JP6513151B2 - Method and disinfectant for disinfecting ammonia nitrogen containing wastewater - Google Patents
Method and disinfectant for disinfecting ammonia nitrogen containing wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 33
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims description 17
- 230000000249 desinfective effect Effects 0.000 title claims description 17
- 239000000645 desinfectant Substances 0.000 title claims description 11
- 239000003814 drug Substances 0.000 claims description 101
- 229940079593 drug Drugs 0.000 claims description 100
- 239000000460 chlorine Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 241000588724 Escherichia coli Species 0.000 claims description 27
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 18
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 11
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 9
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 8
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 7
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 6
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 6
- 229950009390 symclosene Drugs 0.000 claims description 6
- 229940006460 bromide ion Drugs 0.000 claims description 5
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- -1 hypochlorite ions Chemical class 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 18
- 239000010865 sewage Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 241000894006 Bacteria Species 0.000 description 14
- 230000001954 sterilising effect Effects 0.000 description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000005708 Sodium hypochlorite Substances 0.000 description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000012136 culture method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UWMJRBYGKZOPCC-UHFFFAOYSA-N 1-chloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)NC1=O UWMJRBYGKZOPCC-UHFFFAOYSA-N 0.000 description 1
- AYMLREHJPJPZBD-UHFFFAOYSA-N CC1(C(=O)NC(=O)N1)C.Cl Chemical compound CC1(C(=O)NC(=O)N1)C.Cl AYMLREHJPJPZBD-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 241000588923 Citrobacter Species 0.000 description 1
- SXZGXHCIBASYDO-UHFFFAOYSA-N Cl[O-].[Na+].[Na+].ClO.Cl[O-] Chemical compound Cl[O-].[Na+].[Na+].ClO.Cl[O-] SXZGXHCIBASYDO-UHFFFAOYSA-N 0.000 description 1
- 241000588914 Enterobacter Species 0.000 description 1
- 241000588748 Klebsiella Species 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000607768 Shigella Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 208000037386 Typhoid Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 229940005989 chlorate ion Drugs 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002550 fecal effect Effects 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 244000000074 intestinal pathogen Species 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 229940124561 microbicide Drugs 0.000 description 1
- 239000002855 microbicide agent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- IFIDXBCRSWOUSB-UHFFFAOYSA-N potassium;1,3-dichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [K+].ClN1C(=O)NC(=O)N(Cl)C1=O IFIDXBCRSWOUSB-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 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
- XSXSKSKONCDOMZ-UHFFFAOYSA-N sodium;1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [Na+].ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O XSXSKSKONCDOMZ-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 201000008297 typhoid fever Diseases 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Description
本発明は、アンモニア性窒素含有排水の消毒方法及び消毒剤に関し、特に、下水処理場、ポンプ場、雨水吐き口から公共用水域に放流されるアンモニア性窒素を含む排水中の大腸菌又は大腸菌群を殺菌処理する消毒方法及び消毒剤に関する。 The present invention relates to a method and an agent for disinfecting ammonia nitrogen-containing wastewater, and in particular, E. coli or coliform bacteria in wastewater containing ammonia nitrogen discharged from a sewage treatment plant, a pumping station, or a stormwater outlet into public waters. The present invention relates to a disinfecting method and disinfectant to be disinfected.
下水処理場は、家庭や工場から排出される汚水等を無害化して公共用水域に放流するための施設であるが、設計値を上回る降雨があった場合には、中継基地であるポンプ場や雨水吐き口から、雨水の混ざった汚水（以下、雨天時下水という）が、数十秒から数分で、十分に処理されない状態で公共用水域に放流される。この場合、粗大浮遊物やＳＳ（suspended substance：浮遊物質）が公共用水域に放流されるために、美観上問題となる場合があるばかりか、水質汚濁防止法に定める放流基準値（３０００ＣＦＵ／ｍＬ以下）を大幅に上回る大腸菌群や大腸菌が検出される場合がある。 The sewage treatment plant is a facility to harmonize the sewage discharged from homes and factories and release it to public water areas, but if there is rainfall exceeding the design value, the pumping station or relay station will Sewage mixed with rainwater (hereinafter referred to as rain-time sewage) is discharged from the rainwater outlet into public waters without being sufficiently treated in a few dozen seconds to a few minutes. In this case, large floats and SS (suspended substance) may be released to the public water area, which may cause cosmetic problems, and the standard value of discharge defined by the Water Pollution Control Law (3000 CFU / mL E. coli groups and E. coli that are significantly higher than the following may be detected.
下水処理場においても、流入下水が処理能力を大幅に上回る場合には、一部の雨天時下水を簡易処理し放流する場合がある。この場合、細菌の殺菌が十分に実施されないため、水質汚濁防止法に定める放流基準値（３０００ＣＦＵ／ｍＬ以下）を大幅に上回る大腸菌群や大腸菌が検出される場合がある。これらは、特に合流式下水道にみられる現象であるが、分流式下水道においても、土壌性大腸菌群や粗大浮遊物が流入するため、それらが越流して公共水域に放流された場合には、合流式下水道と同様の問題が生じていた。 In the case of sewage treatment plants, when inflowing sewage greatly exceeds the treatment capacity, some of the rainy weathered sewage may be simply treated and released. In this case, since sterilization of bacteria is not sufficiently carried out, coliforms and coliforms may be detected significantly exceeding the discharge standard value (less than 3000 CFU / mL) specified in the Water Pollution Control Law. These are phenomena that are particularly found in combined sewers, but also in diversion sewers, because soil-borne coliforms and coarse floats flow in, when they are overflowed and released into public waters, they are joined. The same problem as the type sewerage had occurred.
