JP5725273B2 - Method for deodorizing liquid or mud, deodorant and method for producing the same - Google Patents
Method for deodorizing liquid or mud, deodorant and method for producing the same Download PDFInfo
- Publication number
- JP5725273B2 JP5725273B2 JP2010079193A JP2010079193A JP5725273B2 JP 5725273 B2 JP5725273 B2 JP 5725273B2 JP 2010079193 A JP2010079193 A JP 2010079193A JP 2010079193 A JP2010079193 A JP 2010079193A JP 5725273 B2 JP5725273 B2 JP 5725273B2
- Authority
- JP
- Japan
- Prior art keywords
- chlorine
- mud
- liquid
- sulfamic acid
- deodorant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002781 deodorant agent Substances 0.000 title claims description 70
- 239000007788 liquid Substances 0.000 title claims description 57
- 230000001877 deodorizing effect Effects 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 24
- 239000011499 joint compound Substances 0.000 title 1
- 239000000460 chlorine Substances 0.000 claims description 113
- 229910052801 chlorine Inorganic materials 0.000 claims description 93
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 87
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 60
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 48
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 35
- 239000003513 alkali Substances 0.000 claims description 35
- 239000007800 oxidant agent Substances 0.000 claims description 34
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 31
- 239000012320 chlorinating reagent Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 230000001590 oxidative effect Effects 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical group ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 60
- 235000019645 odor Nutrition 0.000 description 37
- 239000005708 Sodium hypochlorite Substances 0.000 description 35
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 35
- 239000010802 sludge Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 24
- 238000004332 deodorization Methods 0.000 description 21
- 238000003860 storage Methods 0.000 description 19
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 16
- 238000002156 mixing Methods 0.000 description 14
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 12
- -1 amino compound Chemical class 0.000 description 11
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000010998 test method Methods 0.000 description 8
- 239000010865 sewage Substances 0.000 description 7
- 229960003080 taurine Drugs 0.000 description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 6
- 108010077895 Sarcosine Proteins 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 229940043230 sarcosine Drugs 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- 229910001919 chlorite Inorganic materials 0.000 description 5
- 229910052619 chlorite group Inorganic materials 0.000 description 5
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 5
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 3
- 229960002218 sodium chlorite Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical class Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910001902 chlorine oxide Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229960002449 glycine Drugs 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 2
- KEPNSIARSTUPGS-UHFFFAOYSA-N 2-n,4-n,6-n-trichloro-1,3,5-triazine-2,4,6-triamine Chemical compound ClNC1=NC(NCl)=NC(NCl)=N1 KEPNSIARSTUPGS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SDUXGMLGPOQMKO-UHFFFAOYSA-N dichlorosulfamic acid Chemical compound OS(=O)(=O)N(Cl)Cl SDUXGMLGPOQMKO-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- YGNOYUCUPMACDT-UHFFFAOYSA-N dimethylsulfamic acid Chemical compound CN(C)S(O)(=O)=O YGNOYUCUPMACDT-UHFFFAOYSA-N 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical compound CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000012476 oxidizable substance Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- QHFDHWJHIAVELW-UHFFFAOYSA-M sodium;4,6-dioxo-1h-1,3,5-triazin-2-olate Chemical compound [Na+].[O-]C1=NC(=O)NC(=O)N1 QHFDHWJHIAVELW-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229960001479 tosylchloramide sodium Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Treatment Of Sludge (AREA)
Description
本発明は、排水、汚泥、ヘドロ等の臭気が問題となる液または泥状物の消臭方法および消臭剤に関し、特に硫化水素、メルカプタンに起因する臭気を除去する液または泥状物の消臭方法、消臭剤およびその製造方法に関するものである。 The present invention relates to a deodorizing method and deodorant for liquids or sludges in which odors such as drainage, sludge, sludge and the like are problematic, and in particular, for eliminating liquids or sludges that remove odors caused by hydrogen sulfide and mercaptans. The present invention relates to an odor method, a deodorant and a method for producing the same.
工場の排水処理、汚泥処理工程、下水道管路、下水処理場、河川や臨海の浚渫現場等においては、硫化水素、メルカプタンをはじめとした臭気が発生する。また石油精製プロセス、紙パルププロセスなどの製造現場では、溶存硫化物を含んだ排水が発生するため、この排水の溶存硫化物処理、臭気対策が要求されている。 Odors such as hydrogen sulfide and mercaptans are generated in factory wastewater treatment, sludge treatment processes, sewer pipes, sewage treatment plants, rivers and coastal dredging sites. In addition, since wastewater containing dissolved sulfide is generated at manufacturing sites such as petroleum refining processes and paper pulp processes, it is required to treat the wastewater with dissolved sulfides and to prevent odors.
従来より、硫化水素、メルカプタン等に起因する臭気物質を含む液または泥状物などの水系対象物を消臭する場合、酸化剤による処理が行われてきた。すなわち対象物に酸化剤を添加し、対象物の中で臭気物質を酸化反応させることにより、無臭物質や低臭物質に分解、変換する処理が行われてきた。このような酸化剤としては、次亜塩素酸塩、亜塩素酸塩、塩素酸塩などの塩素酸化物を含む薬剤が使われてきた。 Conventionally, when deodorizing an aqueous object such as a liquid or mud containing an odorous substance caused by hydrogen sulfide, mercaptan, etc., a treatment with an oxidizing agent has been performed. In other words, an oxidant is added to an object, and an odorous substance is oxidized in the object to be decomposed and converted into an odorless substance or a low odorous substance. As such an oxidizing agent, agents containing chlorine oxides such as hypochlorite, chlorite and chlorate have been used.
このうち亜塩素酸塩、塩素酸塩などは、酸化性が高く消臭効果に優れるが、爆発性、毒性、取扱性に難点があるため、主として次亜塩素酸塩が使用されてきた。しかし次亜塩素酸塩は消臭効果に劣るため、他の酸化剤との併用、例えば特許文献１（特開平６−３２０１９５）では亜塩素酸塩との併用、特許文献２（特開２０００−１５７９６７）では臭素酸塩との併用により、消臭効果を高める試みがなされてきた。これらで併用される亜塩素酸塩や臭素酸塩は、前述の問題点があり、根本的な解決にならない。 Of these, chlorite, chlorate and the like are highly oxidative and excellent in deodorizing effect, but hypochlorite has been mainly used because of their difficulty in explosiveness, toxicity, and handleability. However, since hypochlorite is inferior in the deodorizing effect, it is used in combination with other oxidizing agents, for example, in Patent Document 1 (Japanese Patent Laid-Open No. 6-320195), in combination with chlorite, Patent Document 2 (Japanese Patent Laid-Open No. 2000-2000) 157967) have attempted to increase the deodorizing effect by using in combination with bromate. Chlorite and bromate used in combination with these have the above-mentioned problems and do not provide a fundamental solution.
また次亜塩素酸塩、亜塩素酸塩、塩素酸塩などの塩素酸化物は、塩素臭（カルキ臭）が発生するため、その対策が求められている。この塩素臭に対応するものとして、特許文献３（特開平７−１４８２３４）には、トイレ、冷蔵庫等の家庭用の消臭剤として、アンモニアおよび／またはアミノ化合物の窒素部位にハロゲン原子を一つ以上保有するクロラミン化合物を含有する消臭剤が提案され、タウリン、ザルコシン、２−アミノエタノール等のクロラミン化合物について、消臭効果が示されている。この特許文献３には、窒素化合物として、スルファミン酸が例示されているが、実際の消臭効果が示されていない。
Further, chlorine oxides such as hypochlorite, chlorite, and chlorate generate a chlorine odor, and therefore countermeasures are required. In order to cope with this chlorine odor, Patent Document 3 (Japanese Patent Laid-Open No. 7-148234) discloses that one halogen atom is present at the nitrogen portion of ammonia and / or an amino compound as a deodorant for household use such as a toilet and a refrigerator. Deodorants containing the chloramine compounds possessed above have been proposed, and deodorizing effects have been shown for chloramine compounds such as taurine, sarcosine and 2-aminoethanol. In
特許文献３には、アミノ化合物に次亜塩素酸ナトリウムを当モル量添加して混合すればクロラミン化合物が得られると記載されているが、例示されたスルファミン酸に次亜塩素酸ナトリウムを直接混合する方法では、添加直後から気泡が次々に発生し、安定した製剤を得ることができなかった。尿素、タウリン、グリシン、サルコシンの場合も、次亜塩素酸ナトリウムを直接混合することにより泡が発生し、安定した製剤が得られなかった。発生する気泡は次亜塩素酸ナトリウムが分解して発生した塩素ガスと想定される。特許文献３が対象とするトイレ、冷蔵庫等の家庭用の消臭剤の場合は、低濃度、小規模のため製造が可能であっても、大規模な排水、汚泥等の液または泥状物の消臭用として適用は困難である。
また特許文献４（特表２００６−５０２７６３）には、便器その他の臭気を発する機器用の洗浄もしくは脱臭製品として、塩素化剤と不溶性緩衝アルカリ塩とを含む脱臭製品が提案され、塩素化剤としてクロラミン−Ｔ、次亜塩素酸ナトリウムとシアヌル酸ナトリウムとを含む塩素化剤、トリクロロメラミンについて消臭効果が示されている。この特許文献４には、塩素化剤としてモノ−もしくはジ−クロロスルファミン酸のナトリウムまたはカリウム塩が例示されているが、実際の消臭効果が示されていない。
Patent Document 4 (Japanese Translation of PCT International Publication No. 2006-502763) proposes a deodorizing product containing a chlorinating agent and an insoluble buffered alkali salt as a cleaning or deodorizing product for toilets and other devices that emit odors. Deodorizing effects are shown for chloramine-T, a chlorinating agent containing sodium hypochlorite and sodium cyanurate, and trichloromelamine. This
一方、特許文献５（特開２００２−１７２１５５）には、ポータブルトイレ用消臭剤として、塩化イソシアヌル酸と有機酸アルカリ金属化合物と無機酸アルカリ金属化合物とを含有する消臭剤が記載され、前記無機酸アルカリ金属化合物として、スルファミン酸ナトリウムを用いることが提案されているが、有機酸アルカリ金属化合物を用いない場合、すなわち塩化イソシアヌル酸とスルファミン酸ナトリウムのみの組合せの場合には、スルファミン酸ナトリウムは消臭に対して何ら影響を与えていないことが実験的に確かめられている。 On the other hand, Patent Document 5 (Japanese Patent Laid-Open No. 2002-172155) describes a deodorant containing isocyanuric chloride, an organic acid alkali metal compound, and an inorganic acid alkali metal compound as a portable toilet deodorant, Although it has been proposed to use sodium sulfamate as the inorganic acid alkali metal compound, when no organic acid alkali metal compound is used, that is, in the case of a combination of isocyanuric chloride and sodium sulfamate alone, sodium sulfamate is It has been experimentally confirmed that it has no effect on deodorization.
