CN107531523B - Method for treating wastewater containing ammonia nitrogen and ammonia nitrogen decomposer - Google Patents
Method for treating wastewater containing ammonia nitrogen and ammonia nitrogen decomposer Download PDFInfo
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- CN107531523B CN107531523B CN201680025926.3A CN201680025926A CN107531523B CN 107531523 B CN107531523 B CN 107531523B CN 201680025926 A CN201680025926 A CN 201680025926A CN 107531523 B CN107531523 B CN 107531523B
- Authority
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- China
- Prior art keywords
- nitrogen
- bromine
- ammonia
- sulfamic acid
- acid compound
- Prior art date
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000002351 wastewater Substances 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 63
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 131
- -1 bromine compound Chemical class 0.000 claims abstract description 130
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 127
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000203 mixture Substances 0.000 claims abstract description 80
- 239000007800 oxidant agent Substances 0.000 claims abstract description 64
- 239000000460 chlorine Substances 0.000 claims abstract description 56
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 55
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 9
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 42
- 230000000694 effects Effects 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 12
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 239000005708 Sodium hypochlorite Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000010865 sewage Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000645 desinfectant Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 229910021529 ammonia Inorganic materials 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
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 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 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000249 desinfective effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- PIEXCQIOSMOEOU-UHFFFAOYSA-N 1-bromo-3-chloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Br)C(=O)N(Cl)C1=O PIEXCQIOSMOEOU-UHFFFAOYSA-N 0.000 description 1
- 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 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- FECFIIXKXJBOSU-UHFFFAOYSA-N butylsulfamic acid Chemical compound 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
- 238000004364 calculation method Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IOISAJSHULNACL-UHFFFAOYSA-N ethyl(methyl)sulfamic acid Chemical compound CCN(C)S(O)(=O)=O IOISAJSHULNACL-UHFFFAOYSA-N 0.000 description 1
- SIVVHUQWDOGLJN-UHFFFAOYSA-N ethylsulfamic acid Chemical compound CCNS(O)(=O)=O SIVVHUQWDOGLJN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- YZVQGLCYZLGIAM-UHFFFAOYSA-N methyl(propyl)sulfamic acid Chemical compound CCCN(C)S(O)(=O)=O YZVQGLCYZLGIAM-UHFFFAOYSA-N 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical compound CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- AMULHDKUJWPBKU-UHFFFAOYSA-L nickel(2+);dichlorite Chemical compound [Ni+2].[O-]Cl=O.[O-]Cl=O AMULHDKUJWPBKU-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 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
- 238000012545 processing Methods 0.000 description 1
- JWQSOOZHYMZRBT-UHFFFAOYSA-N propan-2-ylsulfamic acid Chemical compound CC(C)NS(O)(=O)=O JWQSOOZHYMZRBT-UHFFFAOYSA-N 0.000 description 1
- HLIBNTOXKQCYMV-UHFFFAOYSA-N propylsulfamic acid Chemical compound CCCNS(O)(=O)=O HLIBNTOXKQCYMV-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage 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
- 238000004448 titration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Providing: a method for treating ammonia-nitrogen-containing wastewater, which can treat ammonia-nitrogen-containing wastewater by a simple method. A method for treating ammonia nitrogen-containing wastewater, which comprises allowing a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound to be present in ammonia nitrogen-containing wastewater containing ammonia nitrogen; a bromine-based oxidizing agent, or a reaction product of a bromine compound and a chlorine-based oxidizing agent, or a mixture or a reaction product of a bromine compound and a sulfamic acid compound is caused to exist in ammonia nitrogen-containing wastewater containing ammonia nitrogen; alternatively, a mixture of bromine and a sulfamic acid compound, or a reaction product of bromine and a sulfamic acid compound is caused to exist in ammonia nitrogen-containing wastewater containing ammonia nitrogen.
Description
Technical Field
The present invention relates to a method for treating ammonia nitrogen-containing wastewater for treating wastewater such as sewage containing ammonia nitrogen, and an ammonia nitrogen decomposer.
Background
When industrial and factory wastewater including factory wastewater, sewage treatment water, and the like are discharged to public water areas, these discharged waters are applied to wastewater standards by a method for preventing water contamination. In addition, 3 sea areas, including tokyo bay, iwai bay, and inner garland, are subject to total amount limit based on COD, nitrogen, and phosphorus.
In order to meet wastewater standards and total amount restrictions, for example, for wastewater from sewage and aquaculture plants, it is necessary to sterilize the wastewater before discharge so that the number of coliforms is 3000/mL or less, and it is also desirable to minimize the content of components to be subjected to wastewater restrictions, such as ammonia nitrogen.
Chlorine-based oxidizing agents such as hypochlorite are generally used as disinfectants for sewage water and the like, but when ammonia nitrogen is contained in the water to be treated, the chlorine-based oxidizing agents react with the ammonia nitrogen to generate chloramine, and thus there is a problem that the disinfecting effect is insufficient. Therefore, it has recently been proposed to use bromine-based oxidizing agents as disinfectant components. If a component having an effect of decomposing ammonia nitrogen contained in wastewater is used as the disinfectant component, the load of biological treatment such as nitrification and denitrification at the subsequent stage is reduced, and favorable treatment can be performed from the viewpoint of wastewater treatment.
Patent document 1 discloses a disinfectant containing hypobromous acid or a salt thereof as a disinfectant for wastewater such as sewage. Patent document 2 discloses a method of disinfecting sewage containing ammonia or ammonium ions by using a solid disinfectant containing 1-bromo-3-chloro-5, 5-dimethylhydantoin, and this method can be applied to treatment of sewage in rainy weather.
