JP2021183336A - Method for preventing adhesion of marine organisms and antiadhesive agent used therefor - Google Patents
Method for preventing adhesion of marine organisms and antiadhesive agent used therefor Download PDFInfo
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- chlorine dioxide
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000000181 anti-adherent effect Effects 0.000 title abstract 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 163
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 97
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 81
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 81
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000460 chlorine Substances 0.000 claims abstract description 73
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 73
- 239000013535 sea water Substances 0.000 claims abstract description 69
- 239000000498 cooling water Substances 0.000 claims abstract description 18
- 239000012320 chlorinating reagent Substances 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 58
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 52
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 51
- 229910052794 bromium Inorganic materials 0.000 abstract description 51
- 239000003814 drug Substances 0.000 abstract description 21
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 23
- 229940079593 drug Drugs 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 15
- 239000005708 Sodium hypochlorite Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000002265 prevention Effects 0.000 description 13
- 241000237536 Mytilus edulis Species 0.000 description 12
- 235000020638 mussel Nutrition 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- VWPXUKSDWYXLKV-UHFFFAOYSA-N bromosulfamic acid Chemical compound OS(=O)(=O)NBr VWPXUKSDWYXLKV-UHFFFAOYSA-N 0.000 description 9
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 6
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 6
- 229960002218 sodium chlorite Drugs 0.000 description 6
- ZZDUJRFHYVLCJF-UHFFFAOYSA-N O[Br][Na] Chemical group O[Br][Na] ZZDUJRFHYVLCJF-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 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 3
- UGLFQJOXHCQGFQ-UHFFFAOYSA-N 1,3-dichloro-1,3,5-triazinane-2,4,6-trione;potassium Chemical compound [K].ClN1C(=O)NC(=O)N(Cl)C1=O UGLFQJOXHCQGFQ-UHFFFAOYSA-N 0.000 description 3
- 241000238586 Cirripedia Species 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000007973 cyanuric acids Chemical class 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 3
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 3
- 230000010071 organism adhesion Effects 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- VPMBPDKLCXQCSR-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 VPMBPDKLCXQCSR-UHFFFAOYSA-N 0.000 description 3
- UNWRHVZXVVTASG-UHFFFAOYSA-N 1,3-dichloro-1,3,5-triazinane-2,4,6-trione;sodium Chemical compound [Na].ClN1C(=O)NC(=O)N(Cl)C1=O UNWRHVZXVVTASG-UHFFFAOYSA-N 0.000 description 2
- DTVKQXANIZSFFW-UHFFFAOYSA-N 1-chloro-1,3,5-triazinane-2,4,6-trione;potassium Chemical compound [K].ClN1C(=O)NC(=O)NC1=O DTVKQXANIZSFFW-UHFFFAOYSA-N 0.000 description 2
- GMUGQBODWQCTFZ-UHFFFAOYSA-N 1-chloro-1,3,5-triazinane-2,4,6-trione;sodium Chemical compound [Na].ClN1C(=O)NC(=O)NC1=O GMUGQBODWQCTFZ-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NREBCEOGTRTAPW-UHFFFAOYSA-N NC=1[ClH]C=CC1 Chemical compound NC=1[ClH]C=CC1 NREBCEOGTRTAPW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- -1 tribrolamin Chemical compound 0.000 description 2
- ISAOUZVKYLHALD-UHFFFAOYSA-N 1-chloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)NC(=O)NC1=O ISAOUZVKYLHALD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 102000006835 Lamins Human genes 0.000 description 1
- 108010047294 Lamins Proteins 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 241001646398 Pseudomonas chlororaphis Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SISAYUDTHCIGLM-UHFFFAOYSA-N bromine dioxide Inorganic materials O=Br=O SISAYUDTHCIGLM-UHFFFAOYSA-N 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical class ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000005053 lamin Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- ATMBAYHJONYZNY-UHFFFAOYSA-N potassium;1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [K].ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O ATMBAYHJONYZNY-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、海生生物の付着防止方法およびそれに用いる付着防止剤に関する。さらに詳しくは、本発明は、低濃度の薬剤添加でその効果を長期間持続し、しかも広範な海生生物種の付着を防止し得る海生生物の付着防止方法およびそれに用いる付着防止剤に関する。 The present invention relates to a method for preventing the adhesion of marine organisms and an anti-adhesion agent used thereof. More specifically, the present invention relates to a method for preventing the adhesion of marine organisms, which can maintain the effect for a long period of time by adding a low concentration of a drug, and can prevent the adhesion of a wide range of marine organisms, and an anti-adhesion agent used thereof.
海水は、工業用の冷却水として、特に火力発電所や原子力発電所の復水器の冷却水として多量に使用されている。そのため、海水取水路壁や配管内および熱交換器内には、ムラサキイガイなどのイガイ類やフジツボ類やコケムシ類などの海生生物種が多量に付着して、様々な障害を惹き起こす。これらの中でも足糸で着生するムラサキイガイなどの二枚貝類は、成長が速く、成貝になると熱交換器チューブの一部を閉塞させて海水の通水を阻害し、また乱流を生じさせ、エロージョン腐食などの障害を惹き起こす。 Seawater is used in large quantities as industrial cooling water, especially as cooling water for condensers of thermal power plants and nuclear power plants. Therefore, a large amount of mussels such as mussels and marine species such as barnacles and mussels adhere to the walls of seawater intake channels, pipes, and heat exchangers, causing various disorders. Among these, bivalves such as mussels that grow on byssus grow fast, and when they become adults, they block part of the heat exchanger tube, obstructing the passage of seawater and causing turbulence. Causes obstacles such as erosion corrosion.
これら海生生物種の密集着生（付着）を防止するために、従来から次亜塩素酸ナトリウム、電解塩素もしくは塩素ガスなどの塩素発生剤（「塩素剤」ともいう）、過酸化水素もしくは過酸化水素発生剤（「過酸化水素剤」ともいう）の添加が行われている（例えば、特開平１１−３７６６６号公報：特許文献１および特開２００５−１４４２１２号公報：特許文献２参照）。 In order to prevent the dense formation (adhesion) of these marine species, conventional chlorine generators such as sodium hypochlorite, electrolytic chlorine or chlorine gas (also called "chlorine agents"), hydrogen peroxide or excess A hydrogen oxide generator (also referred to as “hydrogen peroxide agent”) has been added (see, for example, JP-A-11-37666: Patent Document 1 and JP-A-2005-144212: Patent Document 2).
一方、二酸化塩素は、殺菌力が強く、有害な有機塩素化合物を形成しないため、環境への影響が小さいという利点がある。
例えば、特開平１−２７５５０４号公報（特許文献３）には、二酸化塩素または二酸化塩素発生剤を有効成分とする水中付着生物防除剤に関する技術が、特開平６−１５３７５９号公報（特許文献４）には、淡水または海水を使用する施設に設置された淡水または海水を通す水路に、二酸化塩素水溶液を連続的もしくは比較的高濃度の二酸化塩素水溶液を間欠的に注入することからなる、水路に付着する生物の付着防止または防除方法に関する技術が開示されている。
しかしながら、二酸化塩素は化学物質として極めて不安定であり、海生生物の付着防止効果の持続性に問題がある。
また、本出願人は、二酸化塩素と過酸化水素とを併用する海生生物の付着防止方法およびそれに用いる付着防止剤を提案している（特許第５８７９５９６公報：特許文献５参照）。
なお、特開２００５−７２５４号公報（特許文献６）には、殺菌剤として塩素系薬剤と二酸化塩素とを併用する浴槽水の殺菌方法に関する技術が開示されている。しかし、この技術の対象水系は浴槽水であり、海水冷却水系ではなく、その目的はレジオネラ菌などの殺菌やバイオフィルムの破壊であり、海生生物の付着防止ではなく、本発明とは技術分野や目的が異なる。
On the other hand, chlorine dioxide has a strong bactericidal activity and does not form harmful organic chlorine compounds, so that it has an advantage of having a small impact on the environment.
