JP7266224B2 - Method for preventing adherence of marine organisms - Google Patents
Method for preventing adherence of marine organisms Download PDFInfo
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- JP7266224B2 JP7266224B2 JP2021142658A JP2021142658A JP7266224B2 JP 7266224 B2 JP7266224 B2 JP 7266224B2 JP 2021142658 A JP2021142658 A JP 2021142658A JP 2021142658 A JP2021142658 A JP 2021142658A JP 7266224 B2 JP7266224 B2 JP 7266224B2
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- 238000000034 method Methods 0.000 title claims description 33
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 153
- 239000004155 Chlorine dioxide Substances 0.000 claims description 76
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 76
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 70
- 239000000460 chlorine Substances 0.000 claims description 70
- 229910052801 chlorine Inorganic materials 0.000 claims description 70
- 239000013535 sea water Substances 0.000 claims description 62
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000498 cooling water Substances 0.000 claims description 15
- 230000002265 prevention Effects 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 description 99
- 235000017168 chlorine Nutrition 0.000 description 70
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 49
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 49
- 229910052794 bromium Inorganic materials 0.000 description 49
- 230000000694 effects Effects 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000000126 substance Substances 0.000 description 19
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 14
- 239000005708 Sodium hypochlorite Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 241000237536 Mytilus edulis Species 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 235000020638 mussel Nutrition 0.000 description 9
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 8
- VWPXUKSDWYXLKV-UHFFFAOYSA-N bromosulfamic acid Chemical compound OS(=O)(=O)NBr VWPXUKSDWYXLKV-UHFFFAOYSA-N 0.000 description 8
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 229940079593 drug Drugs 0.000 description 7
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 7
- 229960002218 sodium chlorite Drugs 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 241000894007 species Species 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical group [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- 230000001464 adherent effect Effects 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
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 4
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 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
- 241000700670 Bryozoa Species 0.000 description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 3
- 241000238586 Cirripedia Species 0.000 description 3
- 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 3
- 239000002519 antifouling agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000007973 cyanuric acids Chemical class 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
- IFIDXBCRSWOUSB-UHFFFAOYSA-N potassium;1,3-dichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [K+].ClN1C(=O)NC(=O)N(Cl)C1=O IFIDXBCRSWOUSB-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XSXSKSKONCDOMZ-UHFFFAOYSA-N sodium;1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [Na+].ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O XSXSKSKONCDOMZ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 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
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 2
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 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 1
- 239000002028 Biomass Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000589248 Legionella Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 monobroramine Chemical compound 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
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 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
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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。 TECHNICAL FIELD The present invention relates to a method for preventing adhesion of marine organisms and an anti-adhesion agent used therein. More particularly, the present invention relates to a method for preventing adhesion of marine organisms and an anti-adhesion agent used therein, which can maintain its effect for a long period of time with the addition of a low-concentration agent and can prevent adhesion of a wide range of marine organism species.
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。 A large amount of seawater is used as cooling water for industrial use, particularly as cooling water for condensers in thermal power plants and nuclear power plants. Therefore, a large amount of mussels such as mussels, barnacles, bryozoans, and other marine organisms adhere to the walls of the seawater intake channel, pipes, and heat exchangers, causing various problems. Among them, bivalves such as mussels, which are epiphytic by byssus threads, grow rapidly, and when they reach adulthood, they block part of the heat exchanger tube, obstructing the passage of seawater and causing turbulence. Causes problems 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 growth (adherence) of these marine species, conventionally, chlorine generating agents such as sodium hypochlorite, electrolytic chlorine or chlorine gas (also referred to as "chlorine agents"), hydrogen peroxide or excess water are used. A hydrogen oxide generating agent (also referred to as a “hydrogen peroxide agent”) is added (for example, see 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 power and does not form harmful organochlorine compounds, so it has the advantage of having little impact on the environment.
For example, Japanese Patent Application Laid-Open No. 1-275504 (Patent Document 3) discloses a technology related to a biofouling agent containing chlorine dioxide or a chlorine dioxide generating agent as an active ingredient. consists of continuously or intermittently injecting an aqueous solution of chlorine dioxide with a relatively high concentration into a waterway through which freshwater or seawater is installed in a facility using freshwater or seawater. A technique related to a method for preventing or controlling adhesion of living organisms is disclosed.
However, chlorine dioxide is extremely unstable as a chemical substance, and there is a problem in the sustainability of the effect of preventing adhesion of marine organisms.