However, the method described in patent document 1 requires storage facilities for obtaining 2 kinds of chemicals, i.e., a bromide salt and a hypochlorite of hypobromous acid or a salt thereof, and a reaction apparatus for reacting these, and the facilities become huge. In the method described in patent document 2, since the disinfectant is solid, a dissolving device is required, and the equipment becomes bulky in the same manner. In addition, the methods described in patent documents 1 and 2 do not describe any effect of reducing ammonia nitrogen contained in wastewater, sewage, or the like.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2003-012425
Patent document 2: japanese patent No. 4628132
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide: a method for treating ammonia-nitrogen-containing wastewater, which can treat ammonia-nitrogen-containing wastewater by a simple method, and an ammonia-nitrogen decomposer.
Means for solving the problems
The invention relates to a method for treating ammonia nitrogen-containing wastewater, which enables bromine-based oxidant or reactant of bromine compound and chlorine-based oxidant and sulfamic acid compound to exist in ammonia nitrogen-containing wastewater containing ammonia nitrogen.
The invention relates to a method for treating ammonia nitrogen-containing wastewater, which enables bromine-based oxidant, or a reaction product of a bromine compound and a chlorine-based oxidant, and a mixture or a reaction product of a sulfamic acid compound to exist in ammonia nitrogen-containing wastewater containing ammonia nitrogen.
The invention is a method for treating waste water containing ammonia nitrogen, which makes the mixture of bromine and sulfamic acid compound exist in the waste water containing ammonia nitrogen; alternatively, the reaction product of bromine and the sulfamic acid compound is caused to be present in the ammonia nitrogen-containing wastewater containing ammonia nitrogen.
In the method for treating ammonia-nitrogen-containing wastewater, it is preferable that the bromine-based oxidizing agent or the reaction product of the bromine compound and the chlorine-based oxidizing agent and the sulfamic acid compound are present in the ammonia-nitrogen-containing wastewater, and the treated water having reduced ammonia nitrogen is further treated with a reverse osmosis membrane.
In the method for treating ammonia-nitrogen-containing wastewater, it is preferable that the bromine-based oxidizing agent, or a reaction product of the bromine compound and the chlorine-based oxidizing agent, and the sulfamic acid compound are allowed to exist in the ammonia-nitrogen-containing wastewater, and then the treated water having reduced ammonia nitrogen is further treated with a reverse osmosis membrane.
In the method for treating ammonia-nitrogen-containing wastewater, it is preferable that after the mixture of bromine and a sulfamic acid compound is present in the ammonia-nitrogen-containing wastewater, or after the reaction product of bromine and a sulfamic acid compound is present in the ammonia-nitrogen-containing wastewater, the treated water having reduced ammonia nitrogen is further treated with a reverse osmosis membrane.
In the method for treating ammonia-nitrogen-containing wastewater, the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine is preferably in the range of 0.5 to 1.5.
In the method for treating ammonia-nitrogen-containing wastewater, the ratio of the molar concentration of available halogen to the molar concentration of ammonia nitrogen in terms of the available chlorine concentration in the ammonia-nitrogen-containing wastewater is preferably 1.6 or more.
In the method for treating ammonia-nitrogen-containing wastewater, the concentration of ammonia nitrogen in the ammonia-nitrogen-containing wastewater is preferably 5mg/L or more.
The present invention is an ammoniacal nitrogen decomposer for decomposing ammoniacal nitrogen in ammonia-nitrogen-containing wastewater, comprising: a bromine-based oxidizing agent, or a reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound.
The present invention is an ammoniacal nitrogen decomposer for decomposing ammoniacal nitrogen in ammonia-nitrogen-containing wastewater, comprising: bromine-based oxidizing agents, or reactants of bromine compounds and chlorine-based oxidizing agents, and mixtures or reaction products of bromine-based oxidizing agents and chlorine-based oxidizing agents with sulfamic acid compounds.
The present invention is an ammoniacal nitrogen decomposer for decomposing ammoniacal nitrogen in ammonia-nitrogen-containing wastewater, comprising: a mixture of bromine and a sulfamic acid compound, or a reaction product of bromine and a sulfamic acid compound.
In the ammonia nitrogen decomposer, the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine is preferably in the range of 0.5 to 1.5.
In the ammonia nitrogen-decomposing agent, the concentration of ammonia nitrogen in the ammonia nitrogen-containing wastewater is preferably 5mg/L or more.
ADVANTAGEOUS EFFECTS OF INVENTION
In the present invention, the ammonia nitrogen-containing wastewater can be treated by a simple method.
Detailed Description
Hereinafter, embodiments of the present invention will be described. The present embodiment is merely an example for carrying out the present invention, and the present invention is not limited to the present embodiment.
Treatment method of wastewater containing ammonia nitrogen
The method for treating ammonia-nitrogen-containing wastewater according to the embodiment of the present invention is a method comprising: a method in which a "bromine-containing oxidizing agent" and an "sulfamic acid compound" are allowed to exist in ammonia nitrogen-containing wastewater containing ammonia nitrogen; or a method in which a "reaction product of a bromine compound and a chlorine-based oxidizing agent" and a "sulfamic acid compound" are allowed to exist in ammonia nitrogen-containing wastewater containing ammonia nitrogen. From this fact, it is considered that a stabilized hypobromous acid composition is produced in the wastewater containing ammonia nitrogen.
