the quality of the RO permeate is kept better, and slime generation is further suppressed.
水処理システム３のような排水回収のフローでは、水回収率を高めるために第２逆浸透膜処理装置６０（ブラインＲＯ）を設けることが一般的である。第２逆浸透膜処理装置６０は、逆浸透膜処理装置１４の濃縮水を原水とし、透過水をアンモニア低減水槽１２に返送し、濃縮水を系外へ排出する。第２逆浸透膜処理装置６０にもスライム発生リスクはあり、逆浸透膜処理装置１４で殺菌剤の透過率が低いと、第２逆浸透膜処理装置６０の原水に殺菌剤成分が残留することになる。第２逆浸透膜処理装置６０の原水に殺菌剤成分が多く残存し、第２逆浸透膜処理装置６０におけるスライム発生が抑制されることになる。 In the flow of wastewater recovery like the water treatment system 3, it is common to provide the 2nd reverse osmosis membrane processing apparatus 60 (brine RO) in order to raise a water recovery rate. The second reverse osmosis membrane treatment device 60 uses the concentrated water of the reverse osmosis membrane treatment device 14 as raw water, returns the permeated water to the ammonia-reduced water tank 12, and discharges the concentrated water out of the system. The second reverse osmosis membrane treatment device 60 also has a risk of slime generation, and if the reverse osmosis membrane treatment device 14 has a low disinfectant permeability, the disinfectant component remains in the raw water of the second reverse osmosis membrane treatment device 60. become. Many germicide components remain in the raw water of the second reverse osmosis membrane treatment device 60, and slime generation in the second reverse osmosis membrane treatment device 60 is suppressed.
図２の水処理システム３では、逆浸透膜処理の前処理として生物処理を例として説明したが、逆浸透膜処理の前処理工程においては、生物処理、凝集処理、凝集沈殿処理、加圧浮上処理、ろ過処理、膜分離処理、活性炭処理、オゾン処理、紫外線照射処理等の生物学的、物理的または化学的な前処理、およびこれらの前処理のうちの２つ以上の組み合わせが必要に応じて行われてもよい。 In the water treatment system 3 of FIG. 2, the biological treatment is described as an example of the pretreatment of the reverse osmosis membrane treatment. However, in the pretreatment step of the reverse osmosis membrane treatment, the biological treatment, the coagulation treatment, the coagulation sedimentation treatment, and the pressure levitation Biological, physical or chemical pretreatment such as treatment, filtration treatment, membrane separation treatment, activated carbon treatment, ozone treatment, ultraviolet irradiation treatment, and combinations of two or more of these pretreatments as necessary It may be done.
水処理装置１において、システム内に逆浸透膜の他に、ポンプ、安全フィルタ、流量測定装置、圧力測定装置、温度測定装置、酸化還元電位（ＯＲＰ）測定装置、残留塩素測定装置、電気伝導度測定装置、ｐＨ測定装置、エネルギー回収装置等を必要に応じて備えてもよい。 In the water treatment device 1, in addition to the reverse osmosis membrane in the system, a pump, a safety filter, a flow rate measuring device, a pressure measuring device, a temperature measuring device, a redox potential (ORP) measuring device, a residual chlorine measuring device, an electric conductivity A measurement device, a pH measurement device, an energy recovery device, and the like may be provided as necessary.
水処理システム３において、必要に応じて、安定化次亜臭素酸組成物または安定化次亜塩素酸組成物以外のスケール抑制剤や、ｐＨ調整剤が、生物処理水槽５２およびその前後の配管、膜処理水槽５８およびその前後の配管、アンモニア低減水槽１２およびその前後の配管のうちの少なくとも１つにおいて、生物処理水、膜処理水、アンモニア低減水のうちの少なくとも１つに添加されてもよい。 In the water treatment system 3, if necessary, a scale inhibitor other than the stabilized hypobromite composition or the stabilized hypochlorous acid composition, the pH adjuster, the biological treatment water tank 52 and the pipes before and after the biological treatment water tank 52, It may be added to at least one of the biologically treated water, the membrane treated water, and the ammonia reduced water in at least one of the membrane treated water tank 58 and the piping before and after it, the ammonia reducing water tank 12 and the piping before and after it. .
＜殺菌剤＞
本実施形態に係る殺菌剤は、「臭素系酸化剤または塩素系酸化剤」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または安定化次亜塩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。
<Fungicide>
The disinfectant according to the present embodiment contains a stabilized hypobromite composition or a stabilized hypochlorous acid composition containing a mixture of “bromine-based oxidant or chlorine-based oxidant” and “sulfamic acid compound”. And may further contain an alkali.
