JP6490761B2 - Disinfection method of wastewater containing ammonia nitrogen - Google Patents
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- 239000002351 wastewater Substances 0.000 title claims description 60
- 238000000034 method Methods 0.000 title claims description 34
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims description 24
- 238000004659 sterilization and disinfection Methods 0.000 title description 15
- 239000003814 drug Substances 0.000 claims description 116
- 229940079593 drug Drugs 0.000 claims description 114
- 239000000460 chlorine Substances 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 18
- 241000588724 Escherichia coli Species 0.000 claims description 17
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 241000894006 Bacteria Species 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 10
- 230000000249 desinfective effect Effects 0.000 claims description 10
- 230000001954 sterilising effect Effects 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 8
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 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 6
- 239000007844 bleaching agent Substances 0.000 claims description 5
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 5
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 5
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 4
- -1 hypochlorite ions Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229950009390 symclosene Drugs 0.000 claims description 4
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 18
- 239000010865 sewage Substances 0.000 description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection 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
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000013043 chemical agent Substances 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000012136 culture method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 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 1
- 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
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 241000588923 Citrobacter Species 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
- 241000293871 Salmonella enterica subsp. enterica serovar Typhi Species 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
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- YTZIISLVLINEJT-UHFFFAOYSA-N disodium dihypochlorite Chemical compound [Na+].[Na+].[O-]Cl.[O-]Cl YTZIISLVLINEJT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 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
- 238000007689 inspection Methods 0.000 description 1
- 244000000074 intestinal pathogen Species 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000005259 measurement 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
- 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
- 239000002689 soil Substances 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に関する。 The present invention relates to a method for disinfecting wastewater containing ammonia nitrogen, and in particular, sterilizing Escherichia coli or coliform bacteria in wastewater containing ammonia nitrogen discharged from a sewage treatment plant, a pump station, and a rainwater outlet to public water bodies. It relates to disinfection methods.
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 for detoxifying sewage discharged from homes and factories and releasing it into public water areas. From rainwater outlets, sewage mixed with rainwater (hereinafter referred to as sewage in rainy weather) is discharged into public water areas in a few tens of seconds to several minutes without being sufficiently treated. In this case, coarse suspended matters and SS (suspended substance) are released into public water areas, which may cause aesthetic problems, as well as the discharge standard value (3000 CFU / mL) stipulated in the Water Pollution Control Law. In some cases, coliforms or E. coli significantly exceeding the following are 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。 Even in the sewage treatment plant, if the inflow sewage greatly exceeds the treatment capacity, some sewage during rainy weather may be treated and released. In this case, since bacteria are not sufficiently sterilized, coliform bacteria and E. coli that greatly exceed the discharge standard value (3000 CFU / mL or less) defined in the Water Pollution Control Law may be detected. These are phenomena that are especially seen in combined sewers. However, in shunted sewers, soil coliforms and coarse suspended solids flow in, so if they overflow and are discharged into public waters, they join together. A problem similar to the sewerage system was occurring.
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。 Disinfection at the sewage treatment plant, according to "Sewage Facility Planning and Design Guidelines and Explanation" (issued by Japan Sewerage Association, 2009 edition), sodium hypochlorite, liquefied chlorine, chlorinated isocyanuric acid, calcium hypochlorite A method of disinfecting coliform bacteria by contacting them with sewage in a mixing pond for 15 minutes or longer is shown. In addition, “Sewerage facility planning / design guidelines and explanation” also describes disinfection with ozone and ultraviolet rays. Furthermore, by storing temporarily wet-weather sewage is provided a pond tens of thousands m 3, if the overflow has occurred by rainfall or more storage amount is a method of disinfection with chlorine disinfectant of the 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, chlorinated disinfectants have a high rainfall intensity, such as sewage in rainy weather, and