本発明の課題は、前記のような従来の問題点を解決するため、次亜塩素酸塩などの塩素系酸化剤の消臭効果を高めるとともに、塩素臭の発生をなくし、安全性、安定性が高く、腐食性が低く、かつ取扱性、保存安定性が良好であり、少ない添加量で、短時間に効果的に消臭できる液または泥状物の消臭方法および消臭剤、ならびにその効率的な製造方法を提案することである。 In order to solve the conventional problems as described above, the object of the present invention is to enhance the deodorizing effect of a chlorine-based oxidant such as hypochlorite, eliminate the generation of chlorine odor, and improve safety and stability. , Deodorizing method and deodorant for liquids or sludges that are high in corrosion resistance, low in corrosivity, good in handling and storage stability, and can be effectively deodorized in a short amount of time with a small addition amount, and It is to propose an efficient manufacturing method.
本発明は次の液または泥状物の消臭方法、消臭剤およびその製造方法である。
（１） 臭気原因成分を含む液または泥状物に、
アルカリ金属水酸化物からなるアルカリと、スルファミン酸と、塩素系酸化剤とを含有し、スルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１であり、スルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３であり、全体の水の量が５０〜９０重量％である一製剤として調製された結合塩素剤水溶液を含む消臭剤を添加し、
液または泥状物中の還元性硫黄臭気物質を含む臭気原因成分と反応して消臭を行う
ことを特徴とする液または泥状物の消臭方法。
（２） 塩素系酸化剤が次亜塩素酸またはその塩である上記（１）記載の方法。
（３） 液または泥状物が、硫化水素および／またはメルカプタンを含有もしくは生成する臭気原因成分を含むものである上記（１）または（２）記載の方法。
（４） 臭気原因成分を含む液または泥状物に添加し、液または泥状物中の還元性硫黄臭気物質を含む臭気原因成分と反応して消臭する消臭剤であって、
アルカリ金属水酸化物からなるアルカリと、スルファミン酸と、塩素系酸化剤とを含有し、スルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１であり、スルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３であり、全体の水の量が５０〜９０重量％である一製剤として調製された結合塩素剤水溶液を含むことを特徴とする液または泥状物の消臭剤。
（５） 塩素系酸化剤が次亜塩素酸またはその塩である上記（４）記載の消臭剤。
（６） 臭気原因成分を含む液または泥状物に添加し、液または泥状物中の還元性硫黄臭気物質を含む臭気原因成分と反応して消臭する消臭剤を製造する方法であって、
アルカリ金属水酸化物からなるアルカリ水溶液にスルファミン酸をスルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３となる量で添加して溶解し、得られたスルファミン酸−アルカリ混合水溶液に、塩素系酸化剤をスルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１となる量で添加して混合し、全体の水の量が５０〜９０重量％である一製剤として調製することを特徴とする液または泥状物の消臭剤の製造方法。
（７） アルカリ水溶液は、水の量が５５〜８５重量％である上記（６）記載の製造方法。
The present invention provides the following liquid or mud deodorization method, deodorant and production method thereof.
(1) To liquid or mud containing odor-causing component,
It contains an alkali composed of an alkali metal hydroxide, sulfamic acid, and a chlorine-based oxidant, and the content ratio of sulfamic acid and chlorine-based oxidant is 0.2 to 1 in terms of Cl / N (molar ratio). Yes , combined chlorinating agent aqueous solution prepared as one preparation in which the content ratio of sulfamic acid and alkali is 1 to 3 in terms of alkali metal / N (molar ratio), and the total amount of water is 50 to 90% by weight Add deodorant containing
A method for deodorizing a liquid or a mud, characterized by reacting with an odor-causing component containing a reducing sulfur odor substance in the liquid or a mud, to deodorize the liquid or the mud.
(2) The method according to (1) above, wherein the chlorinated oxidant is hypochlorous acid or a salt thereof.
(3) The method according to (1) or (2) above, wherein the liquid or mud contains an odor-causing component that contains or generates hydrogen sulfide and / or mercaptan.
(4) A deodorant which is added to a liquid or mud containing an odor-causing component and deodorizes by reacting with the odor-causing component containing a reducing sulfur odor substance in the liquid or mud,
It contains an alkali composed of an alkali metal hydroxide, sulfamic acid, and a chlorine-based oxidant, and the content ratio of sulfamic acid and chlorine-based oxidant is 0.2 to 1 in terms of Cl / N (molar ratio). Yes , combined chlorinating agent aqueous solution prepared as one preparation in which the content ratio of sulfamic acid and alkali is 1 to 3 in terms of alkali metal / N (molar ratio), and the total amount of water is 50 to 90% by weight A liquid or mud deodorant characterized by comprising
(5) The deodorizer according to (4) above, wherein the chlorinated oxidant is hypochlorous acid or a salt thereof.
(6) A method for producing a deodorant that is added to a liquid or mud containing an odor-causing component and reacts with the odor-causing component containing a reducing sulfur odor substance in the liquid or mud to deodorize it. And
A sulfamic acid obtained by adding and dissolving sulfamic acid in an aqueous alkali solution comprising an alkali metal hydroxide in an amount such that the content ratio of sulfamic acid and alkali is 1 to 3 in terms of alkali metal / N (molar ratio) is obtained. - a mixed alkali aqueous solution, the content of the chlorine-based oxidizing agent sulfamic acid and chlorine-based oxidizing agent, added and mixed in an amount of 0.2 to 1 at Cl / N (mol ratio), the total water A method for producing a liquid or mud deodorant, characterized in that the preparation is prepared as one preparation having an amount of 50 to 90% by weight .
(7) The manufacturing method according to (6), wherein the alkaline aqueous solution has an amount of water of 55 to 85% by weight.
本発明において、消臭の対象となる液または泥状物は、排水、汚泥、ヘドロ等の臭気原因成分を含む液または泥状物であり、特に硫化水素および／またはメルカプタンを含有もしくは生成する臭気原因成分を含む液または泥状物である。このような液または泥状物としては、工場排水、都市下水、家庭排水、その他の有機性排水、これらの処理汚泥、浚渫汚泥、ヘドロ、その他の汚泥、それらの脱水物（脱水ケーキ）など、水系の液または泥状物があげられる。このような液または泥状物としては、それ自体硫化水素および／またはメルカプタン臭、その他の臭気を発するもののほか、反応、分解等により硫化水素および／またはメルカプタン臭、その他の臭気を発するものを含む。 In the present invention, the liquid or mud that is the object of deodorization is a liquid or mud that contains odor-causing components such as drainage, sludge, sludge, etc., and in particular, an odor that contains or generates hydrogen sulfide and / or mercaptan. Liquid or mud containing causative components. Such liquids or sludges include industrial wastewater, municipal sewage, domestic wastewater, other organic wastewater, treated sludge, sludge, sludge, other sludge, and their dehydrated products (dehydrated cake). Aqueous liquid or mud. Such liquids or sludges include those that themselves generate hydrogen sulfide and / or mercaptan odors and other odors, as well as those that generate hydrogen sulfide and / or mercaptan odors and other odors due to reaction, decomposition, etc. .
本発明において、このような液または泥状物を消臭するための消臭剤は、臭気原因成分を含む液または泥状物に添加し、液または泥状物中の還元性硫黄臭気物質を含む臭気原因成分と反応して消臭する消臭剤であって、アルカリ金属水酸化物からなるアルカリと、スルファミン酸と、塩素系酸化剤とを含有し、一製剤として調製された結合塩素剤の水溶液を含むものである。本発明の消臭剤は、上記結合塩素剤の一製剤として調製された水溶液であることが、反応性、安定性、取扱性、無塩素臭等の面から重要であり、水溶液の状態で液または泥状物に添加して、その消臭に使用される。このような消臭剤は、後述の製造方法により使用現場で製造して使用しても良いが、貯蔵安定性が優れるため、予め工場等で製造したものを現地に運搬して使用しても良い。この場合、結合塩素剤水溶液中の水の量は、貯蔵および運搬等の面からは、可能な限り低くするのが望ましいが、製造効率、貯蔵安定性等の面からは、全体の水の量として５０〜９０重量％、好ましくは６０〜７５重量％とするのが好適である。 In the present invention, a deodorant for deodorizing such liquid or mud is added to the liquid or mud containing the odor-causing component, and the reducing sulfur odor substance in the liquid or mud is removed. A deodorant that reacts with an odor-causing component and deodorizes, and contains an alkali consisting of an alkali metal hydroxide, sulfamic acid, and a chlorinated oxidant, and is a combined chlorine agent prepared as a preparation. The aqueous solution is included. It is important that the deodorant of the present invention is an aqueous solution prepared as a preparation of the above-mentioned combined chlorinating agent in terms of reactivity, stability, handleability, chlorine-free odor, etc. Or it is added to mud and used for its deodorization. Such a deodorant may be manufactured and used at the site of use by the manufacturing method described later, but because it has excellent storage stability, it can be transported to the site and used in advance. good. In this case, the amount of water in the combined chlorine solution is preferably as low as possible from the viewpoint of storage and transportation, but the total amount of water from the viewpoint of production efficiency and storage stability. 50 to 90% by weight, preferably 60 to 75% by weight.
上記結合塩素剤は、スルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１、好ましくは０．３〜０．９とされる。高温（４０℃保存）での経時安定性が損なわれるため、Ｃｌ／Ｎ（モル比）は１以下、好ましくは０．９以下とするのが好ましい。Ｃｌ／Ｎ（モル比）がこの範囲より小さいと、結合塩素を高濃度で配合できない。 The combined chlorine agent has a content ratio of sulfamic acid and chlorine-based oxidizing agent of 0.2 to 1, preferably 0.3 to 0.9 in terms of Cl / N (molar ratio). Since the temporal stability at high temperature (stored at 40 ° C.) is impaired, the Cl / N (molar ratio) is preferably 1 or less, preferably 0.9 or less. If Cl / N (molar ratio) is smaller than this range, combined chlorine cannot be blended at a high concentration.