In addition, the present applicant has proposed a method for preventing adhesion of marine organisms using both chlorine dioxide and hydrogen peroxide and an anti-adhesion agent used therein (Patent No. 5879596: see Patent Document 5).
Japanese Unexamined Patent Application Publication No. 2005-7254 (Patent Document 6) discloses a technique relating to a method for sterilizing bathtub water using both a chlorine-based chemical and chlorine dioxide as a sterilizing agent. However, the target water system of this technology is bath water, not seawater cooling water system, and its purpose is sterilization of Legionella bacteria and destruction of biofilm, not prevention of adhesion of marine organisms. or different purpose.
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 adhesion of marine organisms, there is a movement to avoid using halogen-based agents such as chlorine and bromine agents in consideration of the impact on the environment. in some cases, and in other cases, chlorine-based compounds by-produced in the recycling process are effectively used.
Under these circumstances, it is desired to develop a chemical agent that can exhibit an excellent effect of preventing the adhesion of marine organisms while reducing the amount of chlorine agent used in consideration of the impact on the environment, and a method using the same. 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。 The present invention provides a method for preventing adhesion of marine organisms and an anti-adhesion agent for use therein, which can maintain its effect for a long period of time with the addition of a low-concentration chemical and can prevent the adhesion of a wide range of marine species and slimes. 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 inventors of the present invention have found that a combination of a chlorine agent or a bromine agent and chlorine dioxide can effectively prevent adhesion of a wide range of marine species including mussels such as mussels for a long period of time. It was found that effective adhesion prevention effect against marine organisms, slime, etc. can be obtained even if the amount of the agent added is reduced compared to the single use of chlorine agent or bromine agent and chlorine dioxide in the prior art, and the present invention was completed. 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 Chlorine dioxide is added in this order or reverse order or simultaneously with chlorine dioxide 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. ,
wherein said chlorine agent is selected from sodium hypochlorite, N-chlorosulfamate and monochloramine, and said bromine agent is selected from sodium hypobromite, N-bromosulfamate and monobroramine; A method for preventing fouling 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 adhesion of marine organisms, which can maintain its effects for a long period of time with the addition of a low-concentration chemical agent and can prevent the adhesion of a wide range of marine species and slimes.
That is, in the method for preventing adhesion of marine organisms of the present invention, the chlorine agent or bromine agent and chlorine dioxide are added so as to have a synergistic effect in seawater. is exerted continuously for a certain period of time, and a small amount of addition can provide a more excellent effect of preventing adhesion of marine organisms than when a chlorine agent or a bromine agent and chlorine dioxide are used alone.
In addition, the method for preventing adhesion of marine organisms of the present invention is effective in preventing adhesion of a wide range of marine organism species, for example, mussels such as mussels, marine organisms such as barnacles and bryozoans, and slime.
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。
In addition, the method for preventing adherence of marine organisms of the present invention further exhibits the above effects when any one of the following requirements is satisfied.
(1) Chlorine agent or bromine agent and chlorine dioxide are added to seawater so that the available chlorine concentration is 0.005 to 0.3 mg/L and the concentration is 0.002 to 0.2 mg/L, respectively. added.
(2) A chlorine or 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 or bromine agent has been added, that is, the chlorine or bromine agent and chlorine dioxide are added in this order to the seawater of the seawater cooling water system.
(4) a chlorine or bromine agent,
(a) chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, sodium monochloroisocyanurate, potassium monochloroisocyanurate, sodium trichloroisocyanurate and trichloroisocyanurate Substances that generate hypochlorous acid in water at least one selected from potassium phosphate,
(b) one or more substances selected from sodium hypobromite, a reaction product of sodium bromide and sodium hypochlorite, and bromine water that generates hypobromous acid in water;
(c) seawater electrolyte, or (d) one or more combined chlorines or bonds selected from monochloramine, dichloramine, trichloramine, monobrolamine, dibrolamine, tribrolamine, N-chlorosulfamate and N-bromosulfamate. 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。
(Method for preventing adherence of marine organisms)
In the method for preventing adhesion of marine organisms of the present invention, a chlorine agent (excluding chlorine dioxide) or a bromine agent and chlorine dioxide are added in this order or in reverse order so that the concentration in the seawater of the seawater cooling water system exhibits a synergistic effect. or at the same time to prevent adhesion 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 agent or bromine agent)
Examples of the chlorine or bromine agent used in the present invention include known chlorine or bromine agents other than chlorine dioxide used in combination.