また、本実施形態に係る殺菌剤は、「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、または「塩素系酸化剤とスルファミン酸化合物との反応生成物」を含む安定化次亜塩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。 In addition, the bactericide according to the present embodiment includes a stabilized hypobromite composition containing a “reaction product of a bromine-based oxidant and a sulfamic acid compound”, or “a reaction between a chlorine-based oxidant and a sulfamic acid compound. It contains a stabilized hypochlorous acid composition containing a “product” 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.
塩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塩素酸組成物の市販品としては、例えば、栗田工業株式会社製の「クリバーターＩＫ−１１０」が挙げられる。 As a commercial item of the stabilized hypochlorous acid composition containing a chlorine-type oxidizing agent and a sulfamic acid compound, "Kuriverter IK-110" by Kurita Kogyo Co., Ltd. is mentioned, for example.
本実施形態に係る殺菌剤としては、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。 As the disinfectant according to the present embodiment, in order not to further deteriorate the reverse osmosis membrane, one containing bromine and a sulfamic acid compound (containing a mixture of bromine and sulfamic acid compound), for example, bromine and sulfamic acid A mixture of a compound, an alkali and water, or a reaction product containing a reaction product of bromine and a sulfamic acid compound, for example, a reaction product of bromine and a sulfamic acid compound, and a mixture of an alkali and water is preferable.
本実施形態に係る殺菌剤のうち、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含有する殺菌剤、特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含有する殺菌剤は、塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤（クロロスルファミン酸等）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、殺菌剤としては最適である。 Among the bactericides according to the present embodiment, a bactericide containing a stabilized hypobromite composition containing a bromine-based oxidant and a sulfamic acid compound, particularly a stabilized hypobromite containing bromine and a sulfamic acid compound. The disinfectant containing the composition has higher oxidizing power, slime-inhibiting power, and slime-removing power when compared with a disinfectant containing chlorinated oxidant and sulfamic acid compound (chlorosulfamic acid, etc.). In addition, it hardly causes significant film deterioration like hypochlorous acid having high oxidizing power. At normal use concentrations, the effect on film degradation can be substantially ignored. For this reason, it is optimal as a disinfectant.
本実施形態に係る殺菌剤は、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 disinfectant according to the present embodiment hardly permeates the reverse osmosis membrane, and therefore has little influence on the quality of treated water. Further, since the concentration can be measured on site in the same manner as hypochlorous acid or the like, more accurate concentration management is possible.
殺菌剤の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。殺菌剤のｐＨが１３．０以下であると殺菌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 bactericide is, for example, more than 13.0, and more preferably more than 13.2. When the pH of the disinfectant is 13.0 or less, the effective halogen in the disinfectant may become unstable.
殺菌剤中の臭素酸濃度は、５ｍｇ／ｋｇ未満であることが好ましい。殺菌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 disinfectant is preferably less than 5 mg / kg. If the bromate concentration in the bactericide is 5 mg / kg or more, the concentration of bromate ions in the RO permeate may increase.
＜殺菌剤の製造方法＞
本実施形態に係る殺菌剤は、臭素系酸化剤または塩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 disinfectant>
The bactericidal agent according to the present embodiment is obtained by mixing a bromine-based oxidizing agent or a chlorine-based oxidizing agent and a sulfamic acid compound, and may further mix 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殺菌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、殺菌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 disinfectant containing a stabilized hypobromite composition containing bromine and a sulfamic acid compound, bromine is added to a mixed liquid containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere. It is preferable to include a step of reacting or adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere. By adding and reacting under an inert gas atmosphere or adding under an inert gas atmosphere, the bromate ion concentration in the disinfectant is lowered, and the bromate ion concentration in the RO permeated water is lowered.
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。 The inert gas to be used is not limited, but at least one of nitrogen and argon is preferable from the viewpoint of manufacturing and the like, and nitrogen is particularly preferable from the viewpoint of manufacturing cost and the like.
臭素の添加の際の反応器内の酸素濃度は６％以下が好ましいが、４％以下がより好ましく、２％以下がさらに好ましく、１％以下が特に好ましい。臭素の反応の際の反応器内の酸素濃度が６％を超えると、反応系内の臭素酸の生成量が増加する場合がある。 The oxygen concentration in the reactor upon addition of bromine is preferably 6% or less, more preferably 4% or less, further preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reactor during the bromine reaction exceeds 6%, the amount of bromic acid produced in the reaction system may increase.
臭素の添加率は、殺菌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。臭素の添加率が殺菌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 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 bactericide. If the bromine addition rate exceeds 25% by weight with respect to the total amount of the bactericidal agent, the amount of bromic acid produced in the reaction system may increase. If it is less than 1% by weight, the sterilizing power 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 during the addition of bromine is preferably controlled in the range of 0 ° C. to 25 ° C., but more preferably in the range of 0 ° C. to 15 ° C. from the viewpoint of production cost and the like. When the reaction temperature at the time of bromine addition exceeds 25 degreeC, the production amount of the bromic acid in a reaction system may increase, and when it is less than 0 degreeC, it may freeze.