実用的には、製剤中に結合塩素が有効塩素として０．１７ｍｏｌ／ｋｇ以上含まれる製剤が好ましい。この濃度は、１２％Ｃｌ２換算の次亜塩素酸ナトリウム液を製剤中に１０％以上配合した（仕込んだ）結合塩素剤である。これより配合率が低いと、工業用消臭剤としては添加率が高くなりすぎて不適である。更に、製剤中に結合塩素が有効塩素として０．８５ｍｏｌ／ｋｇ以上含まれるものが好ましい。この濃度は、１２％Ｃｌ２換算の次亜塩素酸ナトリウム液を製剤中に５０％以上配合した（仕込んだ）結合塩素剤である。 Practically, a preparation containing 0.17 mol / kg or more of bonded chlorine as effective chlorine is preferable in the preparation. This concentration is a combined chlorine agent containing (prepared) 10% or more of a sodium hypochlorite solution in terms of 12% Cl 2 in the preparation. If the blending ratio is lower than this, the addition ratio becomes too high as an industrial deodorant, which is not suitable. Further, it is preferable that the preparation contains 0.85 mol / kg or more of bonded chlorine as effective chlorine. This concentration (the charged) was blended more than 50% in the formulation of sodium hypochlorite containing acid solution 12% Cl 2 in terms of a combined chlorine agents.
結合塩素剤に用いられるスルファミン酸は、Ｒ１Ｒ２ＮＳＯ３Ｈ・・・〔１〕で表されるアミド硫酸で、Ｒ１、Ｒ２はそれぞれ独立にＨ、炭素数１〜６の炭化水素基である。このようなスルファミン酸としては、Ｒ１、Ｒ２がそれぞれＨである狭義のスルファミン酸が好ましいが、Ｎ−メチルスルファミン酸、Ｎ，Ｎ−ジメチルスルファミン酸、Ｎ−フェニルスルファミン酸なども使用できる。これらのスルファミン酸は、塩で添加してもよく、この場合の使用可能な塩としては、上記結合塩素剤水溶液としたときに可溶性のものがあげられ、スルファミン酸ナトリウム、スルファミン酸カリウム、スルファミン酸アンモニウム等を用いることができる。塩素系酸化剤としては、次亜塩素酸またはその可溶性塩があげられ、好ましくは次亜塩素酸ナトリウム、次亜塩素酸カリウム等のアルカリ金属塩があげられる。アルカリはアルカリ金属水酸化物からなるものであり、このようなアルカリとして、上記結合塩素剤水溶液としたときに可溶性を維持するものがあげられ、水酸化ナトリウム、水酸化カリウム等があげられる。 The sulfamic acid used for the combined chlorine agent is amidosulfuric acid represented by R 1 R 2 NSO 3 H (1), R 1 and R 2 are each independently H, a hydrocarbon having 1 to 6 carbon atoms. It is a group. As such sulfamic acid, sulfamic acid in the narrow sense in which R 1 and R 2 are each H is preferable, but N-methylsulfamic acid, N, N-dimethylsulfamic acid, N-phenylsulfamic acid and the like can also be used. These sulfamic acids may be added as a salt. In this case, usable salts include those soluble in the above-mentioned combined chlorinating agent aqueous solution, such as sodium sulfamate, potassium sulfamate, sulfamic acid. Ammonium and the like can be used. Examples of the chlorine-based oxidant include hypochlorous acid or a soluble salt thereof, preferably alkali metal salts such as sodium hypochlorite and potassium hypochlorite. The alkali is an alkali metal hydroxide, and examples of such an alkali include those that maintain solubility when the above combined chlorine solution is used, such as sodium hydroxide and potassium hydroxide.
本発明においてアルカリは、反応性、安定性、取扱性、無塩素臭等の面から重要である。結合塩素剤は、スルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３、好ましくは１．３〜２の量で含む。 In the present invention, alkali is important in terms of reactivity, stability, handleability, chlorine-free odor, and the like. Combined chlorine agent, the content of the sulfamic acid and the alkali, 1-3 with an alkali metal / N (mol ratio), including preferably in an amount of 1.3 to 2.
アルカリ金属／スルファミン酸（モル比）の値が１より小さいと、中和されないスルファミン酸が残留して酸性となる。この場合、次亜塩素酸ナトリウムを混合して結合塩素を得ようとしても、酸性下では次亜塩素酸ナトリウムが自己分解してしまい、目的の結合塩素剤が得られない。仮に、製剤ができたとしても不安定な製剤となる。また、アルカリ金属／スルファミン酸（モル比）の値が３より大きいと、過剰なアルカリ剤が配合されるため、結合塩素の濃度が低くなり、有効成分濃度が低い製剤となってしまう。実用的には、製剤中に結合塩素が有効塩素として０．１７ｍｏｌ／ｋｇ以上含まれる製剤が好ましい。この濃度は、１２％Ｃｌ２換算の次亜塩素酸ナトリウム液を製剤中に１０％以上配合した（仕込んだ）結合塩素剤である。これより配合率が低いと、工業用消臭剤としては添加率が高くなりすぎて不適である。さらに製剤中に結合塩素が有効塩素として０．８５ｍｏｌ／ｋｇ以上含まれるものが好ましい。この濃度は、１２％Ｃｌ２換算の次亜塩素酸ナトリウム液を製剤中に５０％以上配合した(仕込んだ)結合塩素剤である。製剤中に結合塩素を０．８５ｍｏｌ／ｋｇ以上配合したような高濃度製剤の場合、アルカリ金属／スルファミン酸（モル比）が１．３より小さいと、高温（４０℃保存）での経時安定性が損なわれる。また、アルカリ金属／スルファミン酸（モル比）が２より大きいと、結合塩素を上記のように高濃度配合できない（１２％Ｃｌ２換算次亜塩素酸Ｎａ液、４８％水酸化Ｎａ液を使用した場合）。 If the value of alkali metal / sulfamic acid (molar ratio) is less than 1, sulfamic acid that is not neutralized remains and becomes acidic. In this case, even if sodium hypochlorite is mixed to obtain bonded chlorine, sodium hypochlorite is self-decomposed under acidic conditions, and the target bonded chlorine agent cannot be obtained. Even if a preparation is made, it becomes an unstable preparation. Further, since the value is greater than 3 of the alkali metal / sulfamic acid (molar ratio), excess alkali agent is blended, the concentration of bound chlorine is low, becomes an active ingredient concentration is low formulation. Practically, a preparation containing 0.17 mol / kg or more of bonded chlorine as effective chlorine is preferable in the preparation. This concentration is a combined chlorine agent containing (prepared) 10% or more of a sodium hypochlorite solution in terms of 12% Cl 2 in the preparation. If the blending ratio is lower than this, the addition ratio becomes too high as an industrial deodorant, which is not suitable. Moreover those bound chlorine in the formulation is contained 0.85 mol / kg or more as an active chlorine are preferred. This concentration is a combined chlorinating agent containing (prepared) 50% or more of a sodium hypochlorite solution in terms of 12% Cl 2 in the preparation. In the case of a high-concentration preparation that contains 0.85 mol / kg or more of bound chlorine in the preparation, if the alkali metal / sulfamic acid (molar ratio) is less than 1.3, the stability over time at high temperature (stored at 40 ° C) Is damaged. If the alkali metal / sulfamic acid (molar ratio) is greater than 2, combined chlorine cannot be blended at a high concentration as described above (12% Cl 2 equivalent sodium hypochlorite solution, 48% Na hydroxide solution was used. If).
本発明の消臭剤は、上記の成分のほか、さらに必要に応じて、殺生物剤、増殖抑制剤、腐食防止剤、銅用防食剤、スケール防止剤、消泡剤、界面活性剤などの補助成分を配合することができる。これら補助成分の配合量は、それぞれの機能に応じて必要な量とされる。 In addition to the above components, the deodorant of the present invention may further include a biocide, a growth inhibitor, a corrosion inhibitor, a copper anticorrosive, a scale inhibitor, an antifoaming agent, a surfactant, etc. An auxiliary component can be mix | blended. The blending amount of these auxiliary components is an amount necessary for each function.
上記の消臭剤は、アルカリ金属水酸化物からなるアルカリ水溶液にスルファミン酸を添加して溶解し、得られたスルファミン酸−アルカリ混合水溶液に、塩素系酸化剤を添加して混合し、一製剤の結合塩素剤水溶液として調製することにより製造することができる。このような製造方法により、消臭効果が高く、塩素臭の発生がなく、安全性、安定性が高く、腐食性が低く、かつ取扱性、保存安定性が良好であり、少ない添加量で、短時間に効果的に消臭できる消臭剤を効率的に製造することができる The above deodorizer is prepared by adding sulfamic acid to an aqueous alkali solution made of an alkali metal hydroxide and dissolving it, adding a chlorinated oxidant to the resulting aqueous sulfamic acid-alkali mixed solution, and mixing them together. It can manufacture by preparing as a combined chlorine agent aqueous solution. With such a production method, the deodorizing effect is high, the generation of chlorine odor is not generated, the safety and stability are high, the corrosivity is low, the handling property and the storage stability are good, and the addition amount is small, It is possible to efficiently produce a deodorant that can effectively deodorize in a short time.
スルファミン酸を添加するアルカリ水溶液は、水の量が６０〜８５重量％、好ましくは５５〜８５重量％とする。スルファミン酸の添加量は、スルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３、好ましくは１．３〜２となる量とする。スルファミン酸は、スルファミン酸またはその塩を、粉末状態で、あるいは水溶液の状態で添加することができる。スルファミン酸塩を用いる場合、スルファミン酸塩に含まれるアルカリ金属の量は、アルカリとして加算される。水溶液を用いる場合は、水溶液に含まれる水の量は、前記アルカリ水溶液の水の量として加算される。 The amount of water in the alkaline aqueous solution to which sulfamic acid is added is 60 to 85% by weight, preferably 55 to 85% by weight. The amount of sulfamic acid added is such that the content ratio of sulfamic acid and alkali is 1 to 3, preferably 1.3 to 2 in terms of alkali metal / N (molar ratio). As sulfamic acid, sulfamic acid or a salt thereof can be added in a powder state or in an aqueous solution state. When sulfamate is used, the amount of alkali metal contained in the sulfamate is added as an alkali. When an aqueous solution is used, the amount of water contained in the aqueous solution is added as the amount of water in the alkaline aqueous solution.