下水処理場での消毒は、「下水道施設計画・設計指針と解説」（日本下水道協会発行、２００９年版）によれば、次亜塩素酸ナトリウム、液化塩素、塩素化イソシアヌル酸、次亜塩素酸カルシウムなどの塩素剤を用い、それらを混和池で、１５分以上、下水と接触させることによって大腸菌群を消毒する方法が示されている。また、「下水道施設計画・設計指針と解説」には、オゾンや紫外線による消毒についても記載されている。更に、数万ｍ３の貯留池を設けて雨天時下水を一時貯留し、貯留量以上の降雨量によって越流が起こった場合には、上記の塩素系消毒剤を用いて消毒を行う方法も提案されている。 According to the “Sewerage Facility Planning and Design Guidelines and Comments” published by the Japan Sewerage Association (2009 edition), disinfection at sewage treatment plants is sodium hypochlorite, liquefied chlorine, chlorinated isocyanuric acid, calcium hypochlorite The method of disinfecting coliform bacteria by making them contact with sewage for more than 15 minutes in a mixing tank using a chlorination agent such as is shown. In addition, "Sewer facility plan, design guidelines and commentary" also describes disinfection with ozone and ultraviolet light. Furthermore, a method of storing several tens of thousands of m 3 reservoirs to temporarily store sewage during rainy weather and disinfecting using the above-mentioned chlorine-based disinfectant when overflow occurs due to rainfall more than the storage amount Proposed.
しかし、塩素系消毒剤は、雨天時下水のように降雨強度が大きく短時間で公共用水域に放流される場合には排水との接触時間が短いため殺菌作用が十分に発揮されないこと、及びアンモニア性窒素含有量が多い排水においては、塩素とアンモニア性窒素とが反応してクロラミンを形成しやすく、殺菌作用が低減することから、水質汚濁防止法で定める基準値以下に大腸菌群数を減少させることができないという問題、及び、クロラミンが公共用水域に結合性塩素として長時間残留して環境に悪影響を与えるという問題などがある。そのため、たとえば、次亜塩素酸ナトリウムに対して臭化ナトリウムを等モル以上添加して形成される次亜臭素酸若しくは次亜臭素酸塩の溶液を排水に添加する消毒方法（特許文献１）、（Ａ）次亜塩素酸ナトリウム又は１，３−ジクロロ−５，５−ジメチルヒダントイン、（Ｂ）臭化ナトリウム又は臭化カリウム、及び（Ｃ）Ｌ−アスコルビン酸、グリコール酸又はグリオキシル酸を（Ａ）次亜塩素酸：（Ｂ）臭化物イオン＝１：１〜１：５（モル比）及び（Ａ）次亜塩素酸：（Ｃ）＝１：０．０５〜１：１（モル比）となる量で含む消毒水を排水に添加する消毒方法（特許文献２）、次亜塩素酸、臭化物及び５，５−ジメチルヒダントインを１：（０．２〜３）：（０．２〜０．９）（モル比）で用い、次亜塩素酸類と５，５−ジメチルヒダントインとの反応により残存した次亜塩素酸類に対応して臭化物を混合して形成される次亜臭素酸及びＮ−モノクロロ−５，５−ジメチルヒダントインを含む水溶液である殺微生物剤（特許文献３）など次亜臭素酸を用いる方法が提案されている。 However, chlorine-based disinfectants, such as sewage when it rains, have a large rainfall intensity and are released to public water areas in a short time, and the contact time with the drainage is short, so the sterilization effect is not sufficiently exhibited, and ammonia Chlorinated water and ammoniacal nitrogen react easily to form chloramine in waste water with a large amount of reactive nitrogen content, and the bactericidal action is reduced, so the number of coliform bacteria is reduced below the standard value specified by the Water Pollution Control Law. In addition, there is a problem that chloramines remain in public water areas as binding chlorine for a long time and adversely affect the environment. Therefore, for example, a disinfecting method in which a solution of hypobromous acid or hypobromous acid salt formed by adding equal molar or more of sodium bromide to sodium hypochlorite is added to waste water (Patent Document 1), (A) sodium hypochlorite or 1,3-dichloro-5,5-dimethylhydantoin, (B) sodium bromide or potassium bromide, and (C) L-ascorbic acid, glycolic acid or glyoxylic acid (A) ) Hypochlorous acid: (B) bromide ion = 1: 1 to 1: 5 (molar ratio) and (A) hypochlorous acid: (C) = 1: 0.05 to 1: 1 (molar ratio) The disinfecting method which adds the disinfecting water containing the following amounts to drainage (patent document 2), hypochlorous acid, a bromide, and 5, 5- dimethyl hydantoin 1: (0.2-3): (0.2-0. 9) (molar ratio), hypochlorous acid and 5, 5-dimethyl A microbicide which is an aqueous solution containing hypobromous acid and N-monochloro-5,5-dimethylhydantoin which is formed by mixing a bromide corresponding to hypochlorous acid remaining by reaction with dantoin (Patent Document 3) The method of using hypobromous acid etc. is proposed.