以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.
［安定化次亜臭素酸組成物（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、安定化次亜臭素酸組成物（組成物１）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 Hypobromite Composition (Composition 1)]
Under nitrogen atmosphere, liquid bromine: 16.9% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.94% by weight, water: remaining The components were mixed to prepare a stabilized hypobromite composition (Composition 1). The stabilized hypobromite composition had a pH of 14 and a total chlorine concentration of 7.5% by weight. The detailed method for preparing the stabilized hypobromite composition is as follows.
反応容器内の酸素濃度が１％に維持されるように、窒素ガスの流量をマスフローコントローラでコントロールしながら連続注入で封入した２Ｌの４つ口フラスコに１４３６ｇの水、３６１ｇの水酸化ナトリウムを加え混合し、次いで３００ｇのスルファミン酸を加え混合した後、反応液の温度が０〜１５℃になるように冷却を維持しながら、４７３ｇの液体臭素を加え、さらに４８％水酸化カリウム溶液２３０ｇを加え、組成物全体の量に対する重量比でスルファミン酸１０．７％、臭素１６．９％、臭素の当量に対するスルファミン酸の当量比が１．０４である、目的の安定化次亜臭素酸組成物（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。 Add 1436 g of water and 361 g of sodium hydroxide to a 2 L four-necked flask sealed by continuous injection while controlling the flow rate of nitrogen gas with a mass flow controller so that the oxygen concentration in the reaction vessel is maintained at 1%. Next, after adding 300 g of sulfamic acid and mixing, 473 g of liquid bromine was added while maintaining cooling so that the temperature of the reaction solution was 0 to 15 ° C., and 230 g of 48% potassium hydroxide solution was added. The desired stabilized hypobromite composition, wherein the sulfamic acid is 10.7% by weight relative to the total amount of the composition, 16.9% bromine, and the equivalent ratio of sulfamic acid to the equivalent of bromine is 1.04. Composition 1) was obtained. The pH of the resulting solution was 14 as measured by the glass electrode method. The bromine content of the resulting solution was 16.9% as measured by a redox titration method using sodium thiosulfate after bromine was converted to iodine with potassium iodide, and the theoretical content (16.9% ) Of 100.0%. In addition, the oxygen concentration in the reaction vessel during the bromine reaction was measured using “Oxygen Monitor JKO-02 LJDII” manufactured by Zico Corporation. The bromic acid concentration was less than 5 mg / kg.
なお、ｐＨの測定は、以下の条件で行った。
電極タイプ：ガラス電極式
ｐＨ測定計：東亜ディーケーケー社製、ＩＯＬ−３０型
電極の校正：関東化学社製中性リン酸塩ｐＨ（６．８６）標準液（第２種）、同社製ホウ酸塩ｐＨ（９．１８）標準液（第２種）の２点校正で行った
測定温度：２５℃
測定値：測定液に電極を浸漬し、安定後の値を測定値とし、３回測定の平均値
The pH was measured under the following conditions.
Electrode type: Glass electrode type pH meter: IOL-30 type manufactured by Toa DKK Corporation Electrode calibration: Neutral phosphate pH (6.86) standard solution (type 2) manufactured by Kanto Chemical Co., boric acid manufactured by the same company Salt temperature (9.18) Standard solution (type 2) was measured by two-point calibration Measurement temperature: 25 ° C
Measurement value: Immerse the electrode in the measurement solution and use the value after stabilization as the measurement value.
［安定化次亜塩素酸組成物（組成物２）の調製］
１２％次亜塩素酸ナトリウム水溶液：５０重量％、スルファミン酸：１２重量％、水酸化ナトリウム：８重量％、水：残分を混合して、安定化次亜塩素酸組成物（組成物２）を調製した。組成物２のｐＨは１３．７、全塩素濃度は、６．２重量％であった。
[Preparation of Stabilized Hypochlorous Acid Composition (Composition 2)]
12% sodium hypochlorite aqueous solution: 50% by weight, sulfamic acid: 12% by weight, sodium hydroxide: 8% by weight, water: the remainder is mixed to stabilize a hypochlorous acid composition (Composition 2) Was prepared. Composition 2 had a pH of 13.7 and a total chlorine concentration of 6.2% by weight.