For example, Japanese Patent Application Laid-Open No. 1-275504 (Patent Document 3) describes a technique relating to an aqueous solution-adhering biological control agent containing chlorine dioxide or a chlorine dioxide generating agent as an active ingredient in Japanese Patent Application Laid-Open No. 6-153759 (Patent Document 4). Adhesion to the canal, which consists of continuous or intermittent injection of an aqueous solution of chlorine dioxide into the canal of freshwater or seawater installed in a facility that uses freshwater or seawater. Disclosed is a technique for preventing or controlling the adhesion of living organisms.
However, chlorine dioxide is extremely unstable as a chemical substance, and there is a problem in sustaining the effect of preventing the adhesion of marine organisms.
In addition, the applicant has proposed a method for preventing the adhesion of marine organisms in which chlorine dioxide and hydrogen peroxide are used in combination, and an anti-adhesion agent used thereof (see Patent No. 5879596: Patent Document 5).
Japanese Patent Application Laid-Open No. 2005-7254 (Patent Document 6) discloses a technique for sterilizing bath water in which a chlorine-based agent and chlorine dioxide are used in combination as a sterilizing agent. However, the target water system of this technology is bathtub water, not seawater cooling water system, and its purpose is to sterilize regionella bacteria and destroy biofilms, not to prevent the adhesion of marine organisms, but to the technical field of the present invention. And the purpose is different.
海生生物の付着防止において、環境への影響を考慮して塩素剤や臭素剤などのハロゲン系薬剤の使用を避ける動きがある中、現状では旧来のプラント設備を使用するため塩素剤や臭素剤を使用せざるを得ない場合や、リサイクル処理により副生された塩素系化合物を有効利用する場合がある。
このような状況の中で、環境への影響に配慮して塩素剤の使用量を低減しつつ、優れた海生生物の付着防止効果を発揮し得る薬剤およびそれを用いる方法の開発が望まれている。
In order to prevent the adhesion of marine organisms, there is a movement to avoid the use of halogen-based agents such as chlorine agents and bromine agents in consideration of the environmental impact, but at present, chlorine agents and bromine agents are used because conventional plant equipment is used. There are cases where there is no choice but to use, or there are cases where chlorine-based compounds produced by the recycling process are effectively used.
Under such circumstances, it is desired to develop a drug that can exert an excellent anti-adhesion effect on marine organisms while reducing the amount of chlorine agent used in consideration of the impact on the environment and a method using the agent. ing.
本発明は、低濃度の薬剤添加でその効果を長期間持続し、しかも広範な海生生物種やスライムの付着を防止し得る海生生物の付着防止方法およびそれに用いる付着防止剤を提供することを課題とする。 INDUSTRIAL APPLICABILITY The present invention provides a method for preventing the adhesion of marine organisms, which can maintain the effect for a long period of time by adding a low concentration of a drug, and can prevent the adhesion of a wide range of marine species and slime, and an adhesion inhibitor used thereto. Is the subject.
本発明の発明者は、塩素剤または臭素剤と二酸化塩素との併用により、ムラサキイガイなどのイガイ類を含む広範な海生生物種の付着を長期間持続して有効に防止し得ること、さらには従来技術の塩素剤または臭素剤および二酸化塩素の単独使用と比較して、薬剤添加量を低減させても海生生物やスライム等の有効な付着防止効果が得られることを見い出し、本発明を完成するに到った。 The inventor of the present invention can effectively prevent the adhesion of a wide range of marine organisms including mussels such as purple mussel by using a chlorinating agent or a bromine agent in combination with chlorine dioxide for a long period of time. The present invention was completed by finding that an effective anti-adhesion effect for marine organisms, slime, etc. can be obtained even if the amount of the chemical added is reduced as compared with the conventional conventional use of a chlorine agent or a bromine agent and chlorine dioxide alone. I came to do it.
かくして、本発明によれば、海水冷却水系の海水中で０．０１〜０．３ｍｇ／Ｌの有効塩素濃度になるように塩素剤（但し、二酸化塩素を除く）または臭素剤と、０．００５〜０．０５ｍｇ／Ｌの濃度になるように二酸化塩素とをこの順もしくは逆順でまたは同時に、１日１〜２４時間添加して、海水冷却水系への海生生物の付着を防止することからなり、
前記塩素剤が、次亜塩素酸ナトリウム、Ｎ−クロロスルファマートおよびモノクロラミンから選択され、前記臭素剤が、次亜臭素酸ナトリウム、Ｎ−ブロモスルファマートおよびモノブロラミンから選択されることを特徴とする海生生物の付着防止方法が提供される。
Thus, according to the present invention, a chlorine agent (excluding chlorine dioxide) or a bromine agent and 0.005 so as to have an effective chlorine concentration of 0.01 to 0.3 mg / L in seawater of a seawater cooling water system. Chlorine dioxide is added in this order or in reverse order or simultaneously to a concentration of ~ 0.05 mg / L for 1 to 24 hours a day to prevent marine organisms from adhering to the seawater cooling water system. ,
The chlorinating agent is selected from sodium hypochlorite, N-chlorosulfamate and monobrolamine, and the brominating agent is selected from sodium hypobromous acid, N-bromosulfamate and monobrolamin. A characteristic method for preventing the adhesion of marine organisms is provided.
本発明によれば、低濃度の薬剤添加でその効果を長期間持続し、しかも広範な海生生物種やスライムの付着を防止し得る海生生物の付着防止方法を提供することができる。
すなわち、本発明の海生生物の付着防止方法では、塩素剤または臭素剤と二酸化塩素とが海水中で相乗効果を奏する濃度になるように添加されるため、両者の海生生物の付着防止効果が一定時間持続して発揮され、塩素剤または臭素剤と二酸化塩素とをそれぞれ単独で使用した場合よりも、少量添加でより優れた海生生物の付着防止効果を得ることができる。
また、本発明の海生生物の付着防止方法は、広範な海生生物種、例えば、ムラサキイガイなどのイガイ類やフジツボ類、コケムシ類などの海生生物やスライムの付着防止に有効である。
INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for preventing the adhesion of marine organisms, which can maintain the effect for a long period of time by adding a low concentration of a drug and can prevent the adhesion of a wide range of marine species and slime.
That is, in the method for preventing the adhesion of marine organisms of the present invention, since the chlorine agent or the bromine agent and chlorine dioxide are added so as to have a synergistic effect in seawater, the effect of preventing the adhesion of both marine organisms is achieved. Is exhibited continuously for a certain period of time, and a better anti-adhesion effect on marine organisms can be obtained with a small amount of addition as compared with the case where a chlorine agent or a bromine agent and chlorine dioxide are used alone.
In addition, the method for preventing the adhesion of marine organisms of the present invention is effective in preventing the adhesion of a wide range of marine species, such as mussels such as mussels, barnacles, and marine organisms such as mussels, and slimes.