The method for treating ammonia-nitrogen-containing wastewater according to the embodiment of the present invention is a method comprising: a method of causing a stabilized hypobromous acid composition, which is a "mixture of a brominated oxidizing agent and a sulfamic acid compound" or a "reaction product of a brominated oxidizing agent and a sulfamic acid compound", to be present in ammoniacal nitrogen-containing wastewater containing ammoniacal nitrogen; or a method of allowing a stabilized hypobromous acid composition, which is a reaction product of a bromine compound and a chlorine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound, to be present in ammonia nitrogen-containing wastewater containing ammonia nitrogen.
Specifically, the method for treating ammonia nitrogen-containing wastewater according to the present embodiment is, for example, the following method: the "bromine", "bromine chloride", "hypobromous acid" or "reactant of sodium bromide with hypochlorous acid", and "sulfamic acid compound" are caused to exist in the ammonia-nitrogen-containing wastewater.
The method for treating ammonia-nitrogen-containing wastewater according to the present embodiment is, for example, the following method: the stabilized hypobromous acid composition is caused to exist in the ammonia-nitrogen-containing wastewater as "a mixture of bromine and a sulfamic acid compound", "a mixture of bromine chloride and a sulfamic acid compound", or "a reactant of sodium bromide and hypochlorous acid, a mixture of a sulfamic acid compound". The method for treating ammonia-nitrogen-containing wastewater according to the present embodiment is, for example, the following method: the stabilized hypobromous acid composition, which is the "reaction product of bromine with an aminosulfonic acid compound", "reaction product of bromine chloride with an aminosulfonic acid compound", or "reaction product of sodium bromide with hypochlorous acid, reaction product with an aminosulfonic acid compound", is caused to exist in the ammonia-nitrogen-containing wastewater.
By these methods, the ammonia nitrogen in the ammonia nitrogen-containing wastewater can be efficiently decomposed, and the ammonia nitrogen-containing wastewater can be treated by a simple method. For these methods, the ammonia nitrogen-containing wastewater may be treated with a treating agent. Further, since a component having an effect of reducing the number of escherichia coli groups (disinfection effect) and an effect of decomposing ammonia nitrogen is used as the disinfectant component, the load of biological treatment such as nitrification and denitrification in the subsequent stage is reduced, and favorable treatment can be performed from the viewpoint of wastewater treatment.
Sodium hypochlorite, which is a chlorine-based oxidizing agent, reacts with the ammonium nitrogen in the wastewater containing ammonium nitrogen to generate a bound halogen (chloramine), and the decomposition performance of the ammonium nitrogen is significantly reduced, but the stabilized hypobromous acid composition can decompose the ammonium nitrogen without generating the bound halogen as it is, and therefore, the decomposition effect of the ammonium nitrogen is higher than that of a chlorine-based oxidizing agent such as sodium hypochlorite, and it is considered that more effective treatment can be performed. Further, since the stabilized hypobromous acid composition contains an aminosulfonic acid compound, it is considered that the decomposition effect of the ammoniacal nitrogen is higher than that of hypobromous acid or a salt thereof.
In the method for treating ammonia nitrogen-containing wastewater of the present embodiment, for example, the "bromine-containing oxidizing agent" or the "reactant of the bromine compound and the chlorine-containing oxidizing agent" and the "sulfamic acid compound" may be injected into the ammonia nitrogen-containing wastewater by a syringe pump or the like. The "bromine-containing oxidizing agent" or the "reaction product of a bromine compound and a chlorine-containing oxidizing agent" and the "sulfamic acid compound" may be added to the ammonia-nitrogen-containing wastewater, respectively, or the raw liquids may be mixed with each other to form a mixture and then added to the ammonia-nitrogen-containing wastewater.
For example, the "reaction product of a bromine-based oxidizing agent and a sulfamic acid compound", or the "reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound" may be injected into the ammonia nitrogen-containing wastewater by a syringe pump or the like.
The ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine" or the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine" in the "bromine-based oxidizing agent" or the "reaction product of a bromine compound and a chlorine-based oxidizing agent" is preferably 0.1 or more, more preferably in the range of 0.5 to 1.5, and still more preferably in the range of 1 to 1.5. Here, the ratio of equivalents of the "sulfamic acid compound" to equivalents of the "bromine" means the following ratio: the content of the sulfamic acid compound in the stabilized hypobromous acid composition [ wt.%]The value obtained by dividing the molecular weight of the aminosulfonic acid compound (97.1 in the case where the aminosulfonic acid compound is aminosulfonic acid) is based on the bromine content [ wt% ]inthe stabilized hypobromous acid composition]By bromine (Br)2) The molecular weight of (1) to (4) (159.8). When the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine" is less than 0.1, a sufficient effect of decomposing ammonia nitrogen may not be obtained, and when it exceeds 1.5, the production cost may increase. When the equivalent ratio is in the range of 0.5 to 1.5, more preferably in the range of 0.7 to 1.5, the ammonium nitrogen can be efficiently decomposed. In addition, if the equivalent ratio is 1 or more, the stability of the preparation becomes good.
The effective halogen concentration in the ammonia-nitrogen containing wastewater is preferably 1 to 50mg/L in terms of effective chlorine concentration. If the concentration is less than 1mg/L, a sufficient decomposition effect of ammonia nitrogen may not be obtained, and if the concentration is more than 50mg/L, corrosion of piping or the like may be caused.
The molar concentration of available halogen (molar concentration of stabilized hypobromous acid composition) relative to ammoniacal Nitrogen (NH) in terms of the available chlorine concentration in the wastewater containing ammoniacal nitrogen4The molar concentration ratio of-N) is preferably 1.6 or more, more preferably 2.0 or more. The larger the ratio becomes, the higher the effect of reducing the ammonia nitrogen becomes.