従来提案されている次亜臭素酸を用いる方法であっても、アンモニア性窒素を含む排水の殺菌効果が不十分で、大腸菌群の放流基準値３０００ＣＦＵ／ｍＬ以下に処理できないことや、大腸菌を十分に殺菌できないことがあった。 Even with the method using hypobromous acid, which has been proposed conventionally, the bactericidal effect of the wastewater containing ammonia nitrogen is insufficient, and it can not be processed to the discharge standard value 3000 CFU / mL or less of coliform bacteria, Could not be sterilized.
本発明は、アンモニア性窒素を含む排水中の大腸菌及び大腸菌群の殺菌処理を確実、簡易、且つ経済的に行う方法を提供することを目的とする。 An object of the present invention is to provide a method for reliably, simply and economically carrying out the sterilizing treatment of E. coli and coliform bacteria in waste water containing ammonia nitrogen.
大腸菌とはEsherichia coliであり、大腸菌群とはEsherichia coli以外にCitrobacter属、Enterobacter属、Klebsiella属などを含む。大腸菌群は糞便汚染の指標であり、腸管系病原菌（チフス菌、赤痢菌等）に対する安全性を確認するための検査項目である。本発明者らは、反応して次亜臭素酸塩を生成する２種以上の薬剤を組み合わせて各薬剤の添加量を調整することにより、従来の大腸菌群のみを指標とする殺菌作用ばかりでなく、大腸菌も指標とする殺菌作用が発揮されることを確認し、本発明を完成するに至った。 E. coli is Esherichia coli, and the group of coliforms includes, besides Esherichia coli, Citrobacter, Enterobacter, and Klebsiella. The coliform bacteria group is an index of fecal contamination, and is a test item for confirming the safety against intestinal pathogens (typhoid bacteria, Shigella etc.). The present inventors not only have a bactericidal action not only using conventional coliforms as an indicator, but also by adjusting the addition amount of each drug by combining two or more drugs that react to form hypobromite. It was confirmed that the bactericidal activity indicated by E. coli was also exhibited, and the present invention was completed.
本発明によれば下記実施態様のアンモニア性窒素含有排水中の大腸菌及び大腸菌群を殺菌処理するアンモニア性窒素含有排水の消毒方法及び消毒剤が提供される。
［１］アンモニア性窒素を含有する排水に、水中で次亜塩素酸イオン（ＯＣｌ−）を発生する薬剤（Ａ）と、水中で臭化物イオン（Ｂｒ−）を発生する薬剤（Ｂ）と、を添加して前記排水中の大腸菌及び大腸菌群を殺菌するアンモニア性窒素含有排水の消毒方法であって、前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比がＢｒ／Ｃｌ＜１．０となる量で前記薬剤（Ａ）及び前記薬剤（Ｂ）を前記排水に添加することを特徴とする方法。
［２］前記薬剤（Ａ）は、次亜塩素酸塩、ジクロロイソシアヌル酸またはその塩、トリクロロイソシアヌル酸またはその塩、及び次亜塩素酸カルシウム（さらし粉）から選択される１種以上を含み、前記薬剤（Ｂ）は、臭化ナトリウム、臭化カリウム、臭化アンモニウム、及び臭化カルシウムから選ばれる１種以上を含む、ことを特徴とする［１］に記載の方法。
［３］前記薬剤（Ａ）及び前記薬剤（Ｂ）は、前記排水に添加する前には反応させないことを特徴とする［１］又は［２］に記載の方法。
［４］前記薬剤（Ａ）及び前記薬剤（Ｂ）は、固体として前記排水に添加される、ことを特徴とする［１］〜［３］のいずれか１に記載の方法。
［５］前記薬剤（Ａ）及び前記薬剤（Ｂ）は、それぞれ別個の溶液として前記排水に添加される、ことを特徴とする［１］〜［３］のいずれか１に記載の方法。
［６］アンモニア性窒素を含有する排水中の大腸菌又は大腸菌群を殺菌するアンモニア性窒素含有排水用消毒剤であって、次亜塩素酸塩、ジクロロイソシアヌル酸またはその塩、トリクロロイソシアヌル酸またはその塩、及び次亜塩素酸カルシウム（さらし粉）から選択される１種以上の薬剤（Ａ）、及び臭化ナトリウム、臭化カリウム、臭化アンモニウム、及び臭化カルシウムから選ばれる１種以上の薬剤（Ｂ）を、前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比がＢｒ／Ｃｌ＜１．０となる量で組み合わせることを特徴とするアンモニア性窒素含有排水用消毒剤。
According to the present invention, there are provided a method and an agent for disinfecting ammonia nitrogen-containing wastewater which sterilizes E. coli and coliform bacteria in ammonia nitrogen-containing wastewater according to the following embodiment.
[1] in wastewater containing ammonia nitrogen, hypochlorite ions in water - an agent (A) for generating, bromide ion in water (OCl) (Br -) and drug (B) that generates a A method for disinfecting ammonia nitrogen-containing wastewater, which is added to sterilize E. coli and coliforms in the wastewater, wherein the molar ratio of Cl in the drug (A) to Br in the drug (B) is Br / Cl. Adding the drug (A) and the drug (B) to the waste water in an amount of <1.0.
[2] The agent (A) contains one or more selected from hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof, and calcium hypochlorite (exfoliated powder), The method according to [1], wherein the agent (B) contains one or more selected from sodium bromide, potassium bromide, ammonium bromide and calcium bromide.