また、本発明の海生生物の付着防止方法は、次のいずれか１つの要件を満足する場合に、上記の効果をさらに発揮する。
（１）塩素剤または臭素剤および二酸化塩素が、海水に対してそれぞれ０．００５〜０．３ｍｇ／Ｌの有効塩素濃度および０．００２〜０．２ｍｇ／Ｌの濃度になるように海水中に添加される。
（２）塩素剤または臭素剤と二酸化塩素とが１日１〜２４時間添加される。
（３）塩素剤または臭素剤が添加された海水冷却水系の海水中に二酸化塩素を添加する、すなわち塩素剤または臭素剤と二酸化塩素とがこの順で海水冷却水系の海水中に添加される。
（４）塩素剤または臭素剤が、
（ａ）塩素ガス、次亜塩素酸カルシウム、次亜塩素酸ナトリウム、塩素化イソシアヌル酸、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、モノクロロイソシアヌル酸ナトリウム、モノ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およびトリクロロイソシアヌル酸カリウムの中から選択される一種以上の水中で次亜塩素酸を生成する物質、
（ｂ）次亜臭素酸ナトリウム、臭化ナトリウムと次亜塩素酸ナトリウムとの反応物および臭素水から選択される一種以上の水中で次亜臭素酸を生成する物質、
（ｃ）海水電解液、または
（ｄ）モノクロラミン、ジクロラミン、トリクロラミン、モノブロラミン、ジブロラミン、トリブロラミン、Ｎ−クロロスルファマートおよびＮ−ブロモスルファマートから選択される一種以上の結合塩素または結合臭素
である。
Further, the method for preventing the adhesion of marine organisms of the present invention further exerts the above-mentioned effect when any one of the following requirements is satisfied.
(1) In seawater so that the chlorine agent or bromine agent and chlorine dioxide have an effective chlorine concentration of 0.005 to 0.3 mg / L and a concentration of 0.002 to 0.2 mg / L, respectively, with respect to seawater. Is added.
(2) A chlorine agent or a bromine agent and chlorine dioxide are added for 1 to 24 hours a day.
(3) Chlorine dioxide is added to the seawater of the seawater cooling water system to which the chlorine agent or the bromine agent is added, that is, the chlorine or bromine agent and chlorine dioxide are added to the seawater of the seawater cooling water system in this order.
(4) Chlorine or bromine
(A) Chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, dichloroisocyanuric acid sodium, dichloroisocyanuric acid potassium, monochloroisocyanuric acid sodium, monochloroisocyanuric acid potassium, trichloroisocyanuric acid sodium and trichloroisocyanuric acid. A substance that produces hypochlorous acid in one or more waters selected from potassium acid,
(B) A substance that produces hypobromous acid in one or more waters selected from sodium hypobromous acid, a reaction product of sodium bromide and sodium hypochlorite, and bromine water.
(C) Seawater electrolyte or (d) One or more bound chlorine or bonds selected from monochloramine, dichloramine, trichloramine, monochloramine, dichloramine, tribrolamin, N-chlorosulfamate and N-bromosulfamate. It is bromine.
（海生生物の付着防止方法）
本発明の海生生物の付着防止方法は、海水冷却水系の海水中で相乗効果を奏する濃度になるように塩素剤（但し、二酸化塩素を除く）または臭素剤と二酸化塩素とをこの順もしくは逆順でまたは同時に添加して、海水冷却水系への海生生物の付着を防止することを特徴とする。
(How to prevent the adhesion of marine organisms)
In the method for preventing the adhesion of marine organisms of the present invention, a chlorine agent (excluding chlorine dioxide) or a bromine agent and chlorine dioxide are used in this order or in reverse order so that the concentration has a synergistic effect in the seawater of the seawater cooling water system. It is characterized by being added at or at the same time to prevent the attachment of marine organisms to the seawater cooling water system.
（塩素剤または臭素剤）
本発明において用いられる塩素剤または臭素剤としては、併用する二酸化塩素を除く公知の塩素剤または臭素剤が挙げられ、例えば、
（ａ）塩素ガス、次亜塩素酸塩（次亜塩素酸カルシウム、次亜塩素酸ナトリウムなど）、塩素化イソシアヌル酸、ジクロロイソシアヌル酸塩（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など）、モノクロロイソシアヌル酸塩（モノクロロイソシアヌル酸ナトリウム、モノクロロイソシアヌル酸カリウムなど）、トリクロロイソシアヌル酸塩（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）などの水中で次亜塩素酸を生成する物質、
（ｂ）次亜臭素酸ナトリウム、臭化ナトリウムと次亜塩素酸ナトリウムとの反応物および臭素水などの水中で次亜臭素酸を生成する物質、
（ｃ）海水電解液（海水を電解槽で電解することによって得られる次亜塩素酸を含む電解液）、ならびに
（ｄ）モノクロラミン、ジクロラミン、トリクロラミン、モノブロラミン、ジブロラミン、トリブロラミン、Ｎ−クロロスルファマートおよびＮ−ブロモスルファマートなどの結合塩素（安定化塩素）または結合臭素（安定化臭素）
が挙げられる。これらの中でも、海生生物の付着防止効果、経済性、取扱い性などの実用的な観点から、（ａ）、（ｂ）および（ｃ）が好ましく、工業的な入手し易さの観点から、次亜塩素酸ナトリウム、次亜塩素酸カリウムが特に好ましい。（ｄ）の中では、海生生物の付着防止効果の観点から、モノクロラミン、モノブロラミンが好ましく、次に、Ｎ−クロロスルファマート、Ｎ−ブロモスルファマートが好ましい。
(Chlorine or bromine)
Examples of the chlorine agent or bromine agent used in the present invention include known chlorine agents or bromine agents excluding chlorine dioxide used in combination, and examples thereof include.
(A) Chlorine gas, hypochlorite (sodium hypochlorite, sodium hypochlorite, etc.), chlorinated isocyanuric acid, dichloroisocyanuric acid salt (sodium dichloroisocyanuric acid, potassium dichloroisocyanuric acid, etc.), monochloroisocyanuric acid. Substances that produce hypochlorite in water, such as acid salts (sodium monochloroisocyanurate, potassium monochloroisocyanurate, etc.), trichloroisocyanuric acid salts (sodium trichloroisocyanuric acid, potassium trichloroisocyanurate, etc.), etc.
(B) Sodium hypobromous acid, a reaction product of sodium bromide and sodium hypochlorite, and a substance that produces hypobromous acid in water such as bromine water.
(C) Seawater electrolyte (electrolyte containing hypochloric acid obtained by electrolyzing seawater in an electrolytic cell), and (d) monochloramine, dichloramine, trichloramine, monochloramine, dichloramine, tribroramine, N-chloro. Bound chlorine (stabilized chlorine) or bound bromine (stabilized bromine) such as sulfamate and N-bromosulfamate
Can be mentioned. Among these, (a), (b) and (c) are preferable from the practical viewpoints such as the effect of preventing the adhesion of marine organisms, economy, and handleability, and from the viewpoint of industrial availability, they are preferable. Sodium hypochlorite and potassium hypochlorite are particularly preferable. Among (d), monochlorolamin and monobrolamin are preferable, and then N-chlorosulfamate and N-bromosulfamate are preferable from the viewpoint of the effect of preventing the adhesion of marine organisms.
Ｎ−クロロスルファマートおよびＮ−ブロモスルファマートは、公知の方法、例えば、特表２００３−５０３３２３号公報、特開２００６−０２２０９７号公報、特表平１１−５０６１３９号公報、特表２００１−５０１８６９号公報、特表２００３−５０７３２６号公報、特開２０１４−１０１２５１号および特開２０１７−１５９２７６号公報などに記載の方法により調製することができる。
本発明では、スルファミン酸と、次亜塩素酸および／または次亜臭素酸との反応生成物を好適に用いることができる。
モノクロラミンなどの結合塩素は、特許第４９１４１４６号公報、特開２０１７−１１９２４５号公報および特開２０１７−５３０５４号公報などに記載の方法により調製することができる。
N-chlorosulfamate and N-bromosulfamate are described by known methods, for example, Japanese Patent Application Laid-Open No. 2003-503323, JP-A-2006-022097, Japanese Patent Application Laid-Open No. 11-506139, Japanese Patent Application Laid-Open No. 2001-2001. It can be prepared by the methods described in JP-A-501869, JP-A-2003-507326, JP-A-2014-101251 and JP-A-2017-159276.
In the present invention, a reaction product of sulfamic acid with hypochlorous acid and / or hypobromous acid can be preferably used.