［逆浸透膜のゼータ電位の測定］
逆浸透膜のゼータ電位は、大塚電子株式会社製、ゼータ電位・粒径測定システムＥＬＳＺｓｅｒｉｅｓを用いて、求めた。逆浸透膜のゼータ電位は、測定した電気浸透プロットより、下記森・岡本の式およびＳｍｏｌｕｃｈｏｗｓｋｉの式から計算した。
[Measurement of zeta potential of reverse osmosis membrane]
The zeta potential of the reverse osmosis membrane was determined using a zeta potential / particle size measurement system ELSZseries manufactured by Otsuka Electronics Co., Ltd. The zeta potential of the reverse osmosis membrane was calculated based on the measured electroosmosis plot from the following Mori-Okamoto equation and Smoluchowski equation.
（森・岡本の式）
Ｕｏｂｓ（ｚ）＝ＡＵ０（ｚ／ｂ）２＋ΔＵ０（ｚ／ｂ）＋（１−Ａ）Ｕ０＋Ｕｐ
ここで、
ｚ：セル中心位置からの距離
Ｕｏｂｓ（ｚ）：セル中のｚ位置における見かけの移動度
Ａ：１／［（２／３）−（０．４２０１６６／Ｋ）］
Ｋ＝ａ／ｂ： ２ａと２ｂはセル断面の横と縦の長さ、ａ＞ｂ
Ｕｐ：粒子の真の移動度
Ｕ０：セルの上面、下面における平均移動度
ΔＵ０：セルの上面、下面における移動度の差
（Ｓｍｏｌｕｃｈｏｗｓｋｉの式）
ζ＝４πηＵ／ε
ここで、
Ｕ：電気移動度
ε：溶媒の誘電率
η：溶媒の粘度
(Mori / Okamoto formula)
U obs (z) = AU 0 (z / b) 2 + ΔU 0 (z / b) + (1−A) U 0 + U p
here,
z: Distance from the cell center position U obs (z): Apparent mobility at the z position in the cell A: 1 / [(2/3) − (0.420166 / K)]
K = a / b: 2a and 2b are the horizontal and vertical lengths of the cell cross section, a> b
U p : true mobility of particles U 0 : average mobility on the upper and lower surfaces of the cell ΔU 0 : difference in mobility between the upper and lower surfaces of the cell (Smoluchowski equation)
ζ = 4πηU / ε
here,
U: Electric mobility ε: Dielectric constant of solvent η: Viscosity of solvent
測定液として１０ｍＭ ＮａＣｌ水溶液（ｐＨ約５．４）を使用した。この水溶液と試料のペアを各試料について２組用意し、一方はｐＨを酸性（ｐＨ２，３，４，５，６，７）に、他方はｐＨをアルカリ性（ｐＨ８，９）に調整して、各ｐＨにおけるゼータ電位を測定した。溶媒の物性値は２５℃における純水の値（屈折率：１．３３２８、粘度：０．８８７８、誘電率：７８．３）を使用した。 A 10 mM NaCl aqueous solution (pH about 5.4) was used as a measurement solution. Two pairs of this aqueous solution and sample are prepared for each sample, one is adjusted to acidic (pH 2, 3, 4, 5, 6, 7) and the other is adjusted to alkaline (pH 8, 9), The zeta potential at each pH was measured. As the physical properties of the solvent, pure water values (refractive index: 1.3328, viscosity: 0.8878, dielectric constant: 78.3) at 25 ° C. were used.
＜実施例１＞
［試験条件および試験方法］
平膜試験にて殺菌剤の透過率を測定した。平膜セルは、日東電工社製のメンブレンマスターＣ７０−Ｆフロー式平膜テストセルを用いた。平膜には、日東電工社製の逆浸透膜ＥＳ１５、ＬＦＣ３を用いた。日東電工社製ＥＳ１５は、アニオン荷電膜（ゼータ電位：−３５ｍＶ）、日東電工社製ＬＦＣ３は、中性膜（ゼータ電位：−１．３ｍＶ）である。平膜は円形で、直径が７５ｍｍのものを用いた。フローを図３に示す。
<Example 1>
[Test conditions and test methods]
The transmittance of the bactericide was measured by a flat membrane test. As the flat membrane cell, a membrane master C70-F flow type flat membrane test cell manufactured by Nitto Denko Corporation was used. For the flat membrane, reverse osmosis membrane ES15 and LFC3 manufactured by Nitto Denko Corporation were used. Nitto Denko's ES15 is an anion charged membrane (zeta potential: -35 mV), and Nitto Denko's LFC3 is a neutral membrane (zeta potential: -1.3 mV). The flat membrane was circular and had a diameter of 75 mm. The flow is shown in FIG.