[3] The method according to [1] or [2], wherein the drug (A) and the drug (B) are not reacted before being added to the waste water.
[4] The method according to any one of [1] to [3], wherein the drug (A) and the drug (B) are added to the waste water as a solid.
[5] The method according to any one of [1] to [3], wherein the drug (A) and the drug (B) are added to the waste water as separate solutions.
[6] An ammoniacal nitrogen-containing waste water disinfectant for sterilizing Escherichia coli or coliforms in waste water containing ammoniacal nitrogen, comprising hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof And one or more agents selected from calcium hypochlorite (exfoliated powder), and one or more agents selected from sodium bromide, potassium bromide, ammonium bromide, and calcium bromide (B And a disinfectant for ammoniacal nitrogen-containing waste water, wherein the molar ratio of Cl in the drug (A) to Br in the drug (B) is Br / Cl <1.0.
本発明によれば、従来提案されている次亜塩素酸塩に対して等モル以上の臭化物を添加して形成する消毒剤及び殺菌方法や、有機酸又はヒダントインなどの第３成分を添加する殺菌剤及び殺菌方法と比較して短時間でより優れた大腸菌群や大腸菌に対する殺菌効果を発揮することができ、かつ経済的である、アンモニア性窒素含有排水中の大腸菌及び大腸菌群を殺菌処理する消毒方法及び消毒剤が提供される。 According to the present invention, a disinfectant and sterilization method formed by adding an equimolar or more amount of bromide to hypochlorite which has been conventionally proposed and a sterilization method, and sterilization using a third component such as an organic acid or hydantoin And economical method for disinfecting E. coli and coliforms in ammonia nitrogen-containing waste water, which can exert superior bactericidal effect against coliforms and E. coli in a short time as compared with the use of the agent and the sterilization method, and is economical Methods and disinfectants are provided.
以下、添付図面を参照しながら本発明を詳細に説明する。
本発明は、アンモニア性窒素を含有する排水に、水中で次亜塩素酸イオン（ＯＣｌ−）を発生する薬剤（Ａ）と、水中で臭化物イオン（Ｂｒ−）を発生する薬剤（Ｂ）と、を添加してアンモニア性窒素含有排水中の大腸菌又は大腸菌群を殺菌処理する消毒方法及び消毒剤を提供する。
Hereinafter, the present invention will be described in detail with reference to the attached drawings.
The present invention relates to an agent (A) for generating hypochlorite ion (OCl − ) in water and an agent (B) for generating bromide ion (Br − ) in water, in waste water containing ammonia nitrogen. And a disinfecting method and disinfectant for disinfecting E. coli or coliforms in ammonia nitrogen-containing waste water.
従来の方法は、次亜塩素酸塩１モルに対して金属臭化塩１モル以上を混合して形成される次亜臭素酸塩溶液を排水に添加するが、本発明は、水中で次亜塩素酸イオン（ＯＣｌ−）を発生する薬剤（Ａ）中Ｃｌと、水中で臭化物イオン（Ｂｒ−）を発生する薬剤（Ｂ）中Ｂｒとのモル比がＢｒ／Ｃｌが１．０未満、好ましくは０．５以下、０．２以上となる量で前記薬剤（Ａ）及び前記薬剤（Ｂ）をアンモニア性窒素含有排水に添加することを特徴とする。Ｂｒ／Ｃｌが１．０以上の場合、大腸菌及び大腸菌群の殺菌効果の顕著な向上は認められず、高価な薬剤（Ｂ）の使用量が増大することになり、経済的ではない。 The conventional method adds a hypobromous acid solution formed by mixing one or more moles of metal bromide to one mole of hypochlorite to waste water, but the present invention chlorate ion (OCl -) and medium agent (a) Cl for generating, bromide ion in water (Br -) molar ratio of medium-Br agents (B) which generates the is Br / Cl less than 1.0, preferably Is characterized in that the drug (A) and the drug (B) are added to the ammonia nitrogen-containing wastewater in an amount of 0.5 or less and 0.2 or more. When Br / Cl is 1.0 or more, no remarkable improvement in the bactericidal effect of E. coli and coliform bacteria is observed, and the amount of expensive drug (B) used is increased, which is not economical.
前記薬剤（Ａ）は、次亜塩素酸塩、ジクロロイソシアヌル酸またはその塩、トリクロロイソシアヌル酸またはその塩、及び次亜塩素酸カルシウム（さらし粉）から選択される１種以上を含み、前記薬剤（Ｂ）は、臭化ナトリウム、臭化カリウム、臭化アンモニウム、及び臭化カルシウムから選ばれる１種以上を含むことが好ましく、任意の薬剤（Ａ）と薬剤（Ｂ）の組合せを用いることができる。薬剤（Ａ）の塩としては、次亜塩素酸ナトリウム、次亜塩素酸カリウム、ジクロロイソシアヌル酸ナトリウム、ジクロロイソシアヌル酸カリウム、トリクロロイソシアヌル酸ナトリウム、トリクロロイソシアヌル酸カリウムなどを好適に用いることができる。薬剤（Ａ）と薬剤（Ｂ）との組合せは、次亜塩素酸ナトリウムと臭化ナトリウム、次亜塩素酸カルシウム（さらし粉）と臭化ナトリウム、ジクロロイソシアヌル酸ナトリウムと臭化ナトリウム、ジクロロイソシアヌル酸ナトリウムと臭化カリウム、ジクロロイソシアヌル酸ナトリウムと臭化カルシウムなどを好適に用いることができる。 The agent (A) includes one or more selected from hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof, and calcium hypochlorite (exfoliated powder), and the agent (B) Preferably,) includes one or more selected from sodium bromide, potassium bromide, ammonium bromide and calcium bromide, and a combination of any drug (A) and drug (B) can be used. As a salt of the drug (A), sodium hypochlorite, potassium hypochlorite, sodium dichloroisocyanurate, potassium dichloroisocyanurate, sodium trichloroisocyanurate, potassium trichloroisocyanurate and the like can be suitably used. Combinations of drug (A) and drug (B) are sodium hypochlorite and sodium bromide, calcium hypochlorite (exfoliated powder) and sodium bromide, sodium dichloroisocyanurate and sodium bromide, sodium dichloroisocyanurate And potassium bromide, sodium dichloroisocyanurate, calcium bromide and the like can be suitably used.