Bound chlorine such as monoclonal lamin can be prepared by the methods described in Japanese Patent No. 4914146, Japanese Patent Application Laid-Open No. 2017-11245, Japanese Patent Application Laid-Open No. 2017-53054, and the like.
上記の塩素剤および臭素剤は、添加に際して所望の濃度になるように海水や淡水で希釈または溶解して用いてもよい。
なお、（ａ）水中で次亜塩素酸を生成する物質や（ｃ）海水電解液を海水に添加した場合、次亜塩素酸は海水中に存在する臭化物イオンと反応し、速やかに塩素と臭素が置換する。例えば、次亜塩素酸ナトリウムを海水に添加すると、速やかに次亜臭素酸ナトリウムになる。よって、（ａ）、（ｂ）および（ｃ）のいずれを用いても海生生物に対する付着防止効果は同等である。
The above chlorine and bromine agents may be diluted or dissolved in seawater or fresh water so as to have a desired concentration at the time of addition.
When (a) a substance that produces hypochlorous acid in water or (c) a seawater electrolytic solution is added to seawater, hypochlorous acid reacts with bromide ions existing in seawater and rapidly chlorine and bromine. Replaces. For example, when sodium hypochlorite is added to seawater, it quickly becomes sodium hypobromous acid. Therefore, even if any of (a), (b) and (c) is used, the effect of preventing adhesion to marine organisms is the same.
塩素剤または臭素剤は、併用する二酸化塩素の濃度、添加する海水の状態などにより適宜設定すればよいが、通常、塩素剤または臭素剤を海水に対して有効塩素濃度として０．００５〜０．３ｍｇ／Ｌの濃度になるように添加するのが好ましい。
本明細書では、塩素剤または臭素剤の濃度は「有効塩素濃度」を意味する。
塩素剤または臭素剤の濃度が０．００５ｍｇ／Ｌ未満では、二酸化塩素との併用による海生生物の付着防止効果が十分に得られないことがある。一方、塩素剤または臭素剤の濃度が０．３ｍｇ／Ｌを超えると、それ以上の効果が期待できず、経済的な面から好ましくない。
より好ましい塩素剤または臭素剤の濃度は、０．０１〜０．２ｍｇ／Ｌ、さらに好ましくは０．０１〜０．１ｍｇ／Ｌである。
The chlorine agent or bromine agent may be appropriately set depending on the concentration of chlorine dioxide to be used in combination, the state of the seawater to be added, etc., but usually, the chlorine agent or the bromine agent has an effective chlorine concentration of 0.005 to 0 with respect to the seawater. It is preferable to add it to a concentration of 3 mg / L.
As used herein, the concentration of chlorine or bromine agent means "effective chlorine concentration".
If the concentration of the chlorinating agent or the bromine agent is less than 0.005 mg / L, the effect of preventing the adhesion of marine organisms by the combined use with chlorine dioxide may not be sufficiently obtained. On the other hand, if the concentration of the chlorine agent or the bromine agent exceeds 0.3 mg / L, no further effect can be expected, which is not preferable from the economical point of view.
The concentration of the chlorine agent or the bromine agent is more preferably 0.01 to 0.2 mg / L, still more preferably 0.01 to 0.1 mg / L.
塩素剤または臭素剤の添加時間は、併用する二酸化塩素の添加濃度、添加する海水の状態などにより適宜設定すればよいが、通常、１日当たり１〜２４時間である。
添加時間が１日当たり１時間未満では、二酸化塩素との併用による海生生物の付着防止効果が十分に得られないことがある。
より好ましい塩素剤または臭素剤の添加時間は、１日当たり１４〜２４時間、さらに好ましくは、１日当たり１８〜２２時間である。
The addition time of the chlorine agent or the bromine agent may be appropriately set depending on the concentration of chlorine dioxide added together, the state of the seawater to be added, and the like, but is usually 1 to 24 hours per day.
If the addition time is less than 1 hour per day, the effect of preventing the adhesion of marine organisms by the combined use with chlorine dioxide may not be sufficiently obtained.
The addition time of the chlorine agent or the bromine agent is more preferably 14 to 24 hours per day, still more preferably 18 to 22 hours per day.
（二酸化塩素）
本発明において用いられる二酸化塩素は、極めて不安定な化学物質であるため、その貯蔵や輸送は非常に困難である。したがって、その場で公知の方法により二酸化塩素を製造（生成）し、添加濃度に調整して用いるのが好ましい。
例えば、次のような反応により二酸化塩素を製造することができ、市販の二酸化塩素発生器（装置）を用いることもできる。
（１）次亜塩素酸ナトリウムと塩酸と亜塩素酸ナトリウムとの反応
ＮａＯＣｌ＋２ＨＣｌ＋２ＮａＣｌＯ2 → ２ＣｌＯ2＋３ＮａＣｌ＋Ｈ2Ｏ
（２）亜塩素酸ナトリウムと塩酸との反応
５ＮａＣｌＯ2＋４ＨＣｌ → ４ＣｌＯ2＋５ＮａＣｌ＋２Ｈ2Ｏ
（３）塩素酸ナトリウム、過酸化水素および硫酸との反応
２ＮａＣｌＯ3＋Ｈ2Ｏ2＋Ｈ2ＳＯ4 → ２ＣｌＯ2＋Ｎａ2ＳＯ4＋Ｏ2＋２Ｈ2Ｏ
(Chlorine dioxide)
Chlorine dioxide used in the present invention is an extremely unstable chemical substance, and therefore its storage and transportation are extremely difficult. Therefore, it is preferable to produce (generate) chlorine dioxide on the spot by a known method and adjust the addition concentration before use.
For example, chlorine dioxide can be produced by the following reaction, and a commercially available chlorine dioxide generator (device) can also be used.
(1) Reaction of sodium hypochlorite with hydrochloric acid and sodium chlorite NaOCl + 2HCl + 2NaClO 2 → 2ClO 2 + 3NCl + H 2 O
(2) Reaction between sodium chlorite and hydrochloric acid 5NaClO 2 + 4HCl → 4ClO 2 + 5 NaCl + 2H 2 O
(3) Reaction with sodium chlorate, hydrogen peroxide and sulfuric acid 2NaClO 3 + H 2 O 2 + H 2 SO 4 → 2ClO 2 + Na 2 SO 4 + O 2 + 2H 2 O
二酸化塩素は、併用する塩素剤または臭素剤の濃度、添加する海水の状態などにより適宜設定すればよいが、通常、二酸化塩素を海水に対して０．００２〜０．２ｍｇ／Ｌの濃度になるように添加するのが好ましい。
二酸化塩素の濃度が０．００２ｍｇ／Ｌ未満では、塩素剤または臭素剤との併用による海生生物の付着防止効果が十分に得られないことがある。一方、二酸化塩素の濃度が０．２ｍｇ／Ｌを超えると、それ以上の効果が期待できず、経済的な面から好ましくない。
より好ましい二酸化塩素の濃度は、０．００５〜０．１ｍｇ／Ｌ、さらに好ましくは０．００５〜０．０５ｍｇ／Ｌである。
Chlorine dioxide may be appropriately set depending on the concentration of the chlorinating agent or bromine agent used in combination, the state of the seawater to be added, etc., but usually the concentration of chlorine dioxide is 0.002 to 0.2 mg / L with respect to the seawater. It is preferable to add it as such.
If the concentration of chlorine dioxide is less than 0.002 mg / L, the effect of preventing the adhesion of marine organisms by the combined use with a chlorine agent or a bromine agent may not be sufficiently obtained. On the other hand, if the concentration of chlorine dioxide exceeds 0.2 mg / L, no further effect can be expected, which is not preferable from the economical point of view.