(a) chlorine gas, hypochlorite (calcium hypochlorite, sodium hypochlorite, etc.), chlorinated isocyanuric acid, dichloroisocyanurate (sodium dichloroisocyanurate, potassium dichloroisocyanurate, etc.), monochloroisocyanurate Substances that generate hypochlorous acid in water such as acid salts (sodium monochloroisocyanurate, potassium monochloroisocyanurate, etc.), trichloroisocyanurates (sodium trichloroisocyanurate, potassium trichloroisocyanurate, etc.),
(b) substances that generate hypobromous acid in water, such as sodium hypobromite, a reaction product of sodium bromide and sodium hypochlorite, and bromine water;
(c) seawater electrolyte (electrolyte containing hypochlorous acid obtained by electrolyzing seawater in an electrolytic cell), and (d) monochloramine, dichloramine, trichloramine, monobrolamine, dibrolamine, tribrolamine, N-chloro Combined chlorine (stabilized chlorine) or combined bromine (stabilized bromine) such as sulfamate and N-bromosulfamate
is mentioned. Among these, (a), (b) and (c) are preferable from the practical viewpoint of the effect of preventing adhesion of marine organisms, economic efficiency, and handleability, and from the viewpoint of industrial availability, Sodium hypochlorite and potassium hypochlorite are particularly preferred. Among (d), preferred are monochloramine and monobroramine, followed by N-chlorosulfamate and N-bromosulfamate, from the viewpoint of the effect of preventing 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 can be prepared by known methods, for example, JP-A-2003-503323, JP-A-2006-022097, JP-A-11-506139, JP-A-2001- 501869, JP-A-2003-507326, JP-A-2014-101251 and JP-A-2017-159276, etc. It can be prepared by the method described.
In the present invention, a reaction product of sulfamic acid and hypochlorous acid and/or hypobromous acid can be preferably used.
Combined chlorine such as monochloramine can be prepared by methods described in Japanese Patent No. 4914146, Japanese Patent Application Laid-Open Nos. 2017-119245 and 2017-53054.
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 chlorine and bromine agents described above may be diluted or dissolved in seawater or freshwater to obtain a desired concentration upon addition.
In addition, when (a) a substance that generates hypochlorous acid in water or (c) seawater electrolyte is added to seawater, hypochlorous acid reacts with bromide ions present in seawater, and quickly chlorine and bromine replaces For example, when sodium hypochlorite is added to seawater, it quickly becomes sodium hypobromite. Therefore, even if any of (a), (b) and (c) is used, the antifouling effect on marine organisms is equivalent.
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 according to the concentration of chlorine dioxide to be used in combination, the state of seawater to be added, etc., but usually the effective chlorine concentration of the chlorine agent or bromine agent to seawater is 0.005 to 0.00. Addition to a concentration of 3 mg/L is preferred.
As used herein, the concentration of chlorine or bromine agent means "available chlorine concentration."
If the concentration of the chlorine agent or the bromine agent is less than 0.005 mg/L, the combined use with chlorine dioxide may not be sufficiently effective in preventing adhesion of marine organisms. 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 an economical point of view.
The concentration of the chlorine agent or bromine agent is more preferably 0.01-0.2 mg/L, more preferably 0.01-0.1 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 bromine agent may be appropriately set depending on the concentration of chlorine dioxide to be added and the state of the seawater to be added, but it is usually 1 to 24 hours per day.
If the addition time is less than 1 hour per day, the combined use with chlorine dioxide may not be sufficiently effective in preventing adhesion of marine organisms.
A more preferable addition time of the chlorine or bromine agent is 14 to 24 hours per day, 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)
Since the chlorine dioxide used in the present invention is an extremely unstable chemical substance, its storage and transportation are very difficult. Therefore, it is preferable to manufacture (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 (apparatus) can also be used.
(1) Reaction of sodium hypochlorite, hydrochloric acid and sodium chlorite NaOCl+2HCl+ 2NaClO2 → 2ClO2 +3NaCl+ H2O
(2) Reaction of sodium chlorite and hydrochloric acid 5NaClO 2 +4HCl → 4ClO 2 +5NaCl+2H 2 O
( 3 ) Reaction with sodium chlorate, hydrogen peroxide and sulfuric acid 2NaClO3 + H2O2 + H2SO4 → 2ClO2 + Na2SO4 + O2 + 2H2O
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 chlorine 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 0.2mg / L with respect to seawater. It is preferred to add
If the concentration of chlorine dioxide is less than 0.002 mg/L, the combined use with a chlorine agent or a bromine agent may not be sufficiently effective in preventing adhesion of marine organisms. 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 an economical point of view.