従来の次亜臭素酸塩溶液を排水に添加する態様とは異なり、前記薬剤（Ａ）及び前記薬剤（Ｂ）は、前記排水に添加された後に反応するように、薬剤（Ａ）及び（Ｂ）それぞれ別個の溶液又は固体として、あるいは薬剤（Ａ）及び（Ｂ）の固体混合物として、前記排水に添加することが好ましい。薬剤（Ａ）及び薬剤（Ｂ）を別個に、特に固体のまま、排水に添加することにより、排水の水質に応じたＢｒ／Ｃｌモル比の制御が容易である。このため、それほど大量ではない降雨が長期間にわたり続き、雨水量が多くなり下水が希釈された場合や、降雨量が少なくなり下水の滞留時間が長くなる場合など、経時的に変化する状況であっても、薬剤（Ａ）及び薬剤（Ｂ）の添加量を個別に制御し、好適なモル比で供給することができる。一方、排水に添加する前に薬剤（Ａ）及び薬剤（Ｂ）が反応すると、特に液体の場合、次亜臭素酸塩及び次亜塩素酸塩などが形成され、排水に添加する前に形成された次亜臭素酸塩及び次亜塩素酸塩が分解し殺菌効果が低下するおそれがある。固体では前記のような反応や分解は起こり難いという利点があるが、特に高湿度条件では固体薬剤の凝固や分解などの反応が進行し、殺菌効果や粉体流動性が低下する場合があり、薬剤（Ａ）及び薬剤（Ｂ）を所定比率で供給することができなくなるおそれがある。しかし、固体は液体の場合より、薬剤（Ａ）及び薬剤（Ｂ）を所定比率で供給することができなくなるリスクが低い。 Unlike the conventional hypobromous acid salt solution is added to the waste water, the drug (A) and the drug (B) react in such a way that they are added to the waste water and then react with the drugs (A) and (B). 2.) It is preferred to add to the drainage as separate solutions or solids or as a solid mixture of medicaments (A) and (B). By adding the drug (A) and the drug (B) separately, particularly as solids, to the waste water, it is easy to control the Br / Cl molar ratio according to the water quality of the waste water. For this reason, it is a situation that changes with time, such as when the rainfall which is not so large continues for a long time and the amount of rainwater increases and the sewage is diluted or when the amount of rainfall decreases and the residence time of the sewage becomes long. However, the addition amounts of the drug (A) and the drug (B) can be separately controlled and supplied in a suitable molar ratio. On the other hand, when the drug (A) and the drug (B) react before being added to the waste water, particularly in the case of a liquid, hypobromite and hypochlorite etc. are formed and formed before being added to the waste water There is a possibility that the hypobromite and hypochlorite may be decomposed to reduce the bactericidal effect. In the case of solid, there is an advantage that the above reaction and decomposition do not occur easily, but especially under high humidity conditions, reactions such as solidification and decomposition of solid drug may progress, and the bactericidal effect and powder flowability may decrease. There is a possibility that the drug (A) and the drug (B) can not be supplied at a predetermined ratio. However, the solid has a lower risk of being unable to supply the drug (A) and the drug (B) at a predetermined ratio than in the case of liquid.
前記薬剤（Ａ）及び前記薬剤（Ｂ）は固体として前記排水に添加されることが好ましい。先行技術文献に開示されているような２種類の薬剤をあらかじめ混合して調製した溶液を排水に添加する場合には、溶解装置、溶液貯留槽、溶液注入装置など付属装置が多くなるため設備全体が大型化し、装置構成が複雑になり、輸送及び管理コストが増大するが、薬剤（Ａ）及び薬剤（Ｂ）を固体のまま直接排水に添加することにより、溶液を添加する場合に必要となる設備やコストが不要となる。 Preferably, the drug (A) and the drug (B) are added to the waste water as a solid. When adding a solution prepared by mixing two types of drugs in advance as disclosed in the prior art to the drainage, there are many accessories such as a dissolving device, a solution reservoir, a solution injection device, etc. Increases the size of the equipment, complicates the equipment configuration, and increases transportation and management costs, but it is necessary when adding the solution by adding the drug (A) and the drug (B) directly to the waste water as a solid There is no need for equipment and cost.