A more preferable concentration of chlorine dioxide is 0.005 to 0.1 mg / L, more preferably 0.005 to 0.05 mg / L.
二酸化塩素の添加時間は、併用する塩素剤または臭素剤の海水中での濃度、添加する海水の状態などにより適宜設定すればよいが、通常、１日当たり１〜２４時間である。
添加時間が１日当たり１時間未満では、塩素剤または臭素剤との併用による海生生物の付着防止効果が十分に得られないことがある。
より好ましい二酸化塩素の添加時間は、１日当たり１４〜２４時間、さらに好ましくは、１日当たり１８〜２２時間である。
The chlorine dioxide addition time may be appropriately set depending on the concentration of the chlorinating agent or the bromine agent used in combination in seawater, the state of the seawater to be added, and the like, but is usually 1 to 24 hours per day.
If the addition time is less than 1 hour per day, the effect of preventing the adhesion of marine organisms by the combined use with a chlorine agent or a bromine agent may not be sufficiently obtained.
The addition time of chlorine dioxide is more preferably 14 to 24 hours per day, still more preferably 18 to 22 hours per day.
（塩素剤または臭素剤と二酸化塩素との海水中での相乗効果）
以上のことから、前記塩素剤または臭素剤および二酸化塩素が、前記海水中でそれぞれ０．００５〜０．３ｍｇ／Ｌの有効塩素濃度および０．００２〜０．２ｍｇ／Ｌの濃度になるように添加されるのが好ましい。
海水中における塩素剤または臭素剤および二酸化塩素の濃度は、海水中での各化合物の経時的な濃度低下があることから、厳密には各化合物の添加濃度と等価ではない。
したがって、本発明の実施に当たっては、海水やそこに生息する海生生物の状況などに応じて、海水中での塩素剤または臭素剤および二酸化塩素の濃度が上記の範囲になるように、それらの濃度低下を見越して、添加濃度および添加時間などを適宜設定すればよい。
また、以上のことから、塩素剤または臭素剤と二酸化塩素とは、１日１〜２４時間添加されるのが好ましい。
(Synergistic effect of chlorine or bromine and chlorine dioxide in seawater)
From the above, the chlorine agent or bromine agent and chlorine dioxide are adjusted to have an effective chlorine concentration of 0.005 to 0.3 mg / L and a concentration of 0.002 to 0.2 mg / L in the seawater, respectively. It is preferable to add it.
The concentrations of the chlorine agent or bromine agent and chlorine dioxide in seawater are not strictly equivalent to the added concentration of each compound because the concentration of each compound in seawater decreases with time.
Therefore, in carrying out the present invention, the concentrations of the chlorine agent or the bromine agent and the chlorine dioxide in the seawater should be within the above range depending on the conditions of the seawater and the marine organisms inhabiting the seawater. In anticipation of a decrease in concentration, the addition concentration and addition time may be appropriately set.
From the above, it is preferable that the chlorine agent or the bromine agent and chlorine dioxide are added for 1 to 24 hours a day.
（他の添加剤）
本発明の海生生物の付着防止方法では、本発明の効果を阻害しない限りにおいて、当該技術分野で公知の他の添加剤を併用してもよい。
例えば、ジアルキルジチオカルバミン酸塩、カチオン系界面活性剤等の海生生物付着防止剤、鉄系金属腐食防止剤、消泡剤などが挙げられる。
(Other additives)
In the method for preventing the adhesion of marine organisms of the present invention, other additives known in the art may be used in combination as long as the effects of the present invention are not impaired.
Examples thereof include dialkyldithiocarbamate salts, marine biofouling inhibitors such as cationic surfactants, iron-based metal corrosion inhibitors, and defoaming agents.
（添加場所）
海水冷却水系は、例えば、取水系設備、復水器やその他機器などの冷却対象となる設備および放水系設備などからなる。取水系設備は、導水路、海水中の異物を除去するスクリーン、循環水ポンプ（取水ポンプ）および循環水管（取水管）などからなる。
(Addition place)
The seawater cooling water system includes, for example, water intake system equipment, equipment to be cooled such as a condenser and other equipment, and water discharge system equipment. The intake system equipment consists of a headrace, a screen for removing foreign substances in seawater, a circulating water pump (intake pump), a circulating water pipe (intake pipe), and the like.
本発明における各薬剤の添加場所は、取水路、熱交換器または復水器に付帯する配管中や導水路、熱交換器の入口または復水器の入口のいずれであってもよいが、海生生物の付着による障害防止効果の点で、取水ポンプの取水口近傍、熱交換器または復水器の入口が好ましい。 The place where each drug is added in the present invention may be in the intake channel, the heat exchanger or the pipe attached to the condenser, the headrace, the inlet of the heat exchanger or the inlet of the condenser, but the sea. In terms of the effect of preventing damage due to the adhesion of living organisms, the vicinity of the intake of the intake pump and the inlet of the heat exchanger or condenser are preferable.
発電所などでは、海水生物の付着防止効果を得るために、取水した海水に塩素剤または臭素剤を添加しているが、排水の残留塩素の濃度規制により、十分な塩素剤または臭素剤の添加ができず、熱交換器（復水器）で必要な塩素または臭素濃度を残留させることができず、十分な付着防止効果が得られないことがある。そこで、本発明によれば、このような海水系に低濃度の二酸化塩素を復水器の上流側に添加することで、上記の残留塩素の濃度規制内で十分な海水生物の付着防止効果を得ることができる。したがって、塩素剤または臭素剤の添加後に二酸化塩素を添加する、すなわち塩素剤または臭素剤および二酸化塩素とは、この順で海水冷却水系の海水中に添加されるのが特に好ましい。 At power plants, etc., chlorine agents or bromine agents are added to the taken seawater in order to obtain the effect of preventing the adhesion of seawater organisms, but due to the regulation of the concentration of residual chlorine in wastewater, sufficient chlorine agents or bromine agents are added. In some cases, the required chlorine or bromine concentration cannot be retained in the heat exchanger (condenser), and a sufficient adhesion prevention effect cannot be obtained. Therefore, according to the present invention, by adding a low concentration of chlorine dioxide to the upstream side of the condenser in such a seawater system, a sufficient effect of preventing the adhesion of marine organisms within the above-mentioned regulation of the concentration of residual chlorine can be obtained. Obtainable. Therefore, it is particularly preferable that chlorine dioxide is added after the addition of the chlorine agent or bromine agent, that is, the chlorine agent or bromine agent and chlorine dioxide are added to the seawater of the seawater cooling water system in this order.
（添加方法）
各薬剤の添加方法としては、注入ポンプや散気管、噴霧器などを用いた方法が挙げられる。本発明において微量の薬剤を海水冷却水系中に、迅速にかつ実質的に均一に拡散させるためには、従来の物理的手段を用いることができる。具体的には、該水系中への拡散器、攪拌装置や邪魔板などの設置が挙げられる。また、これらに該当する設備は海水冷却水系に付設されているので、これを転用してもよい。
(Addition method)
Examples of the method for adding each drug include a method using an injection pump, an air diffuser, a sprayer, and the like. In the present invention, conventional physical means can be used to diffuse a trace amount of the drug into the seawater cooling water system quickly and substantially uniformly. Specific examples thereof include installation of a diffuser, a stirrer, a baffle plate, etc. in the water system. In addition, since the equipment corresponding to these is attached to the seawater cooling water system, it may be diverted.