平膜試験の試験水（被処理水）は、純水に５００ｍｇ／Ｌの塩化ナトリウムを溶解させた水に殺菌剤（組成物１（実施例１−１）または組成物２（実施例１−２））を添加し、ｐＨが７．０になるように塩酸または水酸化ナトリウムを用いて調整したものを使用した。殺菌剤の濃度は全塩素濃度で約３〜１０ｍｇ／Ｌとなるように添加した。水温は２５±１℃となるようにチラーを用いて調節した。逆浸透膜の操作圧は０．７５ＭＰａとした。逆浸透膜への供給水は５Ｌ／ｍｉｎで通水した。 The test water (treated water) of the flat membrane test was prepared by disinfecting a disinfectant (Composition 1 (Example 1-1) or Composition 2 (Example 1) in water in which 500 mg / L sodium chloride was dissolved in pure water. 2)) was added, and the mixture was adjusted with hydrochloric acid or sodium hydroxide so that the pH was 7.0. The concentration of the disinfectant was added so that the total chlorine concentration was about 3 to 10 mg / L. The water temperature was adjusted using a chiller so as to be 25 ± 1 ° C. The operating pressure of the reverse osmosis membrane was 0.75 MPa. The water supplied to the reverse osmosis membrane was passed at 5 L / min.
アンモニア濃度が０ｍｇ／Ｌ、１ｍｇ／Ｌ、５ｍｇ／Ｌ、１０ｍｇ／Ｌとなるように塩化アンモニウムを添加し、３時間程度の通水の後、そのときの各殺菌剤の被処理水濃度（全塩素濃度）、透過水濃度（全塩素濃度）、透過率を測定した。測定結果を表１、殺菌剤透過率（％）とアンモニウムイオン濃度（ｍｇ／Ｌ）の相関を図４（組成物１（実施例１−１））、図５（組成物２（実施例１−２））に示す。 Ammonium chloride was added so that the ammonia concentration would be 0 mg / L, 1 mg / L, 5 mg / L, 10 mg / L, and after passing water for about 3 hours, the concentration of water to be treated for each disinfectant at that time (total Chlorine concentration), permeated water concentration (total chlorine concentration), and transmittance were measured. Table 1 shows the measurement results, and FIG. 4 (Composition 1 (Example 1-1)) and FIG. 5 (Composition 2 (Example 1) show the correlation between the germicide permeability (%) and the ammonium ion concentration (mg / L). -2)).
殺菌剤の透過率はアンモニアの濃度とともに上昇した。特にアンモニア濃度５ｍｇ／Ｌ以下では透過率の上昇の傾向が比較的大きく、アンモニア濃度を５ｍｇ／Ｌ以下にする前処理が望ましいと考えられる。 The permeability of the bactericide increased with the concentration of ammonia. In particular, when the ammonia concentration is 5 mg / L or less, the tendency of the transmittance to increase is relatively large, and it is considered that pretreatment for making the ammonia concentration 5 mg / L or less is desirable.
また、本システムにおける逆浸透膜の種類としては、アニオン荷電膜ＥＳ１５よりも中性膜ＬＦＣ３を用いた方が殺菌剤の透過率が低くなることがわかった。 Moreover, as a kind of reverse osmosis membrane in this system, it turned out that the permeability | transmittance of a disinfectant becomes lower when the neutral membrane LFC3 is used than the anion charged membrane ES15.
＜実施例２および３、比較例２および３＞
図６に示すパイロット装置を用いて試験を行った。原水（被処理水）には、純水に塩化ナトリウムを５００ｍｇ／Ｌ溶かした水を、ｐＨ＝７．０に調整したものを使用した。ｐＨ調整剤には、塩酸または水酸化ナトリウムを使用した。逆浸透膜には、日東電工社製ＬＦＣ３またはＥＳ１５を使用し、原水の処理水量は２５ｍ３／ｄ、供給水温は２５℃、供給圧力は０．７５ＭＰａとした。殺菌剤には、安定化次亜臭素酸組成物（組成物１）を使用し、殺菌剤の濃度として全塩素濃度を測定した。
<Examples 2 and 3, Comparative Examples 2 and 3>
The test was conducted using the pilot apparatus shown in FIG. As raw water (treated water), water in which 500 mg / L of sodium chloride was dissolved in pure water was adjusted to pH = 7.0. Hydrochloric acid or sodium hydroxide was used as the pH adjuster. As the reverse osmosis membrane, LFC3 or ES15 manufactured by Nitto Denko Corporation was used, the amount of treated water of raw water was 25 m 3 / d, the supply water temperature was 25 ° C., and the supply pressure was 0.75 MPa. A stabilized hypobromite composition (Composition 1) was used as the disinfectant, and the total chlorine concentration was measured as the disinfectant concentration.