図１に、本発明の消毒方法を下水処理場に適用する場合の処理フローを示す。図中「○」はバルブを示す。通常の下水処理場では、排水は第一沈殿池、曝気槽、第二沈殿池により処理された後、河川に放流される。大量の雨水が流入する場合には、曝気槽及び第二沈殿池における処理能力を超えるため、第一沈殿池における処理の後、雨天時簡易放流水として河川に放流される。本発明の消毒方法は、この雨天時簡易放流水に、薬剤（Ａ）及び薬剤（Ｂ）を好ましくは固体のまま、個別に添加する。薬剤（Ａ）と薬剤（Ｂ）の添加量は、薬剤（Ａ）中Ｃｌと薬剤（Ｂ）中Ｂｒのモル比：Ｂｒ／Ｃｌが１．０未満、好ましくはＢｒ／Ｃｌが０．５以下、０．２以上とする。河川への放流の前に、雨天時簡易放流水の残留ハロゲン濃度を測定し、残留ハロゲン濃度が高い場合には薬剤（Ａ）及び（Ｂ）の全注入量を減らすことが好ましい。 The process flow in the case of applying the disinfection method of this invention to a sewage treatment plant in FIG. 1 is shown. "(Circle)" shows a valve in the figure. In a normal sewage treatment plant, wastewater is treated by the first settling tank, aeration tank, and the second settling tank, and then discharged to the river. When a large amount of rainwater flows in, it exceeds the treatment capacity of the aeration tank and the second sedimentation tank, and therefore, after being treated in the first sedimentation tank, it is released to the river as a simple discharge during rainy weather. In the disinfection method of the present invention, the drug (A) and the drug (B) are added separately, preferably as a solid, to the simple discharge water in rainy weather. The molar ratio of Cl in drug (A) to Br in drug (B): Br / Cl is less than 1.0, preferably Br / Cl is 0.5 or less. , 0.2 or more. Before release to rivers, it is preferable to measure the residual halogen concentration of the simple release water during rainy weather, and to reduce the total injection amount of drugs (A) and (B) when the residual halogen concentration is high.
図２に、本発明の消毒方法を雨水ポンプ所に適用する場合の処理フローを示す。図中「○」はバルブを示す。通常の雨水ポンプ所では、雨水は、沈砂池及びポンプ井にて処理された後、河川に放流される。本発明の消毒方法は、沈砂池に、薬剤（Ａ）及び薬剤（Ｂ）を好ましくは固体のまま、個別に添加する。薬剤（Ａ）と薬剤（Ｂ）の添加量は、薬剤（Ａ）中Ｃｌと薬剤（Ｂ）中Ｂｒのモル比：Ｂｒ／Ｃｌが１．０未満、好ましくはＢｒ／Ｃｌが０．５以下、０．２以上とする。河川への放流の前に、雨水処理放流水の残留ハロゲン濃度を測定し、残留ハロゲン濃度が高い場合には薬剤（Ａ）及び（Ｂ）の全注入量を減らすことが好ましい。 The process flow in the case of applying the disinfection method of this invention to FIG. 2 to a rainwater pump station is shown. "(Circle)" shows a valve in the figure. In normal rainwater pumping stations, rainwater is treated by settling basins and pump wells and then released to the river. In the disinfecting method of the present invention, the drug (A) and the drug (B) are added separately, preferably in solid form, to the sedimentation basin. The molar ratio of Cl in drug (A) to Br in drug (B): Br / Cl is less than 1.0, preferably Br / Cl is 0.5 or less. , 0.2 or more. It is preferable to measure the residual halogen concentration of the storm water treatment effluent before discharging to the river, and reduce the total injection amount of the drugs (A) and (B) if the residual halogen concentration is high.
図１及び２において、Ｃｌ供給機からの薬剤（Ａ）及びＢｒ供給機からの（Ｂ）の注入量は、演算子によって制御する。演算子は、降雨量、降雨時間、雨天時簡易放流開始時間又は雨水ポンプ運転開始時間などの外部因子からの信号を受けて、薬剤（Ａ）及び（Ｂ）の注入量を所定比率となるように制御することが好ましい。薬剤（Ａ）及び（Ｂ）は固体のまま投入されることが好ましく、例えば特開２００４−１８０１３号公報に開示されている粉体供給設備などを用いて投入することができる。 In Figures 1 and 2, the dose of drug (A) from the Cl dispenser and (B) from the Br dispenser is controlled by the operator. The operator receives a signal from an external factor such as rainfall, rainfall time, rainy season simple discharge start time or rain water pump operation start time, and makes the injection amount of drugs (A) and (B) to a predetermined ratio It is preferable to control the The agents (A) and (B) are preferably introduced in solid form, and can be introduced, for example, using a powder supply facility disclosed in JP-A-2004-18013.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。
表１に示すアンモニア性窒素を含む試験水Ａ〜Ｅ各１Ｌをそれぞれビーカーに採取し、ジャーテスターにセットして１２０ｒｐｍで撹拌しながら、表２に示す種類及び比率で薬剤（Ａ）及び（Ｂ）を添加し、３分後に撹拌を停止して試験水を１００ｍｌ採取した。採取後速やかに、試験水の一部を遊離残留塩素濃度及び全残留塩素濃度の分析に供し、試験水の一部をチオ硫酸ナトリウム入り滅菌瓶に採取した。滅菌瓶に採取した試験水を用いて大腸菌数（クロモアガーＥＣＣ培地、平板培養法）及び大腸菌群数（デソキシコール酸塩培地、平板培養法）の測定を行った。結果を表２に示す。
Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited thereto.