（海生生物の付着防止剤）
本発明の海生生物の付着防止剤は、上記の方法に使用される海生生物の付着防止剤であって、
前記付着防止剤が、
塩素剤または臭素剤としての
（ａ）塩素ガス、次亜塩素酸カルシウム、次亜塩素酸ナトリウム、塩素化イソシアヌル酸、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、モノクロロイソシアヌル酸ナトリウム、モノ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およびトリクロロイソシアヌル酸カリウムの中から選択される一種以上の水中で次亜塩素酸を生成する物質、
（ｂ）次亜臭素酸ナトリウム、臭化ナトリウムと次亜塩素酸ナトリウムとの反応物および臭素水から選択される一種以上の水中で次亜臭素酸を生成する物質、
（ｃ）海水電解液、または
（ｄ）モノクロラミン、ジクロラミン、トリクロラミン、モノブロラミン、ジブロラミン、トリブロラミン、Ｎ−クロロスルファマートおよびＮ−ブロモスルファマートから選択される一種以上の結合塩素（安定化塩素）もしくは結合臭素（安定化臭素）と、
二酸化塩素発生源としての
（１）次亜塩素酸ナトリウムと塩酸と亜塩素酸ナトリウムとの組み合わせ、
（２）亜塩素酸ナトリウムと塩酸との組み合わせ、または
（３）塩素酸ナトリウム、過酸化水素および硫酸との組み合わせ
とを含むことを特徴とする。
(Anti-adhesion agent for marine organisms)
The marine organism adhesion inhibitor of the present invention is a marine organism adhesion inhibitor used in the above method.
The anti-adhesion agent
As a chlorinating agent or bromine agent (a) Chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, sodium dichloroisocyanuric acid, potassium dichloroisocyanuric acid, sodium monochloroisocyanuric acid, potassium monochloroisocyanuric acid, A substance that produces hypochlorite in one or more waters selected from sodium trichloroisocyanuric acid and potassium trichloroisocyanuric acid,
(B) A substance that produces hypobromous acid in one or more waters selected from sodium hypobromous acid, a reaction product of sodium bromide and sodium hypochlorite, and bromine water.
(C) Seawater electrolyte or (d) One or more bound chlorine (stable) selected from monochloramine, dichloramine, trichloramine, monochloramine, dichloramine, tribrolamin, N-chlorosulfamate and N-bromosulfamate. Chlorine bromide) or bound bromine (stabilized bromine),
As a source of chlorine dioxide (1) Combination of sodium hypochlorite, hydrochloric acid and sodium chlorite,
It is characterized by containing (2) a combination of sodium chlorite and hydrochloric acid, or (3) a combination of sodium chlorate, hydrogen peroxide and sulfuric acid.
本発明を以下の試験例により具体的に説明するが、本発明はこれらにより限定されるものではない。 The present invention will be specifically described with reference to the following test examples, but the present invention is not limited thereto.
［試験例１］
次亜塩素酸と二酸化塩素との併用による海生生物の付着防止効果を確認した。
太平洋に面した和歌山県沿岸の某所に水路試験装置を設け、試験を行った。
水中ポンプを用いて揚水した未濾過の海水（ｐＨ８）を、１５系統に分岐させた水路（試験区）に流量１ｍ3／ｈで７０日間、一過式に通水し、各水路に下記のように調製した添加薬剤（次亜塩素酸と二酸化塩素）を表１に示す薬剤濃度になるように、表１に示す１日当たりの添加時間で添加した。
なお、薬剤濃度は下記の付着防止効果確認用のアクリル製カラム内での設定濃度であり、次亜塩素酸の濃度は有効塩素濃度である。
また、薬剤濃度が同じ試験区の薬剤添加量は同量である。例えば、実施例１、実施例２および比較例１の次亜塩素酸の添加量は同じであり、実施例２および比較例６の二酸化塩素の添加量は同じである。
[Test Example 1]
It was confirmed that the combined use of hypochlorous acid and chlorine dioxide has an effect of preventing the adhesion of marine organisms.
A waterway test device was installed at a certain location on the coast of Wakayama Prefecture facing the Pacific Ocean, and tests were conducted.
Unfiltered seawater (pH 8) pumped up using a submersible pump was transiently passed through a channel (test plot) branched into 15 systems at a flow rate of 1 m 3 / h for 70 days, and the following was performed in each channel. The additive agents (hypochlorous acid and chlorine dioxide) prepared as described above were added at the daily addition time shown in Table 1 so as to have the agent concentrations shown in Table 1.
The drug concentration is the set concentration in the acrylic column for confirming the adhesion prevention effect below, and the concentration of hypochlorous acid is the effective chlorine concentration.
In addition, the amount of the drug added in the test group having the same drug concentration is the same. For example, the amount of hypochlorous acid added to Example 1, Example 2, and Comparative Example 1 is the same, and the amount of chlorine dioxide added to Example 2 and Comparative Example 6 is the same.
また、各水路内には、付着防止効果確認用にアクリル製カラム（内径６４ｍｍ×長さ３００ｍｍ×厚さ２ｍｍ、表面積６０２．８８ｃｍ2）を挿入し、通水終了後にカラムに付着した付着生物量を測定し、付着防止効果を評価した。
なお、ブランクとして薬剤無添加についても試験した。
得られた結果を、各添加薬剤およびそれらの濃度、時間と共に表１に示す。
In addition, an acrylic column (inner diameter 64 mm x length 300 mm x thickness 2 mm, surface area 602.88 cm 2 ) was inserted into each channel to confirm the effect of preventing adhesion, and the amount of biomass attached to the column after the completion of water flow. Was measured and the adhesion prevention effect was evaluated.
In addition, it was also tested that no drug was added as a blank.
The obtained results are shown in Table 1 together with each additive agent and their concentration and time.
（添加薬剤）
二酸化塩素は、表１に示す二酸化塩素濃度が得られるように、亜塩素酸ナトリウムおよび塩酸をそれぞれ適宜純水で希釈した水溶液を、薬剤添加ポイント前のチューブ内で混合し、１時間の滞留時間を持たせることで発生した二酸化塩素水溶液を付着防止効果確認用アクリル製カラムの手前から定量ポンプを用いて添加した。なお、二酸化塩素の発生については、予備試験において発生を確認すると共に、亜塩素酸ナトリウムが残留しないことを確認している。
次亜塩素酸は、有効塩素として１２％の次亜塩素酸ナトリウム水溶液を適宜純水で希釈することで海水に添加する薬剤濃度に調整し、二酸化塩素と同様に付着防止効果確認用アクリル製カラムの手前から定量ポンプを用いて添加した。
(Additive drug)
For chlorine dioxide, an aqueous solution obtained by appropriately diluting sodium chlorite and hydrochloric acid with pure water is mixed in a tube before the chemical addition point so that the chlorine dioxide concentration shown in Table 1 can be obtained, and the residence time is 1 hour. The chlorine dioxide aqueous solution generated by the addition was added from the front of the acrylic column for confirming the adhesion prevention effect using a metering pump. Regarding the generation of chlorine dioxide, it was confirmed in a preliminary test that sodium chlorite did not remain.
Hypochlorous acid is adjusted to the concentration of chemicals added to seawater by appropriately diluting a 12% sodium hypochlorite aqueous solution as effective chlorine with pure water, and an acrylic column for confirming the adhesion prevention effect like chlorine dioxide. It was added from this side using a metering pump.
（付着防止効果の確認）
試験後、水路から取り外したカラムの質量Ｗａ（ｇ）を測定した。予め試験前に測定しておいた乾燥時のカラムの質量Ｗｂと共に、次式により付着生物量（ｇ）を算出した。
付着生物量（ｇ）＝Ｗａ−Ｗｂ
付着生物は、主としてムラサキイガイなどのイガイ類やフジツボ類、コケムシ類などの海生付着生物に由来する。また、カラムには、付着生物やスライムの排泄物や死骸、細胞外分泌物などの有機質を多く含むデトリタス様物質、海水中に含まれる粘度粒子や浮遊物も付着するが、これらも付着生物量に含める。
ブランクでの海生生物の付着状況から、本試験例では付着生物量が１５ｇ以下の場合に十分な海生生物の付着防止効果があると判断できる。また、付着生物量が５ｇ以下の場合には、生物や汚れの付着が目視では全く確認されず、最良の海生生物の付着防止と判断できる。
(Confirmation of adhesion prevention effect)
After the test, the mass Wa (g) of the column removed from the water channel was measured. The attached biomass (g) was calculated by the following formula together with the mass Wb of the column at the time of drying measured in advance before the test.