A more preferred 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 addition time of chlorine dioxide may be appropriately set according to the concentration of the chlorine agent or bromine agent used in combination in the seawater, the state of the seawater to be added, etc., but it is usually 1 to 24 hours per day.
If the addition time is less than 1 hour per day, the combined use of the chlorine agent or the bromine agent may not be sufficiently effective in preventing adhesion of marine organisms.
A more preferable addition time of chlorine dioxide is 14 to 24 hours per day, 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 Agent or Bromine Agent and Chlorine Dioxide in Seawater)
From the above, the chlorine agent or bromine agent and chlorine dioxide are adjusted to have an available 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 preferably added.
Strictly speaking, the concentration of the chlorine agent or bromine agent and chlorine dioxide in seawater is not equivalent to the concentration of each compound added because the concentration of each compound in seawater decreases over time.
Therefore, in carrying out the present invention, depending on the conditions of seawater and marine organisms living there, the concentration of the chlorine agent or bromine agent and chlorine dioxide in seawater is adjusted to the above range. In anticipation of the decrease in concentration, the addition concentration and addition time may be appropriately set.
In view of the above, the chlorine or bromine agent and chlorine dioxide are preferably 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 adhesion of marine organisms of the present invention, other additives known in the art may be used together as long as the effects of the present invention are not impaired.
Examples thereof include dialkyldithiocarbamates, antifouling agents for marine organisms such as cationic surfactants, iron-based metal corrosion inhibitors, antifoaming agents, and the like.
（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。
(Place of addition)
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 water intake system consists of a water conduit, a screen that removes foreign matter in the seawater, a circulating water pump (intake pump), and a circulating water pipe (intake pipe).
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 of addition of each agent in the present invention may be any of the intake channel, the pipe attached to the heat exchanger or the condenser, the water conduit, the inlet of the heat exchanger or the inlet of the condenser. From the point of view of the effect of preventing damage due to adherence of living organisms, the vicinity of the water intake of the water intake pump and the entrance 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。 In power plants, etc., chlorinating agents or brominating agents are added to the seawater taken in in order to obtain the effect of preventing adhesion of marine organisms. , the necessary chlorine or bromine concentration cannot be left in the heat exchanger (condenser), and a sufficient anti-adhesion effect may not be obtained. Therefore, according to the present invention, by adding low-concentration chlorine dioxide to such a seawater system to the upstream side of the condenser, a sufficient effect of preventing adhesion of marine organisms can be obtained within the above-described residual chlorine concentration regulation. Obtainable. Therefore, it is particularly preferable to add chlorine dioxide after adding the chlorine or bromine agent, that is, add the chlorine or bromine agent and chlorine dioxide in this order to the seawater of the seawater cooling water system.
（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 methods for adding each drug include a method using an injection pump, an air diffuser, an atomizer, or the like. Conventional physical means can be used in the present invention to rapidly and substantially uniformly diffuse a trace amount of a chemical into a seawater cooling water system. Specifically, installation of a diffuser, a stirring device, a baffle plate, or the like in the water system can be mentioned. In addition, since the equipment corresponding to these is attached to the seawater cooling water system, this 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。
(Adhesion prevention agent for marine organisms)
The antifouling agent for marine organisms of the present invention is an antifouling agent for marine organisms used in the above method,
The anti-adhesion agent is
(a) chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, sodium monochloroisocyanurate, potassium monochloroisocyanurate, as a chlorine or bromine agent; one or more substances selected from sodium trichloroisocyanurate and potassium trichloroisocyanurate that generate hypochlorous acid in water;
(b) one or more substances selected from sodium hypobromite, a reaction product of sodium bromide and sodium hypochlorite, and bromine water that generates hypobromous acid in water;
(c) seawater electrolyte; or (d) one or more bound chlorine (stable chlorine) or combined bromine (stabilized bromine),
(1) a combination of sodium hypochlorite, hydrochloric acid and sodium chlorite as a chlorine dioxide generating source;
(2) a combination of sodium chlorite and hydrochloric acid; or (3) a combination of sodium chlorite, 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 by the following test examples, but the present invention is not limited by these.