1 L of each of test waters A to E containing ammoniacal nitrogen shown in Table 1 is collected in a beaker, set in a jar tester and stirred at 120 rpm, and drugs (A) and (B) in the types and ratios shown in Table 2 ) Was added, and after 3 minutes, the stirring was stopped and 100 ml of test water was collected. Immediately after collection, part of the test water was subjected to analysis of free residual chlorine concentration and total residual chlorine concentration, and part of the test water was collected in a sodium thiosulfate-containing sterile bottle. Using the test water collected in a sterile bottle, the number of E. coli (chromager ECC medium, plate culture method) and the number of E. coli group (desoxycholate medium, plate culture method) were measured. The results are shown in Table 2.
用いた薬剤は以下のとおりである。
薬剤（Ａ）
・ジクロロイソシアヌル酸ナトリウム
ネオクロール・60（四国化成製、有効塩素含有量64.48%、白色結晶性固体）
・さらし粉
高度さらし粉（日本ソーダ工業会規格JSIA07-1-1998 I種、有効塩素70%以上）
・次亜塩素酸ナトリウム
次亜塩素酸ソーダ試薬（和光純薬工業 試薬特級 有効塩素12%）
・トリクロロイソシアヌル酸
ネオクロール・90（四国化成製、有効塩素含有量90%、白色結晶性固体）
薬剤（Ｂ）
・臭化ナトリウム（和光純薬工業 試薬特級）
・臭化アンモニウム（和光純薬工業 試薬特級）
・臭化カルシウム（和光純薬工業 試薬特級）
・臭化カリウム（和光純薬工業 試薬特級）
The drugs used are as follows.
Drug (A)
-Sodium dichloroisocyanurate neochlor-60 (manufactured by Shikoku Kasei Co., effective chlorine content 64.48%, white crystalline solid)
Exfoliated powder Highly exfoliated powder (Japan Soda Industry Association Standard JSIA 07-1-1998 Class I, available chlorine 70% or more)
・ Hypochlorous acid sodium hypochlorite sodium reagent (Wako Pure Chemical Industries reagent special grade 12% effective chlorine)
Trichloroisocyanuric acid Neochlor 90 (manufactured by Shikoku Kasei Co., effective chlorine content 90%, white crystalline solid)
Drug (B)
・ Sodium bromide (Wako Pure Chemical Industries, reagent grade special grade)
-Ammonium bromide (Wako Pure Chemical Industries, reagent grade special grade)
· Calcium Bromide (Wako Pure Chemical Industries, Reagent grade)
-Potassium bromide (Wako Pure Chemical Industries, reagent grade special grade)
排水に対して、薬剤（Ａ）を３ｍｇ／Ｌ（as Cl2）又は４ｍｇ／Ｌ（as Cl2）、薬剤（Ｂ）中のＢｒが薬剤（Ａ）中のＣｌに対して０．２〜２倍（モル比）となるように、薬剤（Ａ）及び薬剤（Ｂ）をそれぞれ固体のまま別個に添加した。薬剤（Ａ）のみを用いる比較例１、３、７、８、１０、１１は、大腸菌群数が４，３００ＣＦＵ／ｍＬ以上と放流基準値（３，０００ＣＦＵ／ｍＬ以下）を大幅に超えている。薬剤（Ｂ）中のＢｒが薬剤（Ａ）中のＣｌに対して１倍（モル比）以上の比較例２、４、５、６、９は大腸菌群数が低下するものの、やはり放流基準値（３，０００ＣＦＵ／ｍＬ以下）を満たさなかった。また、薬剤（Ａ）及び（Ｂ）にさらに５，５−ジメチルヒダントインを添加した比較例１２は、大腸菌数は減少したものの、大腸菌群数は１０，２００ＣＦＵ／ｍＬと非常に高く、放流基準値（３，０００ＣＦＵ／ｍＬ以下）を満たさなかった。薬剤（Ａ）及び薬剤（Ｂ）から生成される次亜臭素酸塩及び次亜塩素酸塩が５，５−ジメチルヒダントインと反応し、５，５−ジメチルヒダントインの塩素化物及び臭素化物が生成され、酸化活性が弱まることに起因すると推察される。一方、薬剤（Ａ）を４ｍｇ／Ｌ（as Cl2）、薬剤（Ｂ）中のＢｒが薬剤（Ａ）中のＣｌに対して１倍（モル比）未満である実施例１〜８、及び薬剤（Ａ）を３ｍｇ／Ｌ（as Cl2）、薬剤（Ｂ）中のＢｒが薬剤（Ａ）中のＣｌに対して１倍（モル比）未満である実施例９〜１０は、大腸菌及び大腸菌群に対する殺菌効果が高く、放流基準値（３，０００ＣＦＵ／ｍＬ以下）を満たすことが確認できた。 For drainage, 3 mg / L (as Cl 2 ) or 4 mg / L (as Cl 2 ) of drug (A), Br in drug (B) is 0.2 to Cl in drug (A) The drug (A) and the drug (B) were separately added in solid form so as to be 2 times (molar ratio). In Comparative Examples 1, 3, 7, 8, 10, 11 using only the drug (A), the number of coliforms is 4,300 CFU / mL or more and significantly exceeds the discharge standard value (3,000 CFU / mL or less) . Comparative Examples 2, 4, 5, 6 and 9 in which Br in the drug (B) is 1-fold (molar ratio) or more relative to Cl in the drug (A), although the number of coliforms is reduced, the release standard value also (Less than 3,000 CFU / mL) was not satisfied. In addition, in Comparative Example 12 in which 5,5-dimethylhydantoin was further added to the drugs (A) and (B), although the number of E. coli decreased, the number of E. coli groups was very high at 10,200 CFU / mL, and the discharge standard value (Less than 3,000 CFU / mL) was not satisfied. Hypobromite and hypochlorite produced from the drug (A) and the drug (B) react with 5,5-dimethylhydantoin to form 5,5-dimethylhydantoin chloride and bromide. It is presumed that this is due to the weakening of the oxidation activity. On the other hand, Drug (A) is 4 mg / L (as Cl 2 ), Examples 1 to 8 in which Br in Drug (B) is less than 1 time (molar ratio) to Cl in Drug (A), and Drug (A) is 3 mg / L (as Cl 2 ), Br in drug (B) is less than 1-fold (molar ratio) to Cl in drug (A). It was confirmed that the bactericidal effect against coliform bacteria is high, and the discharge standard value (3,000 CFU / mL or less) is satisfied.