（実施例２、比較例２）
実施例２では、アンモニア低減手段としてアンモニアストリッピング装置を使用し、比較例２では、アンモニアストリッピング装置を使用しなかった。原水（被処理水）のアンモニア濃度が２００ｍｇ／Ｌ、１００ｍｇ／Ｌ、２０ｍｇ／Ｌとなるように塩化アンモニウムを添加した。アンモニアストリッピングを行う液温は８０℃とし、ｐＨは１０とした。このとき、被処理水および逆浸透膜入口水のアンモニア濃度、逆浸透膜入口水および処理水の殺菌剤濃度（全塩素）を測定し、各条件における殺菌剤透過率を算出した。結果を表２に示す。
(Example 2, comparative example 2)
In Example 2, an ammonia stripping device was used as an ammonia reduction means, and in Comparative Example 2, an ammonia stripping device was not used. Ammonium chloride was added so that the ammonia concentration of the raw water (treated water) was 200 mg / L, 100 mg / L, and 20 mg / L. The liquid temperature for ammonia stripping was 80 ° C., and the pH was 10. At this time, the ammonia concentration of the water to be treated and the reverse osmosis membrane inlet water, the bactericide concentration (total chlorine) of the reverse osmosis membrane inlet water and the treated water were measured, and the bactericidal permeability in each condition was calculated. The results are shown in Table 2.
実施例２では、比較例２に比べて、殺菌剤の透過率を低減することができた。また、被処理水のアンモニア濃度が１００ｍｇ／Ｌ以下のとき、逆浸透膜入口におけるアンモニア濃度が５ｍｇ／Ｌ以下となり、比較例と比較して殺菌剤の透過率が０．０６９倍以下となり、特に効果的に透過率を低減することができた。 In Example 2, as compared with Comparative Example 2, the transmittance of the bactericide could be reduced. In addition, when the ammonia concentration of the water to be treated is 100 mg / L or less, the ammonia concentration at the reverse osmosis membrane inlet is 5 mg / L or less, and the transmittance of the bactericide is 0.069 times or less compared to the comparative example. The transmittance can be effectively reduced.
（実施例３、比較例３）
実施例３では、アンモニア低減手段として酸化剤を添加し、比較例３では酸化剤を添加しなかった。酸化剤としては、後段の逆浸透膜で添加される、安定化次亜臭素酸組成物（組成物１）を添加した。原水（被処理水）のアンモニア濃度が２０ｍｇ／Ｌ、１５ｍｇ／Ｌ、３ｍｇ／Ｌとなるように塩化アンモニウムを添加した。添加した酸化剤の濃度は、全塩素で１０ｍｇ／Ｌとし、ｐＨは７．２とした。酸化分解の反応時間は３０分とした。結果を表３に示す。
(Example 3, Comparative Example 3)
In Example 3, an oxidizing agent was added as a means for reducing ammonia, and in Comparative Example 3, no oxidizing agent was added. As an oxidizing agent, the stabilized hypobromite composition (composition 1) added in a reverse osmosis membrane of the latter stage was added. Ammonium chloride was added so that the ammonia concentration of the raw water (treated water) was 20 mg / L, 15 mg / L, and 3 mg / L. The concentration of the added oxidant was 10 mg / L of total chlorine, and the pH was 7.2. The reaction time for oxidative decomposition was 30 minutes. The results are shown in Table 3.
実施例３では、比較例３に比べて、殺菌剤の透過率を低減することができた。また、被処理水のアンモニア濃度が１５ｍｇ／Ｌ以下のとき、逆浸透膜入口におけるアンモニア濃度が５ｍｇ／Ｌ以下となり、比較例と比較して殺菌剤の透過率が０．０５６倍以下となり、特に効果的に透過率を低減することができた。 In Example 3, compared with Comparative Example 3, the transmittance of the bactericide could be reduced. In addition, when the ammonia concentration of the water to be treated is 15 mg / L or less, the ammonia concentration at the reverse osmosis membrane inlet is 5 mg / L or less, and the transmittance of the bactericide is 0.056 times or less as compared with the comparative example. The transmittance can be effectively reduced.