when they are released into public water areas in a short time, the contact time with the wastewater is short, so that the sterilizing effect is not sufficiently exhibited, and ammonia In wastewater with a high nitrogen content, chlorine and ammonia nitrogen react with each other to form chloramine and reduce bactericidal action, reducing the number of coliforms below the standard value set by the Water Pollution Control Law. And the problem that chloramine remains in the public waters as bound chlorine for a long time, adversely affecting the environment. Therefore, for example, a disinfecting method of adding a solution of hypobromite or hypobromite formed by adding equimolar or more of sodium bromide to sodium hypochlorite (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) Disinfecting method (Patent Document 2) in which disinfecting water containing a certain amount is added to waste water, hypochlorous acid, bromide and 5,5-dimethylhydantoin 1: (0.2-3): (0.2-0. 9) (Molar ratio) used for hypochlorous acid and 5,5-dimethyl A microbicide which is an aqueous solution containing hypobromite and N-monochloro-5,5-dimethylhydantoin formed by mixing bromide corresponding to hypochlorous acid remaining by the reaction with danthoin (Patent Document 3) A method using hypobromite has been 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 conventionally proposed method using hypobromite, the sterilization effect of the wastewater containing ammonia nitrogen is insufficient, and it cannot be treated to a discharge standard value of 3000 CFU / mL or less for coliforms, 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 sterilizing E. coli and coliform bacteria in wastewater 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排水中のアンモニア性窒素濃度に応じて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。 Escherichia coli is Esherichia coli, and Escherichia coli group includes the genus Citrobacter, Enterobacter, Klebsiella, etc. in addition to Esherichia coli. The coliform group is an index of fecal contamination, and is an inspection item for confirming safety against intestinal pathogens (such as Salmonella typhi and Shigella). The present inventors combine two or more kinds of drugs that react to produce hypobromite and adjust the amount of each drug added according to the concentration of ammoniacal nitrogen in the wastewater, thereby allowing the conventional coliforms It was confirmed that not only the bactericidal action using only Escherichia coli as an index but also the bactericidal action using Escherichia coli as an index was 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が提供される。具体的態様は以下のとおりである。
［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、前記排水中のアンモニア性窒素濃度に応じて、前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比を調節して、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］前記排水中のアンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、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）を前記排水に添加し、前記排水中のアンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、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［１］に記載の方法。
［３］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］又は［２］に記載の方法。
［４］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］〜［３］のいずれかに記載の方法。
［５］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］〜［４］のいずれかに記載の方法。
［６］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］〜［４］のいずれかに記載の方法。
［７］前記薬剤（Ａ）及び前記薬剤（Ｂ）を含む混合溶液として前記排水に添加する、ことを特徴とする［１］〜［３］のいずれかに記載の方法。
According to the present invention, there is provided a method of disinfecting ammonia nitrogen-containing wastewater for sterilizing Escherichia coli and coliform bacteria in ammonia nitrogen-containing waste water according to the following embodiment. Specific embodiments are as follows.
[1] A chemical agent (A) that generates hypochlorite ions (OCl − ) in water and a chemical agent (B) that generates bromide ions (Br − ) in water in wastewater containing ammoniacal nitrogen. A method for disinfecting ammonia nitrogen-containing wastewater that is added to sterilize Escherichia coli and coliform bacteria in the wastewater, wherein Cl in the medicine (A) and the medicine ( B) Adjusting the molar ratio with Br in the medium, and adding the drug (A) and the drug (B) to the waste water.
[2] When the ammoniacal nitrogen concentration in the waste water is 30 mg / L or less, the molar ratio of Cl in the drug (A) and Br in the drug (B) is Br / Cl <1.0. When the chemical (A) and the chemical (B) are added to the waste water in an amount such that the ammoniacal nitrogen concentration in the waste water exceeds 30 mg / L, Cl in the chemical (A) and the chemical (B) The method according to [1], wherein the drug (A) and the drug (B) are added to the waste water in such an amount that a molar ratio with Br in the formula is Br / Cl ≧ 1.0. .
[3] The drug (A) includes one or more selected from hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof, and calcium hypochlorite (bleaching powder), The method according to [1] or [2], wherein the drug (B) contains one or more selected from sodium bromide, potassium bromide, ammonium bromide, and calcium bromide.
[4] The method according to any one of [1] to [3], wherein the drug (A) and the drug (B) are not reacted before being added to the waste water.
[5] The method according to any one of [1] to [4], wherein the drug (A) and the drug (B) are added to the waste water as solids.
[6] The method according to any one of [1] to [4], wherein the drug (A) and the drug (B) are added to the waste water as separate solutions.
[7] The method according to any one of [1] to [3], wherein a mixed solution containing the drug (A) and the drug (B) is added to the waste water.