［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]
We confirmed the effectiveness of combined use of hypochlorous acid and chlorine dioxide to prevent adhesion of marine organisms.
A hydrographic test equipment was installed at a certain place on the coast of Wakayama Prefecture facing the Pacific Ocean, and tests were conducted.
Unfiltered seawater (pH 8) pumped using a submersible pump was passed through 15 branched channels (test area) at a flow rate of 1 m 3 /h for 70 days, and the following conditions were applied to each channel. The additive agents (hypochlorous acid and chlorine dioxide) prepared as described above were added at the addition time per day shown in Table 1 so that the agent concentration shown in Table 1 was obtained.
The chemical concentration is the set concentration in the acrylic column for confirming the anti-adhesion effect described below, and the concentration of hypochlorous acid is the effective chlorine concentration.
In addition, the amount of drug added was the same in test plots having the same drug concentration. For example, the amount of hypochlorous acid added in Examples 1, 2 and Comparative Example 1 is the same, and the amount of chlorine dioxide added in 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 water channel to confirm the anti-adhesion effect. was measured to evaluate the anti-adhesion effect.
In addition, as a blank, the test was also performed without the addition of the drug.
The results obtained are shown in Table 1 together with each added agent, 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 agent)
Chlorine dioxide is obtained by mixing aqueous solutions of sodium chlorite and hydrochloric acid, each of which is appropriately diluted with pure water, in a tube before the chemical addition point so that the chlorine dioxide concentration shown in Table 1 is obtained, and the retention time is 1 hour. An aqueous solution of chlorine dioxide generated by holding was added from before the acrylic column for checking the anti-adhesion effect using a metering pump. Regarding the generation of chlorine dioxide, it was confirmed in a preliminary test that no sodium chlorite remained.
Hypochlorous acid is adjusted to the chemical concentration to be added to seawater by diluting 12% sodium hypochlorite aqueous solution as effective chlorine with pure water as appropriate, and acrylic column for checking adhesion prevention effect similar to chlorine dioxide It was added using a metering pump from this side.
（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 anti-adhesion effect)
After the test, the mass Wa (g) of the column removed from the channel was measured. Together with the weight Wb of the column at the time of drying, which had been measured in advance before the test, the amount of adherent organisms (g) was calculated by the following formula.
Adhering biomass (g) = Wa - Wb
The sessile organisms are mainly derived from marine sessile organisms such as mussels such as mussels, barnacles, and bryozoans. In addition, detritus-like substances containing a large amount of organic matter such as excreta and corpses of adherent organisms and slimes, extracellular secretions, and viscous particles and suspended matter contained in seawater also adhere to the column. include.
Based on the state of adhesion of marine organisms to the blank, it can be judged that, in this test example, when the amount of adhered organisms is 15 g or less, there is a sufficient effect of preventing adhesion of marine organisms. In addition, when the amount of adhered organisms is 5 g or less, no adhesion of organisms or dirt is visually observed, and it can be judged that the adhesion of marine organisms is best prevented.
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 results in Table 1 show the following.
(1) When hypochlorous acid was used alone, the additive concentration was 0.075 mg/L (Comparative Example 3), and when chlorine dioxide was used alone, the additive concentration was 0.030 mg/L (Comparative Example 3). Example 8) provides a sufficient effect of preventing adhesion of marine organisms (2). L (Example 1), that is, a sufficient effect of preventing adhesion of marine organisms can be obtained at concentrations of 1/3 and 1/6 of the above (1), respectively. (3) Hypochlorous acid and chlorine dioxide was added at concentrations of 0.025 mg/L and 0.010 mg/L (Examples 2 and 5), respectively, that is, when used together at an addition concentration of 1/3 and 1/3 of the above (1), respectively, Even if the addition time is shorter (18 hours / day) than in the case of (1) above (22 hours / day), the effect of preventing adhesion of marine organisms superior to that of (2) above is obtained (4) First When comparing the case of adding hypochlorous acid to and then adding chlorine dioxide (Example 2) and the case of adding chlorine dioxide first and then adding hypochlorous acid (Example 5), Although both have a sufficient effect of preventing adhesion of marine organisms, 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) Above (1) above, that is, even if hypochlorous acid and chlorine dioxide are added at concentrations higher than the addition concentration that shows a sufficient effect of preventing adhesion of marine organisms by itself, the amount of adherent organisms is 8.7 g with chlorine. (Comparative Example 4), chlorine dioxide only reduces to 7.8 g (Comparative Example 8) (6). Example 2), 4.8 g (Example 3), 4.6 g (Example 4), and 6.1 g (Example 5) The above results show that hypochlorous acid and chlorine dioxide in seawater coexistence of both, that is, an effect corresponding to a synergistic effect. It is an unexpected fact that such a synergistic effect can be obtained by using hypochlorous acid together with chlorine dioxide, which is used as a substitute for hypochlorous acid (chlorine).