Attached biomass (g) = Wa-Wb
The attached organisms are mainly derived from mussels such as mussels and marine attached organisms such as barnacles and mussels. Detritus-like substances containing a large amount of organic substances such as adhering organisms, slime excrement and carcasses, and extracellular secretions, and viscous particles and suspended matter contained in seawater also adhere to the column. include.
From the state of attachment of marine organisms in the blank, it can be judged that in this test example, there is a sufficient effect of preventing the attachment of marine organisms when the amount of attached biomass is 15 g or less. Further, when the amount of adhered biomass is 5 g or less, the adherence of organisms and dirt is not visually confirmed at all, and it can be judged that the best prevention of adherence of marine organisms is achieved.
表１の結果から次のことがわかる。
（１）次亜塩素酸を単独で使用した場合には、添加濃度０．０７５ｍｇ／Ｌ（比較例３）で、二酸化塩素を単独で使用した場合には、添加濃度０．０３０ｍｇ／Ｌ（比較例８）で十分な海生生物の付着防止効果が得られること
（２）一方、次亜塩素酸と二酸化塩素とを併用した場合には、それぞれ添加濃度０．０２５ｍｇ／Ｌおよび０．００５ｍｇ／Ｌ（実施例１）、すなわち、それぞれ上記（１）の１／３および１／６の添加濃度で十分な海生生物の付着防止効果が得られること
（３）次亜塩素酸と二酸化塩素とをそれぞれ添加濃度０．０２５ｍｇ／Ｌおよび０．０１０ｍｇ／Ｌ（実施例２および５）、すなわち、それぞれ上記（１）の１／３および１／３の添加濃度で併用した場合には、１日当たりの添加時間が上記（１）の場合（２２時間／日）より短くても（１８時間／日）、上記（２）よりも優れた海生生物の付着防止効果が得られること
（４）先に次亜塩素酸を添加して後から二酸化塩素を添加する場合（実施例２）および先に二酸化塩素を添加して後から次亜塩素酸を添加する場合（実施例５）を比較すると、共に十分な海生生物の付着防止効果が得られるものの、前者が優れていること
The following can be seen from the results in Table 1.
(1) When hypochlorous acid is used alone, the addition concentration is 0.075 mg / L (Comparative Example 3), and when chlorine dioxide is used alone, the addition concentration is 0.030 mg / L (comparison). Example 8) provides a sufficient effect of preventing the adhesion of marine organisms (2) On the other hand, when hypochlorous acid and chlorine dioxide are used in combination, the addition concentrations are 0.025 mg / L and 0.005 mg / L, respectively. L (Example 1), that is, a sufficient effect of preventing the adhesion of marine organisms can be obtained with the addition concentrations of 1/3 and 1/6 of the above (1), respectively (3) Hypochlorous acid and chlorine dioxide. In combination with the addition concentrations of 0.025 mg / L and 0.010 mg / L (Examples 2 and 5), that is, the addition concentrations of 1/3 and 1/3 of the above (1), respectively, per day. Even if the addition time of (1) is shorter than that of (22 hours / day) (18 hours / day), a better effect of preventing adhesion of marine organisms than that of (2) above can be obtained (4). Comparing the case where hypochlorous acid is added and then chlorine dioxide is added (Example 2) and the case where chlorine dioxide is added first and then hypochlorous acid is added (Example 5), Both have a sufficient effect of preventing the adhesion of marine organisms, but the former is superior.
（５）上記（１）以上、すなわち単独で十分な海生生物の付着防止効果を示す添加濃度以上に次亜塩素酸および二酸化塩素をそれぞれ添加しても、付着生物量が塩素では８．７ｇ（比較例４）、二酸化塩素では７．８ｇ（比較例８）までしか低減しないこと
（６）一方、次亜塩素酸と二酸化塩素とを併用した場合には、付着生物量が４．６ｇ（実施例２）、４．８ｇ（実施例３）、４．６ｇ（実施例４）、６．１ｇ（実施例５）まで低減すること
上記の結果は、海水中に次亜塩素酸と二酸化塩素とが共存して両者の効果、つまり相乗効果に相当する効果が発揮されることによるものと考えられる。次亜塩素酸（塩素）の代替として用いられる二酸化塩素を次亜塩素酸と併用することにより、このような相乗効果が得られることは意外な事実である。
(5) Even if hypochlorous acid and chlorine dioxide are added at a concentration equal to or higher than that of (1) above, that is, an addition concentration that alone exhibits a sufficient effect of preventing the adhesion of marine organisms, the amount of adhered organisms is 8.7 g for chlorine. (Comparative Example 4), Chlorine dioxide can only be reduced to 7.8 g (Comparative Example 8) (6) On the other hand, when hypochlorous acid and chlorine dioxide are used in combination, the amount of adhered organisms is 4.6 g (Comparative Example 8). Example 2) Reduce to 4.8 g (Example 3), 4.6 g (Example 4), 6.1 g (Example 5) The above results show that hypochlorous acid and chlorine dioxide are in seawater. It is considered that this is due to the coexistence of and the effects of both, that is, the effect equivalent to the synergistic effect. It is a surprising fact that such a synergistic effect can be obtained by using chlorine dioxide, which is used as a substitute for hypochlorous acid (chlorine), in combination with hypochlorous acid.
塩素系酸化剤の海生生物に対する付着防止効果は、一般的に薬剤添加後の海水のＯＲＰに比例すると考えられている。ＯＲＰは海水の性状や水温などにより常に一定の数値を示す訳ではないが、本試験例では、次亜塩素酸と二酸化塩素とを併用した実施例１および２ではＯＲＰがそれぞれ４０６および４１４となり、同濃度の次亜塩素酸を単独で使用した比較例１でもＯＲＰが同等の４１２となった。このような結果から、次亜塩素酸と二酸化塩素との併用により一方もしくは両方の薬剤の一部が酸化還元反応により分解していることが推測され、上記のような相乗効果は得られないと類推される。しかしながら、上記のような海生生物に対する優れた付着防止効果が得られたことは、当業者が容易に想到し得ない意外な事実といえる。 The effect of the chlorine-based oxidant on marine organisms is generally considered to be proportional to the ORP of seawater after the addition of the agent. The ORP does not always show a constant value depending on the properties of seawater and the water temperature, but in this test example, the ORPs were 406 and 414, respectively, in Examples 1 and 2 in which hypochlorous acid and chlorine dioxide were used in combination. Even in Comparative Example 1 in which the same concentration of hypochlorous acid was used alone, the ORP was 412, which was the same. From these results, it is presumed that a part of one or both of the drugs is decomposed by the redox reaction by the combined use of hypochlorous acid and chlorine dioxide, and the above synergistic effect cannot be obtained. It is inferred. However, it can be said that the fact that the above-mentioned excellent anti-adhesion effect on marine organisms has been obtained is a surprising fact that cannot be easily conceived by those skilled in the art.