本発明によれば、排水中のアンモニア性窒素濃度に応じて最適な次亜臭素酸塩による大腸菌及び大腸菌群の殺菌作用を利用することにより、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が提供される。 According to the present invention, by utilizing the optimal bactericidal action of Escherichia coli and coliforms by hypobromite according to the ammoniacal nitrogen concentration in the wastewater, Disinfectant and sterilization method formed by adding equimolar or more bromide, and more excellent for coliforms and coliforms in a short time compared to disinfectant and sterilization method adding third component such as organic acid or hydantoin A disinfecting method for disinfecting Escherichia coli and coliform bacteria in ammoniacal nitrogen-containing wastewater, which can exert a bactericidal effect and is economical, is 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を提供する。
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
The present invention relates to a chemical agent (A) that generates hypochlorite ions (OCl − ) in water and a chemical agent (B) that generates bromide ions (Br − ) in water to wastewater containing ammoniacal nitrogen. To disinfect the Escherichia coli or coliform bacteria in the ammoniacal nitrogen-containing wastewater.
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、排水中のアンモニア性窒素濃度に応じて、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とのモル比を調製することを特徴とする。具体的には、排水中アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、薬剤（Ａ）中のＣｌに対して薬剤（Ｂ）中のＢｒのモル比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し、排水中アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、薬剤（Ａ）中のＣｌに対して薬剤（Ｂ）中のＢｒのモル比Ｂｒ／Ｃｌが１．０以上、好ましくは１．５以上、２．０以下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。排水中のアンモニア性窒素濃度に応じて、薬剤（Ａ）及び薬剤（Ｂ）の添加比率を調整することにより、最適な殺菌作用を経済的に達成し得る。 In the conventional method, a hypobromite solution formed by mixing 1 mol or more of metal bromide with 1 mol of hypochlorite is added to wastewater. The molar ratio of Cl in the drug (A) that generates hypochlorite ions (OCl − ) in water and Br in the drug (B) that generates bromide ions (Br − ) in water according to the concentration of reactive nitrogen It is characterized by preparing. Specifically, when the ammoniacal nitrogen concentration in the wastewater is 30 mg / L or less, the molar ratio Br / Cl of Br in the drug (B) to Cl in the drug (A) is less than 1.0, Preferably, 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, and the ammonia nitrogen concentration in the waste water exceeds 30 mg / L. Is a molar ratio Br / Cl of Br in the drug (B) to Cl in the drug (A) is 1.0 or more, preferably 1.5 or more and 2.0 or less. ) And the chemical (B) are added to ammoniacal nitrogen-containing wastewater. By adjusting the addition ratio of the drug (A) and the drug (B) according to the ammoniacal nitrogen concentration in the waste water, the optimum bactericidal action can be achieved economically.
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 drug (A) includes one or more selected from hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof, and calcium hypochlorite (bleaching powder), and the drug (B ) Preferably contains one or more selected from sodium bromide, potassium bromide, ammonium bromide, and calcium bromide, and any combination of drug (A) and drug (B) can be used. As the salt of the drug (A), sodium hypochlorite, potassium hypochlorite, sodium dichloroisocyanurate, potassium dichloroisocyanurate, sodium trichloroisocyanurate, potassium trichloroisocyanurate and the like can be suitably used. The combination of drug (A) and drug (B) is sodium hypochlorite and sodium bromide, calcium hypochlorite (bleaching powder) and sodium bromide, sodium dichloroisocyanurate and sodium bromide, sodium dichloroisocyanurate And potassium bromide, sodium dichloroisocyanurate and calcium bromide can be preferably used.
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が好ましい。薬剤（Ａ）及び薬剤（Ｂ）を個別に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。 The drug (A) and the drug (B) are preferably not reacted before being added to the waste water. By individually adding the chemical (A) and the chemical (B) to the wastewater, it is easy to control the Br / Cl molar ratio according to the quality of the wastewater. For this reason, it is a situation that changes over time, such as when rainfall that is not so large continues for a long period of time, when the amount of rainwater increases and sewage is diluted, or when the amount of rainfall decreases and the residence time of sewage increases. However, the addition amounts of the drug (A) and the drug (B) can be individually controlled and supplied at a suitable molar ratio.
一方、被処理水の水質変動が小さく、アンモニア性窒素濃度が安定している場合、薬剤（Ａ）と薬剤（Ｂ）の混合比率を変化させる必要はなく、一定比率における運転制御が可能となる。この場合、薬剤（Ａ）と薬剤（Ｂ）の添加量を別個に制御する必要がないので混合してから添加することができる。薬剤（Ａ）と薬剤（Ｂ）を混合してから添加することにより、被処理水への添加ラインを1系統とすることができ、運転管理や注入量を制御し易くなる。 On the other hand, when the water quality fluctuation of the treated water is small and the ammoniacal nitrogen concentration is stable, it is not necessary to change the mixing ratio of the drug (A) and the drug (B), and operation control at a constant ratio becomes possible. . In this case, since it is not necessary to control separately the addition amount of a chemical | medical agent (A) and a chemical | medical agent (B), it can add after mixing. By adding the drug (A) and the drug (B) after mixing, the addition line to the water to be treated can be made one system, and the operation management and the injection amount can be easily controlled.