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 anti-adhesion effect of chlorine-based oxidizing agents on marine organisms is generally considered to be proportional to the ORP of seawater after addition of the agents. ORP does not always show a constant value depending on the properties of seawater and water temperature, but in this test example, in Examples 1 and 2 in which hypochlorous acid and chlorine dioxide were used in combination, the ORP was 406 and 414, respectively. Even in Comparative Example 1 in which the same concentration of hypochlorous acid was used alone, the ORP was the same 412. From these results, it is speculated that a part of one or both of the agents is decomposed by the redox reaction when hypochlorous acid and chlorine dioxide are used in combination, and the synergistic effect described above cannot be obtained. It is inferred. However, it can be said that it is an unexpected fact that a person skilled in the art could not have easily conceived that such an excellent effect of preventing adhesion to marine organisms was obtained.
［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 using N-chlorosulfamate or monochloramine as a chlorine agent in combination with chlorine dioxide, and when using N-bromosulfamate or monobroramine as a bromine agent in combination with chlorine dioxide We confirmed the effect.
A hydrographic test equipment was installed at a certain place 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 passed once-through at a flow rate of 1 m 3 /h for 68 days through 17 branched channels (test plots). An additive agent prepared as described below was added to each water channel so as to have the agent concentration shown in Table 2 and the addition time per day shown in Table 2.
The chemical concentration is the set concentration in the acrylic column for confirming the anti-adhesion effect described below, and the chemical concentration of the chlorine agent and the bromine agent is the effective chlorine concentration (effective chlorine equivalent concentration).
In addition, the amount of drug added was the same in test plots having the same drug concentration. 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) was inserted into each channel to check the anti-adhesion effect. was measured and the anti-adhesion effect was evaluated.
In addition, as a blank, the test was also performed without the addition of the drug.
The obtained results are shown in Table 2 together with each additive agent, 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 agent)
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 (e.g., the method described in JP-A-2017-159276), and monochloramine and monobroramine are prepared by a known method (e.g., the method described in JP-A-2017-159276). 2017-53054), and then diluted with pure water as appropriate to adjust the chemical concentration to be added to seawater, and the acrylic column for checking the anti-adhesion effect 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 anti-adhesion effect)
In the same manner as in Test Example 1, the amount of adherent organisms (g) on the column was calculated to confirm the effect of preventing adherence of marine organisms.
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 results in Table 2 show the following.
(1) When a chlorine agent or a bromine agent is used alone, a sufficient effect of preventing adhesion of marine organisms cannot be obtained (Comparative Examples 10 to 12), but when used in combination with chlorine dioxide, sufficient marine organisms Obtaining an anti-adhesion effect for organisms (Examples 6 to 8)
(2) Sufficient anti-adhesion effect of marine organisms can be obtained when the chlorine agent alone is used (Comparative Example 14). When used in combination with chlorine, a sufficient effect of preventing adhesion of marine organisms can be obtained (Example 10)
(3) Even when a chlorine agent or a bromine agent is used alone, a sufficient effect of preventing adhesion of marine organisms can be obtained (Comparative Examples 13 to 15), but when used in combination with chlorine dioxide, the best marine organisms to obtain an anti-adhesion effect (Examples 9, 11 and 12)
(4) Sufficient anti-adhesion effect of marine organisms can be obtained When chlorine dioxide is used alone (Comparative Example 18), a sufficient effect cannot be expected at a chlorine dioxide concentration of 1/6 to 2/3. , When used in combination with a chlorine agent or a bromine agent, a sufficient effect of preventing adhesion of marine organisms can be obtained (Examples 6 to 12)
The above results show that the coexistence of N-chlorosulfamate, N-bromosulfamate, monochloramine, monobroramine, and chlorine dioxide in seawater produces an effect corresponding to the synergistic effect of both. This is thought to be due to
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