塩素系酸化剤の添加量は、スルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１、好ましくは０．３〜０．９となる量とする。塩素系酸化剤は次亜塩素酸またはその塩が好ましく、有効塩素（Ｃｌ２）濃度として５〜２０重量％、好ましくは１０〜１５重量％水溶液として添加するのが好ましい。これにより発泡や塩素臭の発生はなく、反応性、安定性、取扱性、無塩素臭等に優れた結合塩素剤水溶液を効率よく製造することができる。この場合でも、塩素系酸化剤を徐々に添加して混合するのが好ましい。 The amount of the chlorinated oxidant added is such that the content ratio of sulfamic acid and chlorinated oxidant is 0.2 to 1, preferably 0.3 to 0.9 in terms of Cl / N (molar ratio). . The chlorine-based oxidizing agent is preferably hypochlorous acid or a salt thereof, and is added as an aqueous solution having an effective chlorine (Cl 2 ) concentration of 5 to 20% by weight, preferably 10 to 15% by weight. Thereby, there is no generation | occurrence | production of foaming and a chlorine odor, and it can manufacture efficiently the coupling | bonding chlorine agent aqueous solution excellent in reactivity, stability, handleability, a chlorine-free odor, etc. Even in this case, it is preferable to gradually add and mix the chlorine-based oxidizing agent.
本発明における結合塩素および有効塩素量は、ＪＩＳ Ｋ ０４００−３３−１０：１９９９のＤＰＤ法で測定した値である。スルファミン酸およびアルカリ金属の量は、天子天秤で測定した値である。 The amount of combined chlorine and effective chlorine in the present invention is a value measured by the DPD method of JIS K 0400-33-10: 1999. The amount of sulfamic acid and alkali metal is a value measured with a Tenshi balance.
本発明の消臭方法は、前記臭気原因成分を含む液または泥状物に、前記結合塩素剤水溶液を含む消臭剤を添加し、液または泥状物の消臭を行う。この場合、被処理液または泥状物の上面に添加するだけで消臭できる場合があるが、一般的には消臭剤を添加して液または泥状物を攪拌混合することにより消臭を行うことができる。消臭剤の添加量は、液または泥状物の種類、性状、臭気原因成分の種類、性状、量、消臭剤の組成等により異なるが、一般的には有効塩素として０．０１〜１００ｍｍｏｌ／Ｌ、好ましくは０．１〜１０ｍｍｏｌ／Ｌとすることができる。 In the deodorizing method of the present invention, a deodorant containing the combined chlorine solution is added to a liquid or mud containing the odor-causing component to deodorize the liquid or mud. In this case, there are cases where deodorization can be achieved simply by adding to the top surface of the liquid to be treated or mud, but in general, deodorization can be achieved by adding a deodorant and stirring and mixing the liquid or mud. It can be carried out. The amount of deodorant added varies depending on the type of liquid or mud, the properties, the type of odor-causing components, the properties, the amount, the composition of the deodorant, etc., but generally 0.01 to 100 mmol as effective chlorine. / L, preferably 0.1 to 10 mmol / L.
添加混合の方法は限定されないが、液または泥状物と消臭剤が均一に混合されて反応するように、攪拌器、混合機、混練機等の機械的混合手段を用いるのが好ましい。添加混合は開放系または密閉系で行ってもよく、また常温、加温または冷却下に行ってもよい。 The method of addition and mixing is not limited, but it is preferable to use a mechanical mixing means such as a stirrer, a mixer, a kneader or the like so that the liquid or mud and the deodorant are uniformly mixed and reacted. Addition and mixing may be performed in an open system or a closed system, or may be performed at room temperature, heating or cooling.
消臭剤の添加場所は、消臭効果を得たい場所そのもの、消臭効果を得たい場所に対象物が流れ込む配管、流路などの手前などがあり、このような場所において、対象系に結合塩素化合物を添加して消臭することができる。消臭剤はあらかじめ各成分を混合して調製しておいたものを、上記添加場所に運搬して添加してもよいが、添加場所（オンサイト）で添加直前に各成分を混合して、スルファミン酸アルカリ塩の結合塩素化合物を調製し、そのまま対象物に添加することにより、活性の高い消臭剤処理を行うことができる。 The deodorant is added to the location where you want to obtain the deodorizing effect, or to the location where you want to obtain the deodorizing effect. It can be deodorized by adding a chlorine compound. The deodorant may be prepared by mixing each component in advance and may be transported to the above-mentioned addition site and added, but each component is mixed immediately before addition at the addition site (onsite) A highly active deodorant treatment can be performed by preparing a combined chlorine compound of an alkali sulfamic acid salt and adding it directly to the object.
消臭剤添加の具体的な場所としては、以下の場所が挙げられる。
１）貯留タンクやサービスタンクなど、水系対象物が滞留する場所。
２）濃縮機や脱水機や吸引機など、水系対象物の処理機器。
３）処理機器の手前の水系対象物の供給部。
４）配管、管路、暗渠など、水系対象物の流路。
The following places are mentioned as a specific place of deodorant addition.
1) A place where water-based objects stay, such as storage tanks and service tanks.
2) Equipment for processing water-based objects such as concentrators, dehydrators and suction machines.
3) Supply unit for water-based objects in front of the processing equipment.
4) Flow paths for water-based objects such as pipes, pipelines, and underdrains.
消臭剤を添加することにより、液または泥状物に含まれる臭気原因成分は、消臭剤に含まれる結合塩素剤により消臭される。この場合、結合塩素剤がスルファミン酸と、塩素系酸化剤とから形成されていることにより、硫化水素、メルカプタンをはじめとした還元性硫黄臭気物質との反応性に優れ、他の被酸化物質に消費されることなく、先の臭気原因物質と反応するため、同塩素量の次亜塩素酸塩よりも少ない添加量で消臭効果が得られるものと推測される。 By adding the deodorant, the odor-causing component contained in the liquid or mud is deodorized by the combined chlorine agent contained in the deodorant. In this case, the combined chlorinating agent is formed from sulfamic acid and a chlorinated oxidant, so it has excellent reactivity with reducing sulfur odorous substances such as hydrogen sulfide and mercaptans, and other oxidizable substances. Since it reacts with the previous odor-causing substance without being consumed, it is presumed that the deodorizing effect can be obtained with an addition amount smaller than the hypochlorite having the same chlorine content.
消臭剤の添加後は、開放もしくは密閉状態で、静止または攪拌状態に維持することにより、長期にわたり消臭状態を維持することができる。消臭剤の添加後液または泥状物は、貯留、処理、脱水、処分等が行われるが、いずれの状態でも、消臭状態を維持することが可能である。例えば貯留中に消臭効果が低下したときには、再度消臭剤を添加して消臭処理を行うことができる。 After the deodorant is added, the deodorized state can be maintained over a long period of time by keeping it stationary or stirring in an open or sealed state. The liquid or mud after the addition of the deodorant is stored, treated, dehydrated, disposed of, etc., but in any state, the deodorized state can be maintained. For example, when the deodorizing effect decreases during storage, a deodorizing agent can be added again to perform the deodorizing process.
上記のようにして臭気原因成分を含む液または泥状物に、本発明の消臭剤を添加することにより、同じ塩素系酸化剤を添加するときよりも、少ない添加量で、短時間に脱臭を行うことができ、脱臭剤は安全で、塩素臭がなく、取扱も容易であり、作業性もよい。 By adding the deodorant of the present invention to the liquid or mud containing the odor-causing component as described above, it is possible to deodorize in a short time with a smaller amount of addition than when the same chlorinated oxidant is added. The deodorizer is safe, has no chlorine odor, is easy to handle, and has good workability.
本発明によれば、臭気原因成分を含む液または泥状物に、アルカリ金属水酸化物からなるアルカリと、スルファミン酸と、塩素系酸化剤とを含有し、スルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１であり、スルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３であり、全体の水の量が５０〜９０重量％である一製剤として調製された結合塩素剤水溶液を含む消臭剤を添加することにより、液または泥状物中の還元性硫黄臭気物質を含む臭気原因成分と反応して消臭を行うことができ、次亜塩素酸塩などの塩素系酸化剤の消臭効果を高めるとともに、塩素臭の発生をなくし、安全性、安定性が高く、腐食性が低く、かつ取扱性、保存安定性が良好であり、少ない添加量で、短時間に効果的に液または泥状物の消臭を行うことができる消臭効果（即効性）を有する。また本発明の消臭剤の製造方法によれば、上記のような消臭剤を効率よく製造することができる。
According to the present invention, the liquid or mud containing the odor-causing component contains an alkali composed of an alkali metal hydroxide, sulfamic acid, and a chlorine-based oxidant, and contains sulfamic acid and a chlorine-based oxidant. The content ratio is 0.2 to 1 in terms of Cl / N (molar ratio), the content ratio of sulfamic acid and alkali is 1 to 3 in terms of alkali metal / N (molar ratio), and the total amount of water By reacting with the odor-causing component containing the reducing sulfur odorous substance in the liquid or mud, by adding a deodorant containing a combined chlorinating agent aqueous solution prepared as one preparation having a 50 to 90% by weight Can deodorize, enhance the deodorizing effect of chlorine-based oxidants such as hypochlorite, eliminate the generation of chlorine odor, have high safety and stability, low corrosiveness, and handleability Good storage stability, small amount added, and short time Having a deodorizing effect (immediate), which can perform deodorization effectively liquid or slurry product. Moreover, according to the manufacturing method of the deodorizer of this invention, the above deodorizers can be manufactured efficiently.
以下、本発明を実施例、比較例について説明する。各例中の％および部は、特に指示のない限り重量％および重量部を示す。
消臭剤の製造方法は次の通りである。
〔消臭剤の製造方法〕：
各例の表に示す量の純水に水酸化ナトリウムを添加して溶解し、さらにスルファミン酸ナトリウムを添加して溶解し、その後、各表に示す量の次亜塩素酸ナトリウム水溶液を添加して溶解し、各実施例の消臭剤を製造した。実施例の消臭剤における特定の成分を変更または省略して、各比較例の消臭剤を製造した。
Examples of the present invention and comparative examples will be described below. Unless otherwise indicated, “%” and “parts” in each example indicate “% by weight” and “parts by weight”.