次に、表１に示す５種類の試験水に対して、ジクロロイソシアヌル酸ナトリウム及び臭化ナトリウムのモル比を表３に示すように変えてそれぞれ固体のまま別個に添加し、消毒効果を比較した。結果を表３及び図３〜１２に示す。図３〜１２から明らかなように、薬剤（Ｂ）中のＢｒが薬剤（Ａ）中のＣｌに対して１．０倍（モル比）以上では大腸菌数及び大腸菌群数ともに増加する傾向が見られ、大腸菌及び大腸菌群の殺菌率が低下する傾向が見られる。 Next, the molar ratio of sodium dichloroisocyanurate and sodium bromide was changed as shown in Table 3 with respect to the five types of test water shown in Table 1, and they were separately added as solids, respectively, and their disinfecting effects were compared . The results are shown in Table 3 and FIGS. As is apparent from FIGS. 3 to 12, it can be seen that when Br in the drug (B) is 1.0 or more (molar ratio) relative to Cl in the drug (A), the number of E. coli and the number of E. coli groups tend to increase. There is a tendency to reduce the killing rate of E. coli and coliform bacteria.
Claims (4)
前記薬剤（Ａ）は、次亜塩素酸塩、ジクロロイソシアヌル酸またはその塩、トリクロロイソシアヌル酸またはその塩、及び次亜塩素酸カルシウム（さらし粉）から選択される１種以上を含み、固体として前記排水に添加され、
前記薬剤（Ｂ）は、臭化ナトリウム、臭化カリウム、臭化アンモニウム、及び臭化カルシウムから選ばれる１種以上を含み、
前記薬剤（Ａ）及び前記薬剤（Ｂ）は、前記排水に添加する前には反応させず、
前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比がＢｒ／Ｃｌ＜１．０となる量で前記薬剤（Ａ）及び前記薬剤（Ｂ）を前記排水に添加することを特徴とする方法。 The wastewater containing ammonia nitrogen, hypochlorite ions in water - an agent (A) for generating, bromide ion in water (OCl) (Br -) and drug (B) that generates, with the addition of A method for disinfecting ammonia nitrogen-containing wastewater, comprising the steps of: disinfecting E. coli and coliforms in the wastewater;
The agent (A) contains at least one selected from hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof, and calcium hypochlorite (exfoliated powder), and the waste water as a solid Added to
The agent (B) contains one or more selected from sodium bromide, potassium bromide, ammonium bromide and calcium bromide,
The drug (A) and the drug (B) are not reacted before being added to the waste water,
Adding the drug (A) and the drug (B) to the waste water in an amount such that the molar ratio of Cl in the drug (A) to Br in the drug (B) is Br / Cl <1.0 How to feature
次亜塩素酸塩、ジクロロイソシアヌル酸またはその塩、トリクロロイソシアヌル酸またはその塩、及び次亜塩素酸カルシウム（さらし粉）から選択される１種以上の薬剤（Ａ）、及び臭化ナトリウム、臭化カリウム、臭化アンモニウム、及び臭化カルシウムから選ばれる１種以上の薬剤（Ｂ）を、前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比がＢｒ／Ｃｌ＜１．０となる量で組み合わせること、
前記薬剤（Ａ）は固体として前記排水に添加され、前記薬剤（Ａ）と前記薬剤（Ｂ）は前記排水に添加する前には反応させないこと
を特徴とするアンモニア性窒素含有排水用消毒剤。 It is a disinfectant for ammonia nitrogen containing drainage which disinfects E. coli or coliforms in waste water containing ammonia nitrogen,
Hypochlorite, dichloroisocyanuric acid or its salt, trichloroisocyanuric acid or its salt, and one or more agents (A) selected from calcium hypochlorite (exfoliated powder), and sodium bromide, potassium bromide And the molar ratio of Cl in the agent (A) to Br in the agent (B) is at least one of an agent (B) selected from Combining in quantities that
The ammoniacal nitrogen-containing wastewater, wherein the drug (A) is added as a solid to the waste water, and the drug (A) and the drug (B) are not reacted before being added to the waste water. Disinfectant.
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