［試験例２］
塩素剤としてＮ−クロロスルファマートまたはモノクロラミンを使用し二酸化塩素と併用した場合、臭素剤としてＮ−ブロモスルファマートまたはモノブロラミンを使用し二酸化塩素と併用した場合の海生生物の付着防止効果を確認した。
太平洋に面した和歌山県沿岸の某所に水路試験装置を設け、試験を行った。
水中ポンプを用いて揚水した未濾過の海水（ｐＨ８）を、１７系統に分岐させた水路（試験区）に流量１ｍ3／ｈで６８日間、一過式に通水した。各水路には下記のように調製した添加薬剤を表２に示す薬剤濃度になるように、表２に示す１日当たりの添加時間になるように添加した。
なお、薬剤濃度は下記の付着防止効果確認用のアクリル製カラム内での設定濃度であり、塩素剤および臭素剤の薬剤濃度は有効塩素濃度（有効塩素換算濃度）である。
また、薬剤濃度が同じ試験区の薬剤添加量は同量である。例えば、実施例６および比較例１０のＮ−クロロスルファマートの添加量は同じであり、実施例７および比較例１６の二酸化塩素の添加量は同じである。
[Test Example 2]
Prevention of adhesion of marine organisms when N-chlorosulfamate or monobrolamin is used as a chlorine agent and used in combination with chlorine dioxide, and when N-bromosulfamate or monobrolamin is used as a bromine agent and used in combination with chlorine dioxide. The effect was confirmed.
A waterway test device was installed at a certain location on the coast of Wakayama Prefecture facing the Pacific Ocean, and tests were conducted.
Unfiltered seawater (pH 8) pumped using a submersible pump was transiently passed through a channel (test plot) branched into 17 systems at a flow rate of 1 m 3 / h for 68 days. Additives prepared as described below were added to each water channel so as to have the drug concentrations shown in Table 2 and the addition time per day shown in Table 2.
The drug concentration is the set concentration in the acrylic column for confirming the adhesion prevention effect below, and the drug concentration of the chlorine agent and the bromine agent is the effective chlorine concentration (effective chlorine equivalent concentration).
In addition, the amount of the drug added in the test group having the same drug concentration is the same. For example, the amount of N-chlorosulfamate added in Example 6 and Comparative Example 10 is the same, and the amount of chlorine dioxide added in Example 7 and Comparative Example 16 is the same.
また、各水路内には、付着防止効果確認用にアクリル製カラム（内径６４ｍｍ×長さ３００ｍｍ×厚さ２ｍｍ、表面積６０２．８８ｃｍ２）を挿入し、通水終了後にカラムに付着した付着生物量を測定し、付着防止効果を評価した。
なお、ブランクとして薬剤無添加についても試験した。
得られた結果を、各添加薬剤およびそれらの濃度、時間と共に表２に示す。
In addition, an acrylic column (inner diameter 64 mm x length 300 mm x thickness 2 mm, surface area 602.88 cm2) is inserted into each waterway to confirm the effect of preventing adhesion, and the amount of attached biomass attached to the column after the completion of water flow is measured. It was measured and the adhesion prevention effect was evaluated.
In addition, it was also tested that no drug was added as a blank.
The obtained results are shown in Table 2 together with each additive agent and their concentration and time.
（添加薬剤）
二酸化塩素は、試験例１と同様に調整し添加した。
Ｎ−クロロスルファマートおよびＮ−ブロモスルファマートは、公知の方法（例えば、特開２０１７−１５９２７６号公報に記載の方法）によって、モノクロラミンおよびモノブロラミンは、公知の方法（例えば、特開２０１７−５３０５４号公報に記載の方法）によって、それぞれ生成させた後、適宜純水で希釈することで海水に添加する薬剤濃度に調整し、二酸化塩素と同様に付着防止効果確認用アクリル製カラムの手前から定量ポンプを用いて添加した。
(Additive drug)
Chlorine dioxide was adjusted and added in the same manner as in Test Example 1.
N-chlorosulfamate and N-bromosulfamate are prepared by a known method (for example, the method described in JP-A-2017-159276), and monochlorolamin and monobrolamin are prepared by a known method (eg, JP-A-2017). After each of them is produced by the method described in JP-A-2017-53054), the concentration of the chemical to be added to seawater is adjusted by appropriately diluting with pure water, and the acrylic column for confirming the adhesion prevention effect is used in the same manner as chlorine dioxide. It was added from the front using a metering pump.
（付着防止効果の確認）
試験例１と同様にして、カラムの付着生物量（ｇ）を算出し、海生生物の付着防止効果を確認した。
(Confirmation of adhesion prevention effect)
In the same manner as in Test Example 1, the amount of adhered biomass (g) on the column was calculated, and the effect of preventing the adherence of marine organisms was confirmed.
表２の結果から次のことがわかる。
（１）塩素剤または臭素剤を単独で使用した場合には十分な海生生物の付着防止効果が得られないが（比較例１０〜１２）、二酸化塩素と併用した場合には十分な海生生物の付着防止効果が得られること（実施例６〜８）
（２）十分な海生生物の付着防止効果が得られる塩素剤を単独で使用する場合（比較例１４）の１／２の塩素剤の添加濃度では十分な効果が期待できないが、少量の二酸化塩素との併用した場合には十分な海生生物の付着防止効果が得られること（実施例１０）
（３）塩素剤または臭素剤を単独で使用した場合にも十分な海生生物の付着防止効果が得られるが（比較例１３〜１５）、二酸化塩素と併用した場合には最良の海生生物の付着防止効果が得られること（実施例９、１１および１２）
（４）十分な海生生物の付着防止効果が得られる二酸化塩素を単独で使用する場合（比較例１８）の１／６〜２／３の二酸化塩素の添加濃度では十分な効果が期待できないが、塩素剤または臭素剤との併用した場合には十分な海生生物の付着防止効果が得られること（実施例６〜１２）
上記の結果は、海水中にＮ−クロロスルファマート、Ｎ−ブロモスルファマート、モノクロラミンおよびモノブロラミンと、二酸化塩素とが共存して両者の効果、つまり相乗効果に相当する効果が発揮されることによるものと考えられる。
The following can be seen from the results in Table 2.
(1) When a chlorine agent or a bromine agent is used alone, a sufficient effect of preventing the adhesion of marine organisms cannot be obtained (Comparative Examples 10 to 12), but when used in combination with chlorine dioxide, a sufficient marine organism is obtained. Obtaining an effect of preventing the adhesion of living organisms (Examples 6 to 8)
(2) When a chlorine agent that can obtain a sufficient effect of preventing the adhesion of marine organisms is used alone (Comparative Example 14), a sufficient effect cannot be expected at a concentration of 1/2 of the chlorine agent, but a small amount of dioxide is used. When used in combination with chlorine, a sufficient effect of preventing the adhesion of marine organisms can be obtained (Example 10).
(3) A sufficient effect of preventing the adhesion of marine organisms can be obtained even when a chlorine agent or a bromine agent is used alone (Comparative Examples 13 to 15), but the best marine organisms are obtained when used in combination with chlorine dioxide. (Examples 9, 11 and 12)
(4) A sufficient effect of preventing the adhesion of marine organisms can be obtained. When chlorine dioxide is used alone (Comparative Example 18), a sufficient effect cannot be expected at a concentration of 1/6 to 2/3 of chlorine dioxide added. , Sufficient marine organism adhesion prevention effect can be obtained when used in combination with chlorine or bromine (Examples 6 to 12).
The above results show that N-chlorosulfamate, N-bromosulfamate, monochromamine and monobrolamine and chlorine dioxide coexist in seawater, and the effects of both, that is, the synergistic effects, are exhibited. It is thought that this is due to the fact.
Claims (2)
前記塩素剤が海水電解液であることを特徴とする海生生物の付着防止方法。 A chlorine agent (excluding chlorine dioxide) so that the effective chlorine concentration is 0.01 to 0.3 mg / L in the seawater of the seawater cooling water system, and the concentration is 0.005 to 0.05 mg / L. Chlorine dioxide and chlorine dioxide are added in this order, in reverse order, or at the same time for 1 to 24 hours a day to prevent the adhesion of marine organisms to the seawater cooling water system.
A method for preventing adhesion of marine organisms, wherein the chlorinating agent is a seawater electrolytic solution.
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