The manufacturing method of a deodorant is as follows.
[Method for producing deodorant]:
Add and dissolve sodium hydroxide in the amount of pure water shown in the table of each example, add sodium sulfamate to dissolve, and then add the amount of sodium hypochlorite aqueous solution shown in each table. It melt | dissolved and the deodorizer of each Example was manufactured. The specific component in the deodorizer of an Example was changed or omitted, and the deodorizer of each comparative example was manufactured.
消臭試験方法は次の通りである。
〔消臭試験方法〕：
１）３００ｍＬポリエチレンビーカーに、排水、汚泥などの被処理物の試料２００ｍＬを採取する。
２）各消臭剤を所定の塩素濃度になるよう添加し、スパーテルにて１０秒間攪拌する。
３）消臭剤添加1分後、上記攪拌試料５０ｍＬを５００ｍＬポリエチレンビンに採取し、開閉式の細孔を設けた蓋をして密閉する。
４）振盪機にて２分間強く振盪する。
５）細孔に検知管を挿入し、ポリエチレンビンの空隙に充満した臭気物質濃度を測定する。
The deodorization test method is as follows.
[Deodorization test method]:
1) Collect a 200 mL sample of wastewater, sludge and other objects to be treated in a 300 mL polyethylene beaker.
2) Add each deodorant to a predetermined chlorine concentration and stir with a spatula for 10 seconds.
3) One minute after adding the deodorant, take 50 mL of the stirred sample in a 500 mL polyethylene bottle, and seal it with a lid provided with open / closed pores.
4) Shake vigorously on a shaker for 2 minutes.
5) Insert a detector tube into the pore and measure the concentration of the odorous substance filled in the voids of the polyethylene bottle.
臭気物質の濃度測定方法は次の通りである。
〔臭気物質濃度測定〕：
１）検知管法にて実施。
２）検知管は次のガステック社製検知管を使用。
３）硫化水素；検知管Ｎｏ‥４ＬＬ、４Ｍ、４Ｈ
４）メチルメルカプタン；検知管Ｎｏ‥７１
５）表記中、０ｐｐｍは検知されないことを示す。
６）検知限界は硫化水素、メチルメルカプタンともに１ｐｐｍである。
The method for measuring the concentration of odorous substances is as follows.
[Odor substance concentration measurement]:
1) Implemented by detector tube method.
2) The following detector tube manufactured by Gastec is used as the detector tube.
3) Hydrogen sulfide; Detector tube No. 4LL, 4M, 4H
4) Methyl mercaptan; Detector tube No. 71
5) In the notation, 0 ppm indicates no detection.
6) The detection limit is 1 ppm for both hydrogen sulfide and methyl mercaptan.
〔実施例１、比較例１、２〕：
上記消臭剤の製造方法に従って表１の消臭剤を製造した。実施例１の消臭剤は、アルカリ、スルファミン酸および次亜塩素酸ナトリウムを含む本発明の結合塩素剤に相当するものである。比較例１の消臭剤は、スルファミン酸を含まない次亜塩素酸ナトリウムに相当するものである。比較例２の消臭剤は、スルファミン酸を含まない亜塩素酸ナトリウムからなるものである。
[Example 1, Comparative Examples 1 and 2]:
The deodorizer of Table 1 was manufactured according to the manufacturing method of the said deodorizer. The deodorant of Example 1 corresponds to the combined chlorine agent of the present invention containing alkali, sulfamic acid and sodium hypochlorite. The deodorant of Comparative Example 1 corresponds to sodium hypochlorite containing no sulfamic acid. The deodorizer of the comparative example 2 consists of sodium chlorite which does not contain sulfamic acid.
これらの消臭剤を、下水処理場の重力濃縮汚泥と機械濃縮汚泥の混合汚泥Ａ（ＳＳ：２．７５％、ＶＳＳ（対ＳＳ）：８７．５％、ＴＳ：２．９１％、ＶＴＳ（対ＴＳ）：８５．４％、繊維（対ＳＳ）：２２．９％、ｐＨ５．１５、ＥＣ：１９０ｍＳ／ｍ）に、図１のＣｌ添加率となるように、上記消臭試験方法に従って添加し、消臭剤添加1分後の硫化水素およびメチルメルカプタンの濃度を臭気物質濃度として測定した。 These deodorants were mixed with gravity-concentrated sludge and mechanical-concentrated sludge A (SS: 2.75%, VSS (vs. SS): 87.5%, TS: 2.91%, VTS (sewage treatment plant). TS): 85.4%, fiber (vs SS): 22.9%, pH 5.15, EC: 190 mS / m), added according to the above deodorization test method so that the Cl addition rate of FIG. The concentration of hydrogen sulfide and methyl mercaptan one minute after the addition of the deodorant was measured as the odorous substance concentration.
上記の消臭試験中、実施例１の結合塩素剤の場合は塩素臭がしなかったが、比較例１、２では塩素臭があり、特に比較例１では激しかった。各例の硫化水素濃度の測定結果を図１（ａ）に示し、メチルメルカプタン濃度の測定結果を図１（ｂ）に示す。図１（ａ）および（ｂ）より、硫化水素およびメチルメルカプタンいずれの場合とも、実施例１の結合塩素剤は、比較例１と同じ量の次亜塩素酸ナトリウムを用いるにもかかわらず、比較例１よりも少ない塩素添加率で消臭効果が得られ、酸化力の強い比較例２の亜塩素酸ナトリウムと同等またはそれ以上の消臭効果が得られることが分かる。 During the above deodorization test, the bonded chlorinating agent of Example 1 did not have a chlorine odor, but Comparative Examples 1 and 2 had a chlorine odor, and Comparative Example 1 was particularly intense. The measurement result of the hydrogen sulfide concentration in each example is shown in FIG. 1 (a), and the measurement result of the methyl mercaptan concentration is shown in FIG. 1 (b). 1 (a) and 1 (b), in both cases of hydrogen sulfide and methyl mercaptan, the combined chlorinating agent of Example 1 was compared in spite of using the same amount of sodium hypochlorite as Comparative Example 1. It can be seen that a deodorizing effect can be obtained with a lower chlorine addition rate than in Example 1, and a deodorizing effect equivalent to or higher than that of sodium chlorite in Comparative Example 2 having strong oxidizing power can be obtained.
〔実施例２、比較例３、４〕：
上記消臭剤の製造方法に従って表２の消臭剤を製造した。実施例２、比較例３、４の消臭剤は、前記表１に示した実施例１、比較例１、２の消臭剤における各成分の配合割合を変えたものである。
[Example 2, Comparative Examples 3 and 4]:
The deodorizer of Table 2 was manufactured according to the manufacturing method of the said deodorizer. The deodorizers of Example 2 and Comparative Examples 3 and 4 are obtained by changing the blending ratio of each component in the deodorizers of Example 1 and Comparative Examples 1 and 2 shown in Table 1.
これらの消臭剤を、下水処理場の重力濃縮汚泥Ｂ（ＳＳ：２．４１％、ＶＳＳ（対ＳＳ）：９１．３％、ＴＳ：２．６１％、ＶＴＳ（対ＴＳ）：８４．２％、繊維（対ＳＳ）：４４．０％、ｐＨ５．４５、ＥＣ：１２８．１ｍＳ／ｍ）に、図２のＣｌ添加率となるように、上記消臭試験方法に従って添加し、消臭剤添加1分後の硫化水素およびメチルメルカプタンの濃度を臭気物質濃度として測定した。 These deodorants were added to gravity-concentrated sludge B (SS: 2.41%, VSS (vs SS): 91.3%, TS: 2.61%, VTS (vs TS): 84.2 at the sewage treatment plant. %, Fiber (vs. SS): 44.0%, pH 5.45, EC: 128.1 mS / m) according to the above deodorization test method so that the Cl addition rate of FIG. The concentration of hydrogen sulfide and methyl mercaptan one minute after the addition was measured as the odorous substance concentration.
上記の消臭試験中、実施例２の結合塩素剤の場合は塩素臭がしなかったが、比較例３、４では塩素臭があり、特に比較例３では激しかった。各例の硫化水素濃度の測定結果を図２（ａ）に示し、メチルメルカプタン濃度の測定結果を図２（ｂ）に示す。図２（ａ）および（ｂ）より、硫化水素およびメチルメルカプタンいずれの場合とも、実施例２の結合塩素剤は、比較例３と同じ量の次亜塩素酸ナトリウムを用いるにもかかわらず、比較例３、４よりも少ない塩素添加率で消臭効果が得られ、酸化力の強い比較例４の亜塩素酸ナトリウムより優れた消臭効果が得られることが分かる。 During the above deodorization test, the combined chlorinating agent of Example 2 did not have a chlorine odor, but Comparative Examples 3 and 4 had a chlorine odor, and Comparative Example 3 was particularly intense. The measurement result of the hydrogen sulfide concentration in each example is shown in FIG. 2 (a), and the measurement result of the methyl mercaptan concentration is shown in FIG. 2 (b). 2 (a) and 2 (b), in both cases of hydrogen sulfide and methyl mercaptan, the combined chlorine agent of Example 2 was compared in spite of using the same amount of sodium hypochlorite as Comparative Example 3. It can be seen that the deodorizing effect can be obtained with a lower chlorine addition rate than in Examples 3 and 4, and the deodorizing effect superior to that of the sodium chlorite of Comparative Example 4 having strong oxidizing power can be obtained.