＜実施例４−１〜４−５＞
模擬排水として、活性炭で残留塩素を除去した相模原市水に、アンモニア性窒素（ＮＨ４−Ｎ）の濃度が７．８ｍｇ−Ｎ／Ｌ（０．５６ｍｍｏｌ／Ｌ）になるように塩化アンモニウムを溶解させた水溶液を調製した。調製した模擬排水のｐＨは７．２であった。調製した模擬排水に、安定化次亜臭素酸組成物（組成物１）（実施例４−１〜４−５）を、有効ハロゲンとして１５ｍｇ／Ｌ ａｓＣｌ２（０．２１ｍｍｏｌ／Ｌ）（実施例４−１）、４０ｍｇ／Ｌ ａｓＣｌ２（０．５６ｍｍｏｌ／Ｌ）（実施例４−１）、６１ｍｇ／Ｌ ａｓＣｌ２（０．８７ｍｍｏｌ／Ｌ）（実施例４−３）、７９ｍｇ／Ｌ ａｓＣｌ２（１．１１ｍｍｏｌ／Ｌ）（実施例４−４）、９９ｍｇ／Ｌ ａｓＣｌ２（１．４０ｍｍｏｌ／Ｌ）（実施例４−５）になるように、添加した。試験液をデジタルスターラにより５００ｒｐｍで撹拌しながら、アンモニア性窒素（ＮＨ４−Ｎ）濃度の経時変化（１０分後、３０分後）を測定した。３０分後に、試験水の全塩素濃度を測定した。結果を表４に示す。
<Examples 4-1 to 4-5>
As simulated waste water, ammonium chloride was dissolved in Sagamihara city water from which residual chlorine was removed with activated carbon so that the concentration of ammonia nitrogen (NH 4 -N) would be 7.8 mg-N / L (0.56 mmol / L). An aqueous solution was prepared. The prepared simulated waste water had a pH of 7.2. To the prepared simulated waste water, a stabilized hypobromite composition (Composition 1) (Examples 4-1 to 4-5) was added as an effective halogen at 15 mg / L asCl 2 (0.21 mmol / L) (Examples). 4-1), 40 mg / L asCl 2 (0.56 mmol / L) (Example 4-1), 61 mg / L asCl 2 (0.87 mmol / L) (Example 4-3), 79 mg / L asCl 2 (1.11 mmol / L) (Example 4-4) and 99 mg / L asCl 2 (1.40 mmol / L) (Example 4-5) were added. While the test solution was stirred with a digital stirrer at 500 rpm, the change over time in ammonia nitrogen (NH 4 -N) concentration (after 10 minutes and after 30 minutes) was measured. After 30 minutes, the total chlorine concentration of the test water was measured. The results are shown in Table 4.
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。アンモニア性窒素（ＮＨ４−Ｎ）濃度（ｍｇ／Ｌ ａｓＮ）は、株式会社共立理化学研究所のパックテスト（アンモニウム態窒素、型式ＷＡＫ−ＮＨ４）により、ＪＩＳ Ｋ ０１０２ ４２．２のインドフェノール青吸光光度法の発色原理を用いて測定した。 The total chlorine concentration is a value (mg / L asCl 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. Ammonia nitrogen (NH 4 -N) concentration (mg / L asN) was measured according to the pack test (ammonium nitrogen, model WAK-NH 4) of Kyoritsu Riken Co., Ltd. according to JIS K 0102 42.2 indophenol blue absorbance. Measurements were made using the photometric color development principle.
表４において、処理前の模擬排水中のアンモニア性窒素（ＮＨ４−Ｎ）のモル濃度（０．５６ｍｍｏｌ／Ｌ）に対する、有効塩素濃度換算の有効ハロゲンのモル濃度（安定化次亜臭素酸組成物の添加モル濃度）の比が大きくなればなるほど、アンモニア性窒素の低減効果も高くなることが明らかになった。特に、模擬排水中のアンモニア性窒素（ＮＨ４−Ｎ）のモル濃度に対する、有効塩素濃度換算の有効ハロゲンのモル濃度（安定化次亜臭素酸組成物の添加モル濃度）の比が１．６（実施例４−３）以上の場合に、アンモニア性窒素をほぼ完全に分解できることが明らかとなった。 In Table 4, the effective halogen molar concentration in terms of effective chlorine concentration (stabilized hypobromite composition) relative to the molar concentration (0.56 mmol / L) of ammoniacal nitrogen (NH 4 -N) in the simulated waste water before treatment It has been clarified that the effect of reducing ammonia nitrogen increases as the ratio of the added molar concentration of the product increases. In particular, the ratio of the molar concentration of effective halogen in terms of effective chlorine concentration (added molar concentration of stabilized hypobromite composition) to the molar concentration of ammoniacal nitrogen (NH 4 —N) in simulated waste water is 1.6. (Example 4-3) In the above case, it became clear that ammoniacal nitrogen could be decomposed almost completely.
以上の通り、実施例の方法により、アンモニアを含有する被処理水を逆浸透膜で処理する水処理方法において、塩素系酸化剤または臭素系酸化剤とスルファミン酸化合物とを含む殺菌剤の逆浸透膜の透過を抑制することができた。 As described above, in the water treatment method for treating the water to be treated containing ammonia with the reverse osmosis membrane according to the method of the embodiment, the reverse osmosis of the bactericide containing the chlorine-based oxidizing agent or bromine-based oxidizing agent and the sulfamic acid compound. Permeation of the membrane could be suppressed.