前記薬剤（Ａ）及び前記薬剤（Ｂ）は別個の固体として、あるいは混合された固体として、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、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。 The drug (A) and the drug (B) are preferably added to the waste water as separate solids or as mixed solids. When adding a solution prepared by mixing two kinds of medicines as disclosed in the prior art documents to the wastewater, the number of accessory devices such as a dissolution device, a solution storage tank, and a solution injection device increases. However, the equipment required for adding the solution by adding the drug (A) and the drug (B) directly to the waste water as solids is increased. Cost is not required.
あるいは、前記薬剤（Ａ）及び前記薬剤（Ｂ）はそれぞれ別個に調製された溶液として排水に添加してもよい。この場合、薬剤（Ａ）及び薬剤（Ｂ）の別個の溶液として容易に定量供給することができる。 Alternatively, the drug (A) and the drug (B) may be added to the waste water as separately prepared solutions. In this case, it is possible to easily quantitatively supply the drug (A) and the drug (B) as separate solutions.
あるいは、薬剤（Ａ）及び薬剤（Ｂ）をあらかじめ混合して調製した混合溶液として添加してもよい。被処理水の流動性が著しく低く、薬剤添加位置における薬剤（Ａ）と薬剤（Ｂ）の接触効率が低い場合、または、薬剤（Ａ）と薬剤（Ｂ）の溶解性が低い場合には、あらかじめ混合して調整した混合液として添加することにより殺菌効果を高めることができる。 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、雨天時簡易放流水の放流ラインに設けられたアンモニア性窒素検出器（ＮＨ４−Ｎセンサー）により検出されるアンモニア性窒素濃度に応じて、演算子により決定される。具体的には、アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、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以上とし、アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、薬剤（Ａ）中Ｃｌと薬剤（Ｂ）中Ｂｒのモル比：Ｂｒ／Ｃｌが１．０以上、好ましくは２．０以下とする。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。 Alternatively, the drug (A) and the drug (B) may be added as a mixed solution prepared in advance. When the fluidity of the water to be treated is extremely low and the contact efficiency between the drug (A) and the drug (B) at the drug addition position is low or the solubility of the drug (A) and the drug (B) is low, The sterilizing effect can be enhanced by adding as a mixed solution prepared by mixing in advance. FIG. 1 shows a processing flow when the disinfection method of the present invention is applied to a sewage treatment plant. In the figure, “◯” indicates a valve. In ordinary sewage treatment plants, wastewater is treated by the first sedimentation tank, aeration tank, and second sedimentation tank, and then discharged into the river. When a large amount of rainwater flows in, it exceeds the treatment capacity of the aeration tank and the second settling basin, and is discharged into the river as a simple effluent in the rain after the treatment in the first settling pond. In the disinfection method of the present invention, the drug (A) and the drug (B) are preferably added individually to the simple effluent water in the rain, preferably in a solid state. The amount of drug (A) and drug (B) added depends on the ammonia nitrogen concentration detected by the ammonia nitrogen detector (NH 4 -N sensor) provided in the discharge line of simple discharge water in rainy weather. Determined by the operator. Specifically, when the ammoniacal nitrogen concentration is 30 mg / L or less, the molar ratio of Cl in the drug (A) to Br in the drug (B): Br / Cl is less than 1.0, preferably Br / Cl When the ammonia nitrogen concentration exceeds 30 mg / L, the molar ratio of Cl in the drug (A) to Br in the drug (B): Br / Cl is 1.0. As mentioned above, Preferably it is 2.0 or less. Before discharging into the river, it is preferable to measure the residual halogen concentration of simple discharge water in rainy weather and to reduce the total injection amount of the 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、雨水を沈砂池に供給するラインに設けられたアンモニア性窒素検出器（ＮＨ４−Ｎセンサー）により検出されるアンモニア性窒素濃度に応じて、演算子により決定される。具体的には、アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、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以上とし、アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、薬剤（Ａ）中Ｃｌと薬剤（Ｂ）中Ｂｒのモル比：Ｂｒ／Ｃｌが１．０以上、好ましくは２．０以下とする。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。 FIG. 2 shows a processing flow when the disinfection method of the present invention is applied to a rainwater pump station. In the figure, “◯” indicates a valve. In a normal rainwater pump station, rainwater is discharged into a river after being treated in a sand basin and a pump well. In the disinfection method of the present invention, the drug (A) and the drug (B) are preferably added individually to the sand basin, preferably in a solid state. The amount of drug (A) and drug (B) added depends on the ammonia nitrogen concentration detected by the ammonia nitrogen detector (NH 4 -N sensor) provided in the line that supplies rainwater to the sand basin. Determined by the operator. Specifically, when the ammoniacal nitrogen concentration is 30 mg / L or less, the molar ratio of Cl in the drug (A) to Br in the drug (B): Br / Cl is less than 1.0, preferably Br / Cl When the ammonia nitrogen concentration exceeds 30 mg / L, the molar ratio of Cl in the drug (A) to Br in the drug (B): Br / Cl is 1.0. As mentioned above, Preferably it is 2.0 or less. It is preferable to measure the residual halogen concentration of rainwater treated effluent before discharge into the river and reduce the total injection amount of the drugs (A) and (B) when 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、排水中のアンモニア性窒素濃度に加えて、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）のモル比に加えて全注入量を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。また、薬剤（Ａ）及び（Ｂ）は、別個の溶液として、あるいはあらかじめ混合して溶液として供給されてもよい。 In FIGS. 1 and 2, the injection amount of the drug (A) from the Cl supplier and (B) from the Br supplier is controlled by an operator. In addition to the concentration of ammoniacal nitrogen in the wastewater, the operator receives signals from external factors such as rainfall, rainfall time, simple discharge start time in rainy weather or rainwater pump operation start time, and the drugs (A) and ( It is preferable to control the total injection amount in addition to the molar ratio of B). The chemicals (A) and (B) are preferably charged as they are, and can be charged using, for example, a powder supply facility disclosed in Japanese Patent Application Laid-Open No. 2004-18013. Further, the drugs (A) and (B) may be supplied as separate solutions or mixed in advance and supplied as a solution.
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。
試験水として、降雨量７mm／時の降雨の際の雨天時簡易放流水を用いた。試験水の性状を表１に示す。
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these.
As test water, simple effluent in rainy weather at the time of rainfall of 7 mm / hour was used. Table 1 shows the properties of the test water.
試験水１Lをビーカーに採取し、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。 Collect 1 L of test water in a beaker, set it in a jar tester, stir at 120 rpm, add the drugs (A) and (B) in the types and ratios shown in Table 2, stop stirring after 3 minutes, and test 100 ml of water was collected. Immediately after collection, a part of the test water was subjected to analysis of free residual chlorine concentration and total residual chlorine concentration, and a part of the test water was collected in a sterilized bottle containing sodium thiosulfate. Using the test water collected in a sterilized bottle, the number of E. coli (chromoager ECC medium, plate culture method) and the number of coliforms (desoxycholate medium, plate culture method) were measured.
また、表１に示す試験水に対して所定量の塩化アンモニウムを添加して、表２に示すアンモニア性窒素濃度に調整し、同様の測定を行った。結果を表２に示す。
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）
In addition, a predetermined amount of ammonium chloride was added to the test water shown in Table 1 to adjust the ammoniacal nitrogen concentration shown in Table 2, and the same measurement was performed. The results are shown in Table 2.
The drugs used are as follows.
Drug (A)
・ Sodium dichloroisocyanurate Neochlor 60 (made by Shikoku Chemicals, effective chlorine content 64.48%, white crystalline solid)
・ Sleeping powder Advanced bleaching powder (Japan Soda Industry Association Standard JSIA07-1-1998 Class I, effective chlorine 70% or more)
・ Sodium hypochlorite Sodium hypochlorite reagent (Wako Pure Chemical Industries, reagent special grade, effective chlorine 12%)
・ Trichloroisocyanuric acid Neochlor 90 (made by Shikoku Chemicals, effective chlorine content 90%, white crystalline solid)
Drug (B)
・ Sodium bromide (Wako Pure Chemical Industries, reagent grade)
・ Ammonium bromide (special grade reagent for Wako Pure Chemical Industries)
・ Calcium bromide (special grade reagent for Wako Pure Chemical Industries)
・ Potassium bromide (special grade reagent for Wako Pure Chemical Industries)
排水中アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０未満とすることにより、大腸菌数及び大腸菌群数ともに減少しており、放流基準値（３，０００ＣＦＵ／ｍＬ以下）を満たすが、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０以上とすると、大腸菌群数が放流基準値を満たしていないことがわかる。 When the concentration of ammoniacal nitrogen in the wastewater is 30 mg / L or less, both the number of coliforms and the number of coliform groups are reduced by making Br in the drug (B) less than 1.0 molar ratio to Cl in the drug (A). The release standard value (3,000 CFU / mL or less) is satisfied, but when the Br in the drug (B) has a molar ratio of 1.0 or more with respect to Cl in the drug (A), the number of coliforms is the standard value for release. It can be seen that is not satisfied.
一方、排水中アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０以上とすることにより、大腸菌数及び大腸菌群数ともに減少しており、放流基準値（３，０００ＣＦＵ／ｍＬ以下）を満たすが、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０未満とすると、大腸菌群数が放流基準値を満たしていないことがわかる。 On the other hand, when the concentration of ammoniacal nitrogen in the wastewater exceeds 30 mg / L, both the number of coliforms and the number of coliforms are increased by setting Br in the drug (B) to a molar ratio of 1.0 or more to Cl in the drug (A). Although it is decreasing and satisfies the release standard value (3,000 CFU / mL or less), the number of coliforms is released when Br in the drug (B) is less than 1.0 in molar ratio to Cl in the drug (A). It can be seen that the standard value is not satisfied.
また、従来法である５，５−ジメチルヒダントインを添加した比較例１８及び１９では、アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０未満としても、排水中アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０以上としても、大腸菌群数が放流基準値を満たしていない。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。 Moreover, in Comparative Examples 18 and 19 to which 5,5-dimethylhydantoin, which is a conventional method, was added, when the ammoniacal nitrogen concentration was 30 mg / L or less, Br in the drug (B) was changed to Cl in the drug (A). Even if the molar ratio of ammonia is less than 1.0 and the ammoniacal nitrogen concentration in the waste water exceeds 30 mg / L, the Escherichia coli group can be obtained even if Br in the drug (B) is set to a molar ratio of 1.0 or more to Cl in the drug (A) The number does not meet the discharge standard value. Hypobromite and hypochlorite produced from the drug (A) and drug (B) react with 5,5-dimethylhydantoin to produce chlorinated and brominated 5,5-dimethylhydantoin. This is presumed to be due to the weakening of the oxidation activity.
次に、表１に示す試験水に対して、所定量の塩化アンモニウムを添加してアンモニア性窒素濃度を５ｍｇ／Ｌ、２５ｍｇ／Ｌ及び４０ｍｇ／Ｌとした試験水３種を調製し、次亜塩素酸ナトリウム及び臭化カ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３〜４に示す。 Next, three types of test water were prepared with the ammonia nitrogen concentration of 5 mg / L, 25 mg / L and 40 mg / L by adding a predetermined amount of ammonium chloride to the test water shown in Table 1. The molar ratio of sodium chlorate and potassium bromide was changed as shown in Table 3, and each was added separately as a solid, and the disinfection effect was compared. The results are shown in Table 3 and FIGS.
Claims (6)
前記排水中のアンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、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）を前記排水に添加し、
前記排水中のアンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、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。 A chemical (A) that generates hypochlorite ions (OCl − ) in water and a chemical (B) that generates bromide ions (Br − ) in water are added to wastewater containing ammonia nitrogen. A method for disinfecting ammonia nitrogen-containing waste water for sterilizing Escherichia coli and coliform bacteria in the waste water, wherein Cl in the drug (A) and in the drug (B) according to the ammonia nitrogen concentration in the waste water Adjusting the molar ratio with Br, adding the drug (A) and the drug (B) to the waste water ,
When the ammonia nitrogen concentration in the waste water is 30 mg / L or less, the molar ratio of Cl in the drug (A) and Br in the drug (B) is Br / Cl <1.0. Adding the drug (A) and the drug (B) to the waste water;
When the ammoniacal nitrogen concentration in the waste water exceeds 30 mg / L, the molar ratio of Cl in the drug (A) and Br in the drug (B) is such that Br / Cl ≧ 1.0. Add the drug (A) and the drug (B) to the waste water
A method characterized by that.
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、ことを特徴とする請求項１に記載の方法。 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 (bleaching powder),
The method according to claim 1, wherein the drug (B) includes one or more selected from sodium bromide, potassium bromide, ammonium bromide, and calcium bromide.
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