〔実施例３、比較例５、６〕：
上記消臭剤の製造方法に従って表３の消臭剤を製造した。実施例３の消臭剤は、前記実施例１、２の消臭剤の各成分の配合割合を変えたものである。比較例５の消臭剤は、結合塩素剤としてクロラミンＴを用いたものである。比較例６の消臭剤は、実施例３の消臭剤において、スルファミン酸に代えてジエタノールアミンを用いたものである。実施例３、比較例５、６のいずれの場合も、安定な無色〜黄色透明な液体からなる消臭剤が得られた。
[Example 3, Comparative Examples 5 and 6]:
The deodorizer of Table 3 was manufactured according to the manufacturing method of the said deodorizer. The deodorant of Example 3 is obtained by changing the blending ratio of each component of the deodorizers of Examples 1 and 2. The deodorant of Comparative Example 5 uses chloramine T as a combined chlorine agent. The deodorizer of Comparative Example 6 is the same as the deodorizer of Example 3, except that diethanolamine is used instead of sulfamic acid. In both cases of Example 3 and Comparative Examples 5 and 6, a deodorant composed of a stable colorless to yellow transparent liquid was obtained.
このうち実施例３および比較例５の消臭剤を、下水処理場の重力濃縮汚泥と機械濃縮汚泥の混合汚泥Ｃ（ＳＳ：２．１４％、ＶＳＳ（対ＳＳ）：８６．９％、繊維（対ＳＳ）：１８．０％、ｐＨ５．３６、ＥＣ：３３４ｍＳ／ｍ、硫化水素：６３０ｐｐｍ、メチルメルカプタン：５０ｐｐｍ）に、図３のＣｌ添加率となるように、上記消臭試験方法に従って添加し、消臭剤添加1分後の硫化水素およびメチルメルカプタンの濃度を臭気物質濃度として測定した。 Of these, the deodorizers of Example 3 and Comparative Example 5 were mixed sludge C (SS: 2.14%, VSS (vs. SS): 86.9%, mixed sludge of gravity concentrated sludge and mechanically concentrated sludge in the sewage treatment plant, fiber. (Vs. SS): 18.0%, pH 5.36, EC: 334 mS / m, hydrogen sulfide: 630 ppm, methyl mercaptan: 50 ppm) added according to the above deodorization test method so that the Cl addition rate of FIG. The concentration of hydrogen sulfide and methyl mercaptan one minute after the addition of the deodorant was measured as the odorous substance concentration.
上記の消臭試験中、実施例３および比較例５の結合塩素剤の塩素臭はしなかった。各例の硫化水素濃度の測定結果を図３（ａ）に示し、メチルメルカプタン濃度の測定結果を図３（ｂ）に示す。図３（ａ）および（ｂ）より、硫化水素およびメチルメルカプタンいずれの場合とも、実施例３の結合塩素剤は、比較例５と同じ量の塩素濃度の結合塩素剤を用いるにもかかわらず、比較例５よりも少ない塩素添加率で消臭効果が得られることが分かる。 During the above deodorization test, the combined chlorinating agent of Example 3 and Comparative Example 5 did not smell. The measurement result of the hydrogen sulfide concentration in each example is shown in FIG. 3 (a), and the measurement result of the methyl mercaptan concentration is shown in FIG. 3 (b). 3 (a) and 3 (b), in both cases of hydrogen sulfide and methyl mercaptan, the combined chlorinating agent of Example 3 uses a combined chlorinating agent having the same amount of chlorine as Comparative Example 5, but It can be seen that the deodorizing effect can be obtained with a lower chlorine addition rate than in Comparative Example 5.
次に上記表３のうち実施例３および比較例６の消臭剤を、下水処理場の重力濃縮汚泥と機械濃縮汚泥の混合汚泥Ｄ（ＳＳ：２．４１％、ＶＳＳ（対ＳＳ）：９１．３％、繊維（対ＳＳ）：４４．０％、ｐＨ５．３３、ＥＣ：１２８ｍＳ／ｍ）に、図４のＣｌ添加率となるように、上記消臭試験方法に従って添加し、消臭剤添加1分後の硫化水素およびメチルメルカプタンの濃度を臭気物質濃度として測定した。 Next, in Table 3 above, the deodorizers of Example 3 and Comparative Example 6 are mixed sludge D (SS: 2.41%, VSS (vs. SS): 91) of gravity-concentrated sludge and mechanical-concentrated sludge in a sewage treatment plant. 3%, fiber (vs. SS): 44.0%, pH 5.33, EC: 128 mS / m) according to the above deodorization test method so that the Cl addition rate of FIG. The concentration of hydrogen sulfide and methyl mercaptan one minute after the addition was measured as the odorous substance concentration.
上記の消臭試験中、実施例３および比較例６の結合塩素剤の塩素臭はなかった。各例の硫化水素濃度の測定結果を図４（ａ）に示し、メチルメルカプタン濃度の測定結果を図４（ｂ）に示す。図４（ａ）および（ｂ）より、硫化水素およびメチルメルカプタンいずれの場合とも、実施例３の結合塩素剤は、比較例６と同じ量の塩素濃度の結合塩素剤を用いるにもかかわらず、比較例６よりも少ない塩素添加率で消臭効果が得られることが分かる。 During the above deodorization test, there was no chlorine odor of the combined chlorine agent of Example 3 and Comparative Example 6. The measurement result of the hydrogen sulfide concentration in each example is shown in FIG. 4 (a), and the measurement result of the methyl mercaptan concentration is shown in FIG. 4 (b). 4 (a) and 4 (b), in both cases of hydrogen sulfide and methyl mercaptan, the combined chlorinating agent of Example 3 uses a combined chlorinating agent having the same amount of chlorine as Comparative Example 6, but It can be seen that the deodorizing effect can be obtained with a lower chlorine addition rate than in Comparative Example 6.
〔比較例７〜９〕：
上記消臭剤の製造方法に従って表４の消臭剤を製造した。比較例７〜９の消臭剤は、前記表３の実施例３の消臭剤において、それぞれスルファミン酸に代えて、タウリン、グリシン、サルコシンを用いたものである。比較例７〜９のいずれの場合も、安定な黄色透明の液体からなる消臭剤が得られた。
[Comparative Examples 7 to 9]:
The deodorizers shown in Table 4 were produced according to the above method for producing a deodorant. The deodorizers of Comparative Examples 7 to 9 are those using taurine, glycine and sarcosine in place of sulfamic acid in the deodorizer of Example 3 in Table 3 above. In any case of Comparative Examples 7 to 9, a deodorant composed of a stable yellow transparent liquid was obtained.
これらの消臭剤を、実施例３および比較例５の場合と同じ混合汚泥Ｃ（ＳＳ：２．１４％、ＶＳＳ（対ＳＳ）：８６．９％、繊維（対ＳＳ）：１８．０％、ｐＨ５．３６、ＥＣ：３３４ｍＳ／ｍ）に、図５のＣｌ添加率となるように、上記消臭試験方法に従って添加し、消臭剤添加1分後の硫化水素およびメチルメルカプタンの濃度を臭気物質濃度として測定した。 These deodorizers were mixed sludge C (SS: 2.14%, VSS (vs SS): 86.9%, fiber (vs SS): 18.0% as in Example 3 and Comparative Example 5. , PH 5.36, EC: 334 mS / m) according to the above deodorization test method so that the Cl addition rate of FIG. 5 is obtained, and the concentration of hydrogen sulfide and methyl mercaptan one minute after the addition of the deodorant is added to the odor. The substance concentration was measured.
上記の消臭試験中、比較例７〜９の結合塩素剤の塩素臭はしなかった。各例の硫化水素濃度の測定結果を図５（ａ）に、メチルメルカプタン濃度の測定結果を図５（ｂ）に、図３（ａ）、（ｂ）に示した実施例３および比較例５の結果とともに示す。図５（ａ）および（ｂ）より、硫化水素およびメチルメルカプタンいずれの場合とも、実施例３の結合塩素剤は、比較例７〜９と同じ量の塩素濃度の結合塩素剤を用いるにもかかわらず、比較例７〜９よりもはるかに少ない塩素添加率で消臭効果が得られることが分かる。 During the above deodorization test, the chlorine odors of the combined chlorinating agents of Comparative Examples 7 to 9 were not produced. The measurement results of the hydrogen sulfide concentration in each example are shown in FIG. 5 (a), the measurement results of the methyl mercaptan concentration are shown in FIG. 5 (b), and Example 3 and Comparative Example 5 shown in FIGS. 3 (a) and 3 (b). Together with the results. 5 (a) and 5 (b), in both cases of hydrogen sulfide and methyl mercaptan, the combined chlorinating agent of Example 3 uses a combined chlorinating agent having the same amount of chlorine as Comparative Examples 7-9. In addition, it can be seen that the deodorizing effect can be obtained with a much lower chlorine addition rate than Comparative Examples 7-9.
〔実施例４、比較例１０、１１〕：
上記消臭剤の製造方法に従って表５の消臭剤を製造した。実施例４の消臭剤は、前記実施例３の配合割合を変えたものである。比較例１０の消臭剤は、前記実施例４の結合塩素剤に相当するスルファミン酸を含まない次亜塩素酸ナトリウムからなる製剤であり、前記比較例１の配合割合を変えたものに相当する。比較例１１の消臭剤は、前記表３の実施例３において、水酸化ナトリウムを配合しない例に相当する。実施例４、比較例１０のいずれの場合も、安定な黄色透明の液体からなる消臭剤が得られたが、比較例１１の場合は後述の通り、安定した製剤が得られなかった。
[Example 4, Comparative Examples 10 and 11]:
The deodorizer of Table 5 was manufactured according to the said manufacturing method of a deodorizer. The deodorant of Example 4 is obtained by changing the blending ratio of Example 3. The deodorant of Comparative Example 10 is a preparation composed of sodium hypochlorite that does not contain sulfamic acid corresponding to the combined chlorinating agent of Example 4, and corresponds to a composition in which the mixing ratio of Comparative Example 1 is changed. . The deodorant of Comparative Example 11 corresponds to an example in which sodium hydroxide is not blended in Example 3 of Table 3 above. In both cases of Example 4 and Comparative Example 10, a deodorant composed of a stable yellow transparent liquid was obtained, but in the case of Comparative Example 11, a stable preparation was not obtained as described later.