Examples of the bromine-based oxidizing agent include: bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromous acid, and the like.
Among these, a formulation using "bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound)" or "reaction product of bromine and sulfamic acid compound" using bromine is more preferable because it has less by-product of bromic acid and is less likely to cause corrosion of metal materials such as piping, compared with a formulation using "hypochlorous acid and bromine compound and sulfamic acid" or a formulation using "bromine chloride and sulfamic acid".
That is, in the method for treating ammonia nitrogen-containing wastewater of the present embodiment, it is preferable that bromine and a sulfamic acid compound are present (a mixture of bromine and a sulfamic acid compound is present) in the ammonia nitrogen-containing wastewater. In addition, it is preferable that the reaction product of bromine and the sulfamic acid compound is present in the ammonia nitrogen-containing wastewater.
Examples of the bromine compound include: sodium bromide, potassium bromide, lithium bromide, ammonium bromide, hydrobromic acid, and the like. Among these, sodium bromide is preferred from the viewpoint of the cost of the preparation and the like.
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, and the like. Among these, examples of the salt include: alkali metal hypochlorates such as sodium hypochlorite and potassium hypochlorite, alkaline earth metal hypochlorates such as calcium hypochlorite and barium hypochlorite, alkali metal chlorites such as sodium chlorite and potassium chlorite, alkaline earth metal chlorites such as barium chlorite, other metal chlorites such as nickel chlorite, alkali metal chlorites such as ammonium chlorate, sodium chlorate and potassium chlorate, and alkaline earth metal chlorites such as calcium chlorate and barium chlorate. These chlorine-based oxidizing agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds. As the chlorine-based oxidizing agent, sodium hypochlorite is preferably used from the viewpoint of handling property and the like.
The sulfamic acid compound is a compound represented by the following general formula (1).
R2NSO3H (1)
(wherein R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
Examples of the sulfamic acid compound include, in addition to sulfamic acid (amidosulfuric acid) in which 2R groups are all hydrogen atoms: sulfamic acid compounds in which one of the 2R groups is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, such as N-methylaminosulfonic acid, N-ethylaminosulfonic acid, N-propylaminosulfonic acid, N-isopropylaminosulfonic acid, and N-butylaminosulfonic acid; sulfamic acid compounds in which 2R groups of N, N-dimethylaminesulfonic acid, N-diethylaminosulfonic acid, N-dipropylaminosulfonic acid, N-dibutylaminosulfonic acid, N-methyl-N-ethylaminosulfonic acid, N-methyl-N-propylsulfamic acid, and the like are alkyl groups having 1 to 8 carbon atoms; sulfamic acid compounds such as N-phenyl sulfamic acid, wherein one of the 2R groups is a hydrogen atom, and the other is an aryl group having 6 to 10 carbon atoms; or salts thereof, and the like. Examples of sulfamates include: alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salts, strontium salts, barium salts, etc.; manganese salt, copper salt, zinc salt, iron salt, cobalt salt, nickel salt and other metal salts; ammonium and guanidinium salts, and the like. The sulfamic acid compound and the salts may be used alone in 1 kind or in combination of 2 or more kinds. As the sulfamic acid compound, sulfamic acid (amidosulfuric acid) is preferably used from the viewpoint of environmental load and the like.
In the method for treating ammonia nitrogen-containing wastewater according to the present embodiment, an alkali may be present. Examples of the base include: alkali hydroxides such as sodium hydroxide and potassium hydroxide. From the viewpoint of product stability at low temperature, etc., sodium hydroxide and potassium hydroxide may be used in combination. In addition, the base may be used not in a solid state but in the form of an aqueous solution.
In the method for treating ammonia-nitrogen-containing wastewater of the present embodiment, the pH of the ammonia-nitrogen-containing wastewater to be treated is preferably in the range of 3 to 10, and more preferably in the range of 4 to 9. When the pH of the wastewater containing ammonia nitrogen to be treated is less than 3, hypobromous acid is likely to volatilize as bromine gas, and the decomposition effect of ammonia nitrogen is likely to decrease, and when it exceeds 10, ammonia nitrogen is likely to volatilize as ammonia gas and be removed, and the effectiveness of the treatment according to the present invention is likely to decrease.
The ammonia nitrogen-containing wastewater to be treated by the method for treating ammonia nitrogen-containing wastewater of the present embodiment is, for example, industrial plant wastewater including industrial wastewater of an aquatic product processing plant or the like, sewage, or the like. The concentration of ammonium-nitrogen in the ammonia-nitrogen-containing wastewater to be treated is, for example, preferably 5mg/L or more, and more preferably 5mg/L to 500 mg/L. The method for treating wastewater containing ammonia nitrogen according to the present embodiment is suitably used for treating wastewater containing a large amount of ammonia nitrogen of 5mg/L or more. The effect of decomposing the ammonia nitrogen contained in the ammonia nitrogen-containing wastewater can be exhibited not only by reducing the number of Escherichia coli groups but also by treating wastewater containing a large amount of ammonia nitrogen such as 5mg/L or more. In particular, when wastewater containing ammonia nitrogen is treated with a reverse osmosis membrane, if the pH of the wastewater is high, the following problems occur: free ammonia permeates the reverse osmosis membrane and leaks into the permeated water. In this regard, it is preferable to add a stabilized hypobromous acid composition to the ammonia-nitrogen-containing wastewater to decompose ammonia nitrogen, and then treat the treated water with reduced ammonia nitrogen with a reverse osmosis membrane, as in the method for treating ammonia-nitrogen-containing wastewater of the present embodiment, because the problem of leakage of free ammonia into permeate water can be suppressed.