１ 水処理装置、３ 水処理システム、１０ アンモニア低減装置、１２ アンモニア低減水槽、１４ 逆浸透膜処理装置、１６ 被処理水配管、１８ アンモニア低減水配管、２０ 殺菌剤含有水配管、２２ 透過水配管、２４ 濃縮水配管、２６ 殺菌剤添加配管、５０ 生物処理装置、５２ 生物処理水槽、５４ 膜処理装置、５６ 生物処理システム、５８ 膜処理水槽、６０ 第２逆浸透膜処理装置。 DESCRIPTION OF SYMBOLS 1 Water treatment apparatus, 3 Water treatment system, 10 Ammonia reduction apparatus, 12 Ammonia reduction water tank, 14 Reverse osmosis membrane treatment apparatus, 16 To-be-processed water piping, 18 Ammonia reduction water piping, 20 Bactericidal agent containing water piping, 22 Permeated water piping , 24 Concentrated water piping, 26 Disinfectant addition piping, 50 Biological treatment device, 52 Biological treatment water tank, 54 Membrane treatment device, 56 Biological treatment system, 58 Membrane treatment water tank, 60 Second reverse osmosis membrane treatment device.
Claims (10)
前記アンモニア低減手段によりアンモニアを低減したアンモニア低減水中に臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤を存在させた殺菌剤含有水を、逆浸透膜処理する逆浸透膜処理手段と、
を備えることを特徴とする水処理装置。 Ammonia reducing means for reducing ammonia in the water to be treated containing ammonia;
Reverse osmosis membrane treatment for treating a sterilizer-containing water in which a sterilizer containing a bromine-based oxidant or a chlorine-based oxidant and a sulfamic acid compound is present in ammonia-reduced water in which ammonia has been reduced by the ammonia reducing means. Means,
A water treatment apparatus comprising:
前記アンモニア低減水のアンモニア濃度が、５ｍｇ／Ｌ以下であることを特徴とする水処理装置。 The water treatment device according to claim 1,
A water treatment apparatus, wherein the ammonia concentration of the ammonia-reduced water is 5 mg / L or less.
前記アンモニア低減手段として、アンモニアストリッピング処理装置を備えることを特徴とする水処理装置。 The water treatment device according to claim 1 or 2,
A water treatment device comprising an ammonia stripping treatment device as the ammonia reducing means.
前記アンモニア低減手段として、酸化剤によるアンモニア分解処理手段を備えることを特徴とする水処理装置。 The water treatment device according to claim 1 or 2,
A water treatment apparatus comprising ammonia decomposition treatment means using an oxidizing agent as the ammonia reduction means.
前記逆浸透膜処理手段が、逆浸透膜として中性膜またはカチオン荷電膜を備えることを特徴とする水処理装置。 The water treatment apparatus according to any one of claims 1 to 4,
The water treatment apparatus, wherein the reverse osmosis membrane treatment means includes a neutral membrane or a cation charged membrane as a reverse osmosis membrane.
前記アンモニア低減工程によりアンモニアを低減したアンモニア低減水中に臭素系酸化剤または塩素系酸化剤とスルファミン酸化合物とを含む殺菌剤を存在させた殺菌剤含有水を、逆浸透膜処理する逆浸透膜処理工程と、
を含むことを特徴とする水処理方法。 An ammonia reduction step for reducing ammonia in the water to be treated containing ammonia;
Reverse osmosis membrane treatment for treating a sterilizer-containing water in which a sterilizer containing a bromine-based oxidant or a chlorine-based oxidant and a sulfamic acid compound is present in ammonia-reduced water in which ammonia has been reduced by the ammonia reduction step. Process,
A water treatment method comprising:
前記アンモニア低減水のアンモニア濃度が、５ｍｇ／Ｌ以下であることを特徴とする水処理方法。 The water treatment method according to claim 6,
The ammonia concentration of said ammonia reduction water is 5 mg / L or less, The water treatment method characterized by the above-mentioned.
前記アンモニア低減工程において、アンモニアストリッピング処理を行うことを特徴とする水処理方法。 The water treatment method according to claim 6 or 7,
In the ammonia reduction step, an ammonia stripping treatment is performed.
前記アンモニア低減工程において、酸化剤によるアンモニア分解処理を行うことを特徴とする水処理方法。 The water treatment method according to claim 6 or 7,
A water treatment method comprising performing ammonia decomposition treatment with an oxidizing agent in the ammonia reduction step.
前記逆浸透膜処理工程において、逆浸透膜として中性膜またはカチオン荷電膜を用いることを特徴とする水処理方法。 The water treatment method according to any one of claims 6 to 9,
In the reverse osmosis membrane treatment step, a neutral membrane or a cation charged membrane is used as the reverse osmosis membrane.
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