このうち実施例４および比較例１０の消臭剤を、下水処理場の重力濃縮汚泥と機械濃縮汚泥の混合汚泥Ｃ（ＳＳ：２．１４％、ＶＳＳ（対ＳＳ）：８６．９％、繊維（対ＳＳ）：１８．０％、ｐＨ５．３６、ＥＣ：３３４ｍＳ／ｍ）に、図６のＣｌ添加率となるように、上記消臭試験方法に従って添加し、消臭剤添加1分後の硫化水素およびメチルメルカプタンの濃度を臭気物質濃度として測定した。 Of these, the deodorizers of Example 4 and Comparative Example 10 were mixed sludge C (SS: 2.14%, VSS (vs. SS): 86.9%, mixed sludge of gravity concentrated sludge and mechanically concentrated sludge in the sewage treatment plant, fiber. (To SS): 18.0%, pH 5.36, EC: 334 mS / m), according to the above deodorization test method so that the Cl addition rate of FIG. The concentrations of hydrogen sulfide and methyl mercaptan were measured as odorant concentrations.
上記の消臭試験中、実施例４の結合塩素剤の塩素臭はしなかったが、比較例１０の塩素臭は激しかった。これらの例の硫化水素濃度の測定結果を図６（ａ）に示し、メチルメルカプタン濃度の測定結果を図６（ｂ）に示す。図６（ａ）および（ｂ）より、硫化水素およびメチルメルカプタンいずれの場合とも、実施例４の結合塩素剤は、比較例１０と同じ量の次亜塩素酸ナトリウムを用いるにもかかわらず、比較例１０よりも少ない塩素添加率で消臭効果が得られることが分かる。 During the above deodorization test, the combined chlorinating agent of Example 4 did not smell chlorine, but the chlorine odor of Comparative Example 10 was intense. The measurement result of the hydrogen sulfide concentration in these examples is shown in FIG. 6A, and the measurement result of the methyl mercaptan concentration is shown in FIG. 6B. 6 (a) and 6 (b), in both cases of hydrogen sulfide and methyl mercaptan, the combined chlorine agent of Example 4 was compared in spite of using the same amount of sodium hypochlorite as Comparative Example 10. It can be seen that the deodorizing effect can be obtained with a lower chlorine addition rate than in Example 10.
上記の比較例１１の場合、純水に水酸化ナトリウムを添加することなくスルファミン酸を添加して溶解し、さらに次亜塩素酸ナトリウムを添加したところ、次亜塩素酸ナトリウム添加の直後から泡が発生し、安定した製剤が得られなかった。 In the case of the above Comparative Example 11, sulfamic acid was added and dissolved in pure water without adding sodium hydroxide, and when sodium hypochlorite was further added, bubbles immediately after the addition of sodium hypochlorite. The stable formulation was not obtained.
〔比較例１２〜１４〕：
上記消臭剤の製造方法に従って表６の消臭剤を製造した。比較例１２〜１４の消臭剤は、前記表３の実施例３において、水酸化ナトリウムを配合しない例であって、前記実施例４の結合剤におけるスルファミン酸に代えて、それぞれタウリン、グリシン、サルコシンを用いたものに相当する。
[Comparative Examples 12-14]:
The deodorizers shown in Table 6 were produced according to the above method for producing a deodorant. The deodorizers of Comparative Examples 12 to 14 are examples in which sodium hydroxide was not blended in Example 3 of Table 3 above. Instead of sulfamic acid in the binder of Example 4, taurine, glycine, It corresponds to the one using sarcosine.
タウリンを用いた比較例１２の場合、純水に水酸化ナトリウムを添加することなくタウリンを添加したところ、タウリンが水に完全溶解しなかった。この状態で次亜塩素酸ナトリウムを添加したところ、次亜塩素酸ナトリウム添加の直後から泡が発生し、安定した製剤が得られなかった。 In the case of Comparative Example 12 using taurine, taurine was not completely dissolved in water when taurine was added to pure water without adding sodium hydroxide. When sodium hypochlorite was added in this state, foam was generated immediately after the addition of sodium hypochlorite, and a stable formulation could not be obtained.
グリシンを用いた比較例１３の場合、純水に水酸化ナトリウムを添加することなく、グリシンを添加して溶解し、さらに次亜塩素酸ナトリウムを添加したところ、次亜塩素酸ナトリウムの添加後、次第に泡が発生し、安定した製剤が得られなかった。 In the case of Comparative Example 13 using glycine, glycine was added and dissolved without adding sodium hydroxide to pure water, and sodium hypochlorite was further added. After the addition of sodium hypochlorite, Bubbles gradually formed, and a stable preparation could not be obtained.
サルコシンを用いた比較例１４の場合、純水に水酸化ナトリウムを添加することなく、サルコシンを添加して溶解し、さらに次亜塩素酸ナトリウムを添加したところ、次亜塩素酸ナトリウムの添加後、次第に泡が発生し、安定した製剤が得られなかった。 In the case of Comparative Example 14 using sarcosine, sarcosine was added and dissolved in pure water without adding sodium hydroxide, and sodium hypochlorite was further added. After the addition of sodium hypochlorite, Bubbles gradually formed, and a stable preparation could not be obtained.
以上の結果より、本発明の消臭剤を添加することにより、次亜塩素酸塩の消臭効果を高めるとともに、塩素臭の発生をなくし、安全性、安定性が高く、腐食性が低く、かつ取扱性が良好であり、少ない添加量で、短時間に効果的に液または泥状物の消臭を行うことができることがわかる。 From the above results, by adding the deodorant of the present invention, the deodorizing effect of hypochlorite is enhanced, the generation of chlorine odor is eliminated, safety and stability are high, and corrosivity is low. In addition, it can be seen that the handleability is good and the liquid or mud can be effectively deodorized in a short time with a small addition amount.
〔実施例５〜７〕：
上記消臭剤の製造方法に従って表７の消臭剤を製造した。実施例５〜７の消臭剤は、いずれもアルカリ、スルファミン酸および次亜塩素酸ナトリウムを含む本発明の結合塩素剤に相当するものであり、各成分の添加量を変えて製造試験を行った。
[Examples 5 to 7]:
The deodorizer of Table 7 was manufactured according to the manufacturing method of the said deodorizer. The deodorizers of Examples 5 to 7 correspond to the combined chlorinating agent of the present invention containing alkali, sulfamic acid and sodium hypochlorite, and production tests were carried out by changing the amount of each component added. It was.
〔実施例８、９〕：
上記消臭剤の製造方法に従って表８の消臭剤を製造した。実施例８、９の消臭剤は、いずれも実施例５〜７の消臭剤と同様に、アルカリ、スルファミン酸および次亜塩素酸ナトリウムを含むものであり、添加量を変えて製造試験を行った。
[Examples 8 and 9]:
The deodorizers shown in Table 8 were produced according to the above method for producing a deodorant. The deodorizers of Examples 8 and 9 both contain alkali, sulfamic acid and sodium hypochlorite as in the deodorizers of Examples 5 to 7, and the production amount was changed. went.
表８において、＊１、＊２の製造当日外観は、いずれも次亜塩素酸ナトリウムの添加時、徐々に添加しないと、塩素ガスと推測される泡が発生した。＊３の４０℃保管７日後外観は、少量の針状結晶が析出した。＊４の同７日後外観は、４０℃で分解してガスが発生し、噴出した模様である。結晶の析出も認められた。＊５の４０℃保管１３日後外観は、針状結晶が増加した。＊６の４０℃保管２９日後外観は、４０℃で白色沈殿が生じ、液の淡黄色は退色した。 In Table 8, the appearance of * 1 and * 2 on the day of production produced bubbles presumed to be chlorine gas unless sodium hypochlorite was added gradually when sodium hypochlorite was added. * 3 After 7 days of storage at 40 ° C., a small amount of acicular crystals precipitated on the appearance. The appearance after 7 days of * 4 appears to have decomposed at 40 ° C. to generate gas and erupt. Crystal precipitation was also observed. * 5 After 13 days of storage at 40 ° C., the appearance increased in acicular crystals. * 6 The appearance after storage at 40 ° C. for 29 days was white precipitation at 40 ° C., and the pale yellow color of the liquid was faded.
表７および８より、表８の実施例８、９では、次亜塩素酸ナトリウムを徐々に添加するかぎり、結合塩素剤の製造は可能であり、現地で使用前に製造することは可能であることが分かる。これに対し表７の実施例５〜７では、製剤はアルカリを過剰に添加し、強アルカリ下で安定化すること、特にスルファミン酸に対して、中和相手である水酸化ナトリウムをモル比で１．４倍以上添加することにより安定化し、貯蔵安定性に優れることが分かる。製剤は高温保存にて不安定化するが、４０℃保管でも１月程度の期間では安定性を保つことが分かる。 From Tables 7 and 8, in Examples 8 and 9 of Table 8, as long as sodium hypochlorite is gradually added, it is possible to produce a combined chlorinating agent, and it is possible to produce it on site before use. I understand that. On the other hand, in Examples 5 to 7 in Table 7, the formulation was added with an excessive amount of alkali and stabilized under strong alkali. In particular, sodium hydroxide as a neutralizing partner was added at a molar ratio with respect to sulfamic acid. It can be seen that by adding 1.4 times or more, it is stabilized and excellent in storage stability. It can be seen that the preparation is destabilized by high-temperature storage, but the stability is maintained in a period of about one month even when stored at 40 ° C.
〔実施例１０〜１２〕：
上記消臭剤の製造方法に従って表９の消臭剤を製造した。実施例１０〜１２の消臭剤は、いずれもアルカリ、スルファミン酸および次亜塩素酸ナトリウムを含む本発明の結合塩素剤に相当するものであり、水の量を変えて製造試験を行った。
[Examples 10 to 12]:
The deodorizer of Table 9 was manufactured according to the manufacturing method of the said deodorizer. The deodorizers of Examples 10 to 12 all correspond to the combined chlorinating agent of the present invention containing alkali, sulfamic acid and sodium hypochlorite, and production tests were carried out by changing the amount of water.