< Ammonia nitrogen decomposer >
The ammonia nitrogen decomposer of the present embodiment contains: the "bromine-based oxidizing agent" or the "reactant of a bromine compound and a chlorine-based oxidizing agent", and the "sulfamic acid compound" may further contain a base.
The ammonia nitrogen decomposer of the present embodiment includes: the "mixture of a bromine-based oxidizing agent and a sulfamic acid compound" or the "mixture of a reaction product of a bromine compound and a chlorine-based oxidizing agent and a sulfamic acid compound" may further contain a base. The ammonia nitrogen decomposer of the present embodiment includes: the "reaction product of a bromine-based oxidizing agent and a sulfamic acid compound", or the "reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound", may further contain a base.
The bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent and sulfamic acid compound are as described above.
The ammonia nitrogen decomposer of the present embodiment preferably contains bromine and a sulfamic acid compound (a mixture containing bromine and a sulfamic acid compound), for example, a mixture containing bromine, a sulfamic acid compound, a base and water, or a reaction product of bromine and a sulfamic acid compound, for example, a reaction product of bromine and a sulfamic acid compound, or a mixture of a base and water, from the viewpoints of low corrosivity to metal materials such as piping and less by-production of bromic acid.
The ammonia nitrogen-decomposing agent of the present embodiment is considered to have a higher decomposition effect of ammonia nitrogen, because ammonia nitrogen can be decomposed without being bound to halogen, as compared with a chlorine-based oxidizing agent such as sodium hypochlorite. Further, the ammonia nitrogen decomposer of the present embodiment is considered to have a higher decomposition effect of ammonia nitrogen than hypobromous acid or a salt thereof because it contains a sulfamic acid compound.
The pH of the ammonia nitrogen decomposer is, for example, more than 13.0, more preferably more than 13.2. When the pH of the ammonium nitrogen decomposer is 13.0 or less, the available halogen in the decomposer may become unstable.
The concentration of bromic acid in the ammoniacal nitrogen decomposer is preferably less than 5 mg/kg. When the concentration of bromic acid in the ammonium-nitrogen decomposer is 5mg/kg or more, the concentration of bromic acid ions in the treated water may be increased.
< method for producing ammonia nitrogen decomposer >
The ammonia nitrogen decomposer of the present embodiment can be obtained by mixing a bromine-based oxidizing agent with a sulfamic acid compound, or by mixing a reaction product of a bromine compound and a chlorine-based oxidizing agent with a sulfamic acid compound, and further mixing a base.
The method for producing an ammonia nitrogen decomposer containing bromine and a sulfamic acid compound or an ammonia nitrogen decomposer containing a reaction product of bromine and a sulfamic acid compound preferably comprises the steps of: a step of adding bromine to a mixed solution containing water, a base and a sulfamic acid compound in an inert gas atmosphere to carry out a reaction; or a step of adding bromine to a mixed solution containing water, a base and a sulfamic acid compound in an inert gas atmosphere. The bromic acid ion concentration in the decomposing agent is lowered by adding the bromic acid ion under an inert gas atmosphere to perform the reaction or adding the bromic acid ion under an inert gas atmosphere.
The inert gas to be used is not limited, but at least 1 of nitrogen and argon is preferable from the viewpoint of production and the like, and nitrogen is particularly preferable from the viewpoint of production cost and the like.
The oxygen concentration in the reactor when bromine is added is preferably 6% by volume or less, more preferably 4% by volume or less, still more preferably 2% by volume or less, and particularly preferably 1% by volume or less. When the oxygen concentration in the reactor during the bromine reaction exceeds 6 vol%, the amount of the generated bromic acid in the reaction system may increase.
The bromine addition rate is preferably 25 wt% or less, more preferably 1 wt% or more and 20 wt% or less, based on the total amount of the decomposition agent. When the bromine addition rate exceeds 25% by weight based on the total amount of the decomposer, the amount of the generated bromic acid in the reaction system may increase. If the content is less than 1% by weight, the decomposition effect of ammonia nitrogen is poor.
The reaction temperature when bromine is added is preferably controlled to be in the range of 0 ℃ to 25 ℃, but is more preferably controlled to be in the range of 0 ℃ to 15 ℃ from the viewpoint of production cost and the like. When the reaction temperature at the time of bromine addition exceeds 25 ℃, the amount of generated bromic acid in the reaction system may increase, and when it is lower than 0 ℃, it may freeze.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
< preparation of the composition >
The stabilized hypobromous acid compositions A, B, C-1, C-2, C-3, C-4, and hypobromite composition D used in the examples are as follows.
[ preparation of stabilized hypobromous acid composition A ]
Under a nitrogen atmosphere, adding liquid bromine: 16.9 weight% (wt%), sulfamic acid: 10.7 wt%, sodium hydroxide: 12.9 wt%, potassium hydroxide: 3.94 wt%, water: the remaining amounts are mixed to prepare the composition. The pH of the composition was 14, and the bromine content was 16.9% by weight. The stabilized hypobromous acid composition a is prepared in detail as follows.
A target stabilized hypobromous acid composition A was obtained by charging a 2L 4-neck flask containing nitrogen gas continuously injected while controlling the flow rate of nitrogen gas with a mass flow controller so that the oxygen concentration in the reaction vessel was maintained at 1 vol%, adding 1436g of water and 361g of sodium hydroxide, mixing them, subsequently adding 300g of sulfamic acid, mixing them, cooling them so that the temperature of the reaction mixture became 0 to 15 ℃, adding 473g of liquid bromine, and further adding 230g of 48 wt% potassium hydroxide solution, whereby 10.7 wt% of sulfamic acid and 16.9 wt% of bromine were added, based on the total amount of the composition, and the ratio of the equivalents of sulfamic acid to the equivalents of bromine was 1.04. The pH of the resulting solution was measured by a glass electrode method, and found to be 14. The bromine content of the resulting solution was measured by a method in which bromine was converted into iodine by potassium iodide and then redox titration was performed using sodium thiosulfate, and as a result, 16.9 wt% was 100.0% of the theoretical content (16.9 wt%). The Oxygen concentration in the reaction vessel at the time of bromine reaction was measured by using "Oxygen Monitor JKO-02 LJDII" manufactured by JIKCO Ltd. Incidentally, the concentration of the bromic acid is less than 5 mg/kg.
The pH was measured under the following conditions.
Electrode type: glass electrode type
A pH meter: DKK-TOACORPORATION, IOL-30 type
And (3) correcting the electrodes: the pH of the sample was adjusted to 2 points by using a neutral phosphate pH (6.86) standard solution (type 2) manufactured by Kanto chemical Co., Ltd and a borate pH (9.18) standard solution (type 2) manufactured by the same company
Measuring temperature: 25 deg.C
Measurement value: the electrode was immersed in the measurement solution, and the value after stabilization was defined as the measurement value, and the average value of 3 measurements
[ preparation of stabilized hypobromous acid composition B ]
Stabilized hypobromous acid composition B was prepared based on the disclosure of international patent application publication No. 03/093171. Stabilized hypobromous acid composition B is a composition containing liquid bromine, sulfamate, sodium hydroxide. The stabilized hypobromous acid composition B had a pH of 14, a bromine content of 16.1 wt%, and a ratio of equivalents of sulfamic acid to equivalents of bromine of 1.45.
[ preparation of stabilized hypobromous acid compositions C-1, C-2, C-3, and C-4 ]
The composition was prepared in the following manner based on the contents of Japanese patent application laid-open No. 11-506139. The pH of the composition was 14, and the bromine content was 11.3% by weight.
(1) 27.0g of a mixture of 40 wt% aqueous sodium bromide solution was added to the pure water in the amount of parts by weight shown in Table 1, and the mixture was stirred.
(2) 41.7g of a 12% by weight sodium hypochlorite solution was added to the solution of (1) and stirred.
(3) A stabilized aqueous solution was prepared which was composed of 56.0g of pure water, 26.0g of sulfamic acid and 18.0g of sodium hydroxide.
(4) The stabilized hypobromous acid compositions C-1, C-2, C-3 and C-4 of interest were obtained by adding the stabilized solution of (3) to the solution of (2) in the amounts of the components shown in Table 1 by weight only and stirring the mixture.
[ Table 1]
For example, the ratio of the equivalent of sulfamic acid to the equivalent of bromine in the stabilized hypobromous acid composition C-1 is calculated from the following formula.
The ratio of equivalents of sulfamic acid to equivalents of bromine (2.6 × 0.26/97.1)/(11.3/159.8) is 0.1
[ production of hypobromite composition D ]
Is a composition prepared by the following steps. The hypobromite composition D had a pH of 12 and a bromine content of 11.3 wt%.
(1) A mixture (27.0 g) of a 40 wt% aqueous solution of sodium bromide was added to 31.3g of pure water and stirred.
(2) 41.7g of a 12% by weight sodium hypochlorite solution was added to the solution of (1) and stirred to obtain the objective hypobromite composition D.
< examples 1 to 3, comparative examples 1 and 2 >
As simulated wastewater, ammonium chloride was dissolved in virgin city water of a phase model obtained by removing residual chlorine with activated carbon to prepare ammonia Nitrogen (NH)4-N) was 7.8mg-N/L (0.56mmol/L) of an aqueous solution. The pH of the simulated wastewater produced was 7.2. To the prepared simulated wastewater, stabilized hypobromous acid composition A (example 1-1), stabilized hypobromous acid composition B (example 2), stabilized hypobromous acid compositions C-1, C-2, C-3, C-4 (examples 3-1, 3-2, 3-3, 3-4), hypobromite composition D (comparative example 1), or sodium hypochlorite (comparative example 2) was added so that 10mg/L asCl in terms of effective halogen was obtained2Or making the stabilized hypobromous acid composition A1 mg/L asCl2(example 1-2). While the test solution was stirred at 500rpm with a digital stirrer, ammonia Nitrogen (NH) was measured4-N) change in concentration over time (after 10 minutes, after 30 minutes). After 30 minutes, the total halogen concentration of the test water was determined. The results are shown in Table 2.
The total halogen concentration (effective chlorine concentration) was measured by the following procedure.
The effective halogen concentration is a value (mg/L asCl) measured by an effective chlorine measuring method (DPD (diethyl-p-phenylenediamine) method) using DR/4000 (measurement item: total chlorine) of a multinomial water quality analyzer (HACH Co.) obtained by diluting a sample2). Here, the effective halogen means a value measured by an effective chlorine measurement method (DPD method). Further, the effective bromine concentration (mg/L asCl) as the effective halogen concentration in terms of chlorine can be calculated from the effective chlorine concentration2) The calculation can be performed as a value obtained by multiplying the value measured by the available chlorine measurement method (DPD method) by 2.25(159.8(g/mol)/70.9(g/mol)) (chlorine (Cl)2) Molecular weight of (B) is 70.9(g/mol), bromine (Br)2) Has a molecular weight of 159.8 (g/mol). ).
Ammonium Nitrogen (NH)4-N) concentration (mg/L asN) Using PACK-TEST (ammonium Nitrogen, type WAK-NH) of Co-Ltd4) And measured by using the color development principle of the indophenol blue absorptiometry according to JIS K010242.2.
[ Table 2]
In Table 2, it is found from comparative example 2 that sodium hypochlorite hardly decomposes ammoniacal nitrogen. The reason for this is considered to be that sodium hypochlorite reacts with ammoniacal nitrogen in wastewater to generate bound halogen (chloramine), and the decomposition performance of ammoniacal nitrogen is greatly reduced. In addition, it is clear from comparative example 1 that the ammonium nitrogen is not sufficiently decomposed even when the hypobromite is used. As shown in examples 1 to 3, it was found that when a stabilized hypobromous acid composition containing sulfamic acid was used, ammonia nitrogen was decomposed more efficiently, and the effect of reducing ammonia nitrogen was increased as the ratio of equivalents of sulfamic acid to equivalents of bromine was increased. In particular, it was found that when the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine in the stabilized hypobromous acid composition is 0.50 (example 3-3) or 0.70 (example 3-4) or more, the effect of reducing ammonia nitrogen becomes high. In addition, comparison of examples 1 to 2 with comparative examples 1 and 2 shows that the stabilized hypobromous acid composition a has a high decomposition effect of ammonium nitrogen even at a smaller added concentration.
< examples 1-3 to 1-7 >
As simulated wastewater, ammonium chloride was dissolved in phase model raw city water obtained by removing residual chlorine with activated carbon to prepare ammonia Nitrogen (NH)4-N) was 7.8mg-N/L (0.56mmol/L) of an aqueous solution. The pH of the simulated wastewater produced was 7.2. To the prepared simulated wastewater, stabilized hypobromous acid composition A (examples 1-3 to 1-7) was added so that the concentration of asCl was 15mg/L in terms of effective halogen2(0.21mmol/L) (examples 1-3), 40mg/L asCl2(0.56mmol/L) (examples 1-4), 61mg/L asCl2(0.87mmol/L) (examples 1-5), 79mg/L asCl2(1.11mmol/L) (examples 1-6), 99mg/L asCl2(1.40mmol/L) (examples 1-7). While the test solution was stirred at 500rpm with a digital stirrer, ammonia Nitrogen (NH) was measured4-N) change in concentration over time (after 10 minutes, after 30 minutes). After 30 minutes, the total halogen concentration of the test water was determined. The results are shown in Table 3. The total halogen concentration (effective chlorine concentration), and ammoniacal nitrogen (b)NH4-N) concentration (mg/L asN) was determined as described above.
Table 3 shows the molar concentration of available halogen (molar concentration of stabilized hypobromous acid composition) relative to ammoniacal Nitrogen (NH) in terms of the available chlorine concentration in the model wastewater before treatment4The larger the ratio of the molar concentration (0.56mmol/L) of-N) becomes, the higher the effect of reducing the ammonia nitrogen becomes. In particular, it was revealed that the molar concentration of available halogen (molar concentration of stabilized hypobromous acid composition added) relative to ammoniacal Nitrogen (NH) was calculated as the concentration of available chlorine in the simulated wastewater4and-N) is 1.6 or more (examples 1 to 5), the decomposition of the ammoniacal nitrogen can be substantially completed.
[ Table 3]
< example 4 >
The wastewater containing ammonium nitrogen, which is the water quality described in table 4, was used to perform an evaluation test of the ammonium nitrogen decomposition performance and the disinfection performance of the stabilized hypobromous acid composition. In a 300mL beaker, add the agent (stabilized hypobromous acid composition A) to make 5mg/L asCl as effective halogen2The stirring was carried out at 250rpm using a digital stirrer. 3 minutes after the addition of the chemical, a predetermined amount of treated water was collected and used for measurement of ammonia Nitrogen (NH)4-N) concentration and inactivation of available chlorine, and determination of the number of E.coli colonies was performed using Petrifilm CC plates after addition of sodium thiosulfate.
[ Table 4]
| Analysis item | Measured value (before addition of agent) | Measured value (drug)After 3 minutes of addition of the agent) |
| NH4Concentration of-N [ mg/L] | 15 | 5 |
| Number of E.coli groups [ number/mL ]] | 100,000 | 43 |
From table 4, it was confirmed that the stabilized hypobromous acid composition exhibits an effect of reducing the number of escherichia coli groups even in the case of wastewater containing a large amount of ammonium-nitrogen, and also exhibits an effect of decomposing ammonium-nitrogen.
Claims (11)
1. A method for treating waste water containing ammonia nitrogen is characterized in that,
a reaction product of a bromine-based oxidizing agent or a bromine compound with a chlorine-based oxidizing agent, and
sulfamic acid compound
In the wastewater containing ammonia nitrogen,
the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine is in the range of 0.5 to 1.5,
the ratio of the molar concentration of the available halogen to the molar concentration of the ammoniacal nitrogen in terms of the available chlorine concentration in the ammonia-nitrogen-containing wastewater is 1.6 or more.
2. A method for treating waste water containing ammonia nitrogen is characterized in that,
reacting a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent with
Sulfamic acid compound
Mixtures or reaction products of
In the wastewater containing ammonia nitrogen,
the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine is in the range of 0.5 to 1.5,
the ratio of the molar concentration of the available halogen to the molar concentration of the ammoniacal nitrogen in terms of the available chlorine concentration in the ammonia-nitrogen-containing wastewater is 1.6 or more.
3. A method for treating waste water containing ammonia nitrogen is characterized in that,
allowing a mixture of bromine and a sulfamic acid compound to exist in ammoniacal nitrogen-containing wastewater containing ammoniacal nitrogen; or,
the reaction product of bromine and sulfamic acid compound is made to exist in the ammonia nitrogen-containing wastewater containing ammonia nitrogen,
the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine is in the range of 0.5 to 1.5,
the ratio of the molar concentration of the available halogen to the molar concentration of the ammoniacal nitrogen in terms of the available chlorine concentration in the ammonia-nitrogen-containing wastewater is 1.6 or more.
4. The method for treating ammonia-nitrogen-containing wastewater according to claim 1,
the bromine-based oxidizing agent or the reaction product of the bromine compound and the chlorine-based oxidizing agent and the sulfamic acid compound are allowed to exist in the ammonia nitrogen-containing wastewater, and the treated water having reduced ammonia nitrogen is further treated with a reverse osmosis membrane.
5. The method for treating ammonia-nitrogen-containing wastewater according to claim 2,
the bromine-based oxidizing agent, or a reactant of the bromine compound and the chlorine-based oxidizing agent, or a mixture or a reaction product of the bromine compound and the sulfamic acid compound is allowed to exist in the ammonia-nitrogen-containing wastewater, and then the ammonia-nitrogen-reduced treated water is further treated with a reverse osmosis membrane.
6. The method for treating ammonia-nitrogen-containing wastewater according to claim 3,
after the mixture of bromine and a sulfamic acid compound is allowed to exist in the ammonia-nitrogen-containing wastewater or after the reaction product of bromine and a sulfamic acid compound is allowed to exist in the ammonia-nitrogen-containing wastewater, the treated water with reduced ammonia nitrogen is further treated with a reverse osmosis membrane.
7. The method for treating ammonia nitrogen-containing wastewater according to any one of claims 1 to 6,
the concentration of ammonium-nitrogen in the ammonium-nitrogen-containing wastewater is 5mg/L or more.
8. An ammonium-nitrogen decomposer characterized by decomposing ammonium-nitrogen in an ammonium-nitrogen-containing wastewater,
comprises the following steps: a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent, and
an amino sulfonic acid compound, wherein the amino sulfonic acid compound,
the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine is in the range of 0.5 to 1.5.
9. An ammonium-nitrogen decomposer characterized by decomposing ammonium-nitrogen in an ammonium-nitrogen-containing wastewater,
comprises the following steps: bromine-based oxidizing agent, or reaction product of bromine compound and chlorine-based oxidizing agent, and
sulfamic acid compound
The mixture or the reaction product of (a),
the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine is in the range of 0.5 to 1.5.
10. An ammonium-nitrogen decomposer characterized by decomposing ammonium-nitrogen in an ammonium-nitrogen-containing wastewater,
comprises the following steps: a mixture of bromine and a sulfamic acid compound, or a reaction product of bromine and a sulfamic acid compound,
the ratio of the equivalent of the sulfamic acid compound to the equivalent of bromine is in the range of 0.5 to 1.5.
11. The ammonia nitrogen decomposer according to any one of claims 8 to 10,
the concentration of ammonium-nitrogen in the ammonium-nitrogen-containing wastewater is 5mg/L or more.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015092757 | 2015-04-30 | ||
| JP2015-092757 | 2015-04-30 | ||
| PCT/JP2016/061379 WO2016175006A1 (en) | 2015-04-30 | 2016-04-07 | Method for treating ammoniacal nitrogen-containing wastewater and ammoniacal nitrogen decomposer |
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| CN107531523B true CN107531523B (en) | 2020-12-18 |
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| JP (1) | JP6412639B2 (en) |
| KR (1) | KR102040042B1 (en) |
| CN (1) | CN107531523B (en) |
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| JP7050414B2 (en) * | 2016-10-25 | 2022-04-08 | オルガノ株式会社 | Water treatment method using reverse osmosis membrane |
| JP7013141B2 (en) * | 2017-04-27 | 2022-02-15 | オルガノ株式会社 | Water treatment method using reverse osmosis membrane |
| JP6513151B2 (en) * | 2017-08-10 | 2019-05-15 | 水ｉｎｇ株式会社 | Method and disinfectant for disinfecting ammonia nitrogen containing wastewater |
| JP6490761B2 (en) * | 2017-08-10 | 2019-03-27 | 水ｉｎｇ株式会社 | Disinfection method of wastewater containing ammonia nitrogen |
| JP6970698B2 (en) * | 2017-08-10 | 2021-11-24 | 水ｉｎｇ株式会社 | Disinfection method for ammonia-containing nitrogen-containing wastewater |
| JP6996955B2 (en) * | 2017-11-30 | 2022-01-17 | オルガノ株式会社 | Method for measuring the concentration of stabilized hypobromous acid composition |
| KR102462490B1 (en) * | 2021-02-22 | 2022-11-03 | (주) 테크윈 | Methods for treatment of refractory wastewater to simultaneously remove organic pollutants and ammonia nitrogen |
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| CN107531523A (en) | 2018-01-02 |
| KR102040042B1 (en) | 2019-11-04 |
| JPWO2016175006A1 (en) | 2017-12-21 |
| WO2016175006A1 (en) | 2016-11-03 |
| JP6412639B2 (en) | 2018-10-24 |
| TW201700409A (en) | 2017-01-01 |
| SG11201708538VA (en) | 2017-11-29 |
| TWI698400B (en) | 2020-07-11 |
| KR20170139676A (en) | 2017-12-19 |
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