表９において、＊７の４０℃保管８日後外観は、少量の針状結晶の析出が認められた。＊８の４０℃保管１７日後外観は、針状結晶に加えて白色沈殿が認められた。＊９の４０℃保管２９日後外観は、針状結晶に加えて白色沈殿が認められた。表９より、実施例１２では、Ｃｌ／Ｎ（モル比）１以下とすることにより、結合塩素剤の製造は可能であり、現地で使用前に製造することは可能であることが分かる。これに対し実施例１０、１１では、Ｃｌ／Ｎ（モル比）０．９以下とすることにより、貯蔵安定性に優れる結合塩素剤の製造は可能であることが分かる。製剤は高温保存にて不安定化するが、４０℃保管でも１月程度の期間では安定性を保つことが分かる。 In Table 9, the appearance of * 7 after 8 days storage at 40 ° C. was observed to deposit a small amount of needle-like crystals. As for the appearance of * 8 after storage at 40 ° C. for 17 days, white precipitate was observed in addition to needle-like crystals. The appearance of * 9 after storage at 40 ° C. for 29 days was white precipitate in addition to needle-like crystals. From Table 9, it can be seen that in Example 12, when the Cl / N (molar ratio) is 1 or less, the combined chlorine agent can be manufactured, and can be manufactured on site before use. On the other hand, in Examples 10 and 11, it can be seen that by setting Cl / N (molar ratio) to 0.9 or less, it is possible to produce a bonded chlorine agent having excellent storage stability. It can be seen that the preparation is destabilized by high-temperature storage, but the stability is maintained in a period of about one month even when stored at 40 ° C.
〔実施例１３、１４、比較例１５〕：
上記消臭剤の製造方法に従って表１０の消臭剤を製造した。実施例１３、１４、比較例１５の消臭剤は、いずれもアルカリ、スルファミン酸および次亜塩素酸ナトリウムを含む本発明の結合塩素剤に相当するものであり、アルカリ水溶液の水の量を変えて製造試験を行った。
[Examples 13 and 14, Comparative Example 15]:
The deodorizers shown in Table 10 were produced according to the above deodorant production method. The deodorizers of Examples 13 and 14 and Comparative Example 15 all correspond to the combined chlorine agent of the present invention containing alkali, sulfamic acid and sodium hypochlorite, and the amount of water in the alkaline aqueous solution is changed. A manufacturing test was conducted.
表１０において、比較例１５では、アルカリ水溶液は水の量が５５重量％未満であり、スルファミン酸（粉末）が溶解しないため、スルファミン酸−アルカリ混合水溶液が得られず、結合塩素剤の製造ができなかった。アルカリ水溶液は水の量が５５重量％以上、好ましくは６０重量％以上とすることにより、貯蔵安定性に優れた結合塩素剤を製造できることが分かる。 In Table 10, in Comparative Example 15, since the amount of water in the alkaline aqueous solution is less than 55% by weight and the sulfamic acid (powder) does not dissolve, a sulfamic acid-alkali mixed aqueous solution cannot be obtained, and the combined chlorine agent can be produced. could not. It can be seen that when the amount of water in the alkaline aqueous solution is 55% by weight or more, preferably 60% by weight or more, a combined chlorine agent excellent in storage stability can be produced.
本発明は、排水、汚泥、ヘドロ等の臭気が問題となる液または泥状物の消臭方法および消臭剤、特に硫化水素、メルカプタンに起因する臭気を除去する液または泥状物の消臭方法および消臭剤に利用可能である。 The present invention relates to a deodorizing method and deodorant for liquids or sludges in which odors such as drainage, sludge, sludge, etc. are problematic, and in particular, deodorizing liquids or sludges for removing odors caused by hydrogen sulfide and mercaptans. Available for methods and deodorants.
Claims (7)
アルカリ金属水酸化物からなるアルカリと、スルファミン酸と、塩素系酸化剤とを含有し、スルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１であり、スルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３であり、全体の水の量が５０〜９０重量％である一製剤として調製された結合塩素剤水溶液を含む消臭剤を添加し、
液または泥状物中の還元性硫黄臭気物質を含む臭気原因成分と反応して消臭を行う
ことを特徴とする液または泥状物の消臭方法。 To liquid or mud containing odor-causing components,
It contains an alkali composed of an alkali metal hydroxide, sulfamic acid, and a chlorine-based oxidant, and the content ratio of sulfamic acid and chlorine-based oxidant is 0.2 to 1 in terms of Cl / N (molar ratio). Yes , combined chlorinating agent aqueous solution prepared as one preparation in which the content ratio of sulfamic acid and alkali is 1 to 3 in terms of alkali metal / N (molar ratio), and the total amount of water is 50 to 90% by weight Add deodorant containing
A method for deodorizing a liquid or a mud, characterized by reacting with an odor-causing component containing a reducing sulfur odor substance in the liquid or a mud, to deodorize the liquid or the mud.
アルカリ金属水酸化物からなるアルカリと、スルファミン酸と、塩素系酸化剤とを含有し、スルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１であり、スルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３であり、全体の水の量が５０〜９０重量％である一製剤として調製された結合塩素剤水溶液を含むことを特徴とする液または泥状物の消臭剤。 A deodorant which is added to a liquid or mud containing an odor-causing component and deodorizes by reacting with the odor-causing component containing a reducing sulfur odor substance in the liquid or mud,
It contains an alkali composed of an alkali metal hydroxide, sulfamic acid, and a chlorine-based oxidant, and the content ratio of sulfamic acid and chlorine-based oxidant is 0.2 to 1 in terms of Cl / N (molar ratio). Yes , combined chlorinating agent aqueous solution prepared as one preparation in which the content ratio of sulfamic acid and alkali is 1 to 3 in terms of alkali metal / N (molar ratio), and the total amount of water is 50 to 90% by weight A liquid or mud deodorant characterized by comprising
アルカリ金属水酸化物からなるアルカリ水溶液にスルファミン酸をスルファミン酸とアルカリとの含有割合が、アルカリ金属／Ｎ（モル比）で１〜３となる量で添加して溶解し、得られたスルファミン酸−アルカリ混合水溶液に、塩素系酸化剤をスルファミン酸と塩素系酸化剤との含有割合が、Ｃｌ／Ｎ（モル比）で０．２〜１となる量で添加して混合し、全体の水の量が５０〜９０重量％である一製剤として調製することを特徴とする液または泥状物の消臭剤の製造方法。 A method for producing a deodorant that is added to a liquid or mud containing an odor-causing component and reacts with the odor-causing component containing a reducing sulfur odor substance in the liquid or mud, and deodorizes.
A sulfamic acid obtained by adding and dissolving sulfamic acid in an aqueous alkali solution comprising an alkali metal hydroxide in an amount such that the content ratio of sulfamic acid and alkali is 1 to 3 in terms of alkali metal / N (molar ratio) is obtained. - a mixed alkali aqueous solution, the content of the chlorine-based oxidizing agent sulfamic acid and chlorine-based oxidizing agent, added and mixed in an amount of 0.2 to 1 at Cl / N (mol ratio), the total water A method for producing a liquid or mud deodorant, characterized in that the preparation is prepared as one preparation having an amount of 50 to 90% by weight .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010079193A JP5725273B2 (en) | 2010-03-30 | 2010-03-30 | Method for deodorizing liquid or mud, deodorant and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010079193A JP5725273B2 (en) | 2010-03-30 | 2010-03-30 | Method for deodorizing liquid or mud, deodorant and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011206412A JP2011206412A (en) | 2011-10-20 |
| JP5725273B2 true JP5725273B2 (en) | 2015-05-27 |
Family
ID=44938177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010079193A Active JP5725273B2 (en) | 2010-03-30 | 2010-03-30 | Method for deodorizing liquid or mud, deodorant and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5725273B2 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2991001B2 (en) * | 1993-05-10 | 1999-12-20 | 栗田工業株式会社 | Deodorizing method of dewatered sludge cake |
| JPH07148234A (en) * | 1993-11-26 | 1995-06-13 | Sogo Yatsukou Kk | Odor suppressing agent |
| JP2000157967A (en) * | 1998-11-25 | 2000-06-13 | Ebara Corp | Method for deodorizing sewage and sludge |
| JP2003024994A (en) * | 2001-07-19 | 2003-01-28 | Tokuyama Corp | Sludge treatment method |
| JP3832399B2 (en) * | 2001-08-28 | 2006-10-11 | 栗田工業株式会社 | Bactericidal algicide composition and water-based bactericidal algae method |
| US20040062742A1 (en) * | 2002-09-30 | 2004-04-01 | Winston Anthony E. | Deodorant product containing chlorinating agents and buffered alkaline salts |
| JP5280602B2 (en) * | 2003-01-30 | 2013-09-04 | 水ｉｎｇ株式会社 | Odor generation prevention method |
| JP2006015188A (en) * | 2004-06-30 | 2006-01-19 | Toshiba Corp | Method for reducing organic sulfur odor of sludge and method for reducing oxidizing property of sludge supernatant |
-
2010
- 2010-03-30 JP JP2010079193A patent/JP5725273B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011206412A (en) | 2011-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6068861A (en) | Concentrated aqueous bromine solutions and their preparation | |
| JP5141163B2 (en) | Bactericidal and algae killing method | |
| JP2007526244A5 (en) | ||
| JPH0655183A (en) | Composition and method for suppressing odor of sulfide containing water | |
| JP6412639B2 (en) | Ammonia nitrogen-containing wastewater treatment method and ammonia nitrogen decomposing agent | |
| KR20100057847A (en) | Bactericidal/algicidal method | |
| CN108041073A (en) | Potassium peroxymonosulfate disinfectant | |
| CN102256713A (en) | Aqueous hydrogen peroxide solution of excellent stability | |
| JP6649697B2 (en) | Water sterilization method | |
| JP5725273B2 (en) | Method for deodorizing liquid or mud, deodorant and method for producing the same | |
| US20090223892A1 (en) | Use of nitrate salts for suppressing disturbing odours | |
| JP2002219494A (en) | Deodorant and deodorizing method | |
| JP2006083135A (en) | Method for producing hypobromous acid in water system | |
| JP4102943B2 (en) | Deodorant | |
| KR102006328B1 (en) | Method of preparation of drug cleaning fluids for removing TVOCs and odour-causing substances | |
| JP5982852B2 (en) | Deodorization method and deodorant kit | |
| JP2004216252A (en) | Method for suppressing odor of dehydrated sludge cake | |
| JP2000185290A (en) | Deodorizing method | |
| JP2007083094A (en) | Deodorant for sulfur-based malodorous substance | |
| JP2000005774A (en) | Deodorizing method | |
| JP2001300545A (en) | Deodorizing method | |
| JP2000296170A (en) | Method for removing ammonium odor, and deodorant | |
| JPS6168402A (en) | Antifoulant composition | |
| JP4214366B2 (en) | Deodorizing method and deodorant | |
| JP6834231B2 (en) | Deodorants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130322 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130913 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130924 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140722 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140919 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150304 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150317 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5725273 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |