JP5703456B2 - Manganese scale formation inhibitor in seawater and method for preventing damage of manganese scale - Google Patents
Manganese scale formation inhibitor in seawater and method for preventing damage of manganese scale Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims description 98
- 229910052748 manganese Inorganic materials 0.000 title claims description 95
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 94
- 239000013535 sea water Substances 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 21
- 230000015572 biosynthetic process Effects 0.000 title claims description 19
- 239000003112 inhibitor Substances 0.000 title claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 78
- 239000000498 cooling water Substances 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000002265 prevention Effects 0.000 claims description 9
- 229910001369 Brass Inorganic materials 0.000 description 20
- 239000010951 brass Substances 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000005708 Sodium hypochlorite Substances 0.000 description 12
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 12
- 230000002159 abnormal effect Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 230000003628 erosive effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- -1 iron ions Chemical class 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000004966 inorganic peroxy acids Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/083—Mineral agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Description
本発明は、海水中でのマンガンスケール形成阻害剤およびそれを用いるマンガンスケールの障害防止方法に関する。さらに詳しくは、本発明は、海水中に溶解するマンガンによるスケール形成を阻害するための薬剤およびそれを用いるマンガンスケールの障害防止方法に関する。
本発明は、高濃度の溶解マンガンを含有する海水を冷却水として使用する装置、特にアルミニウム黄銅管からなる熱交換器における障害、具体的には、マンガンスケールの付着およびその付着したスケールの剥離に起因するアルミニウム黄銅管の異常潰食などの障害防止に有用である。
The present invention relates to a manganese scale formation inhibitor in seawater and a method for preventing damage of manganese scale using the same. More specifically, the present invention relates to a drug for inhibiting scale formation by manganese dissolved in seawater and a method for preventing damage of manganese scale using the same.
The present invention relates to an obstacle in a device that uses seawater containing high-concentration dissolved manganese as cooling water, in particular, a heat exchanger composed of an aluminum brass tube, specifically, adhesion of manganese scale and peeling of the adhered scale. It is useful for preventing troubles such as abnormal erosion of the resulting aluminum brass tube.
高濃度（例えば、２０〜１００μｇ／リットル）の溶解マンガンを含有する海水（富マンガン海水）を冷却水として使用する、熱交換器などを構成するアルミニウム黄銅管では、その細管内に富マンガン付着物（マンガンスケール）が形成されて伝熱効率の低下や復水効率の低下を惹き起し、また、硬くかつ脆いマンガンスケールが剥離して細管内の表面に線（溝）状や連点状の孔食（異常潰食）を発生させることが知られている（藤井哲、川邊允志編著、「復水器−理論と実際−」、初版、株式会社愛智出版、2001年12月10日、p.85：非特許文献１参照）。 In an aluminum brass tube that constitutes a heat exchanger or the like that uses seawater (manganese-rich seawater) containing dissolved manganese at a high concentration (for example, 20 to 100 μg / liter) as cooling water, manganese-rich deposits in the narrow tube (Manganese scale) is formed, causing a decrease in heat transfer efficiency and condensate efficiency, and a hard and brittle manganese scale peels off to form a line (groove) or continuous hole on the surface of the narrow tube Known to cause food (abnormal erosion) (Satoshi Fujii, edited by Satoshi Kawamata, "Condenser-Theory and Practice-", First Edition, Aichi Publishing Co., Ltd., December 10, 2001) p.85: See Non-Patent Document 1).
そして、海生生物付着抑制などのために海水を塩素処理する条件下で、マンガンスケールが付着形成されたときに異常潰食が発生することから、マンガンスケールの形成メカニズムは、例えば、水中のＭｎ2+が塩素処理によってＭｎＯ2へと酸化されて管内に付着したものとする説がある。また、マンガン酸化細菌によるものであるとの説がある（川邊允志、外３名編著、「復水器工学ハンドブック」、初版、株式会社愛智出版、1994年3月30日、p.107：非特許文献２参照）。 Then, under the condition that seawater is chlorinated to suppress adhesion of marine organisms and the like, abnormal erosion occurs when manganese scale is deposited, so the mechanism of manganese scale formation is, for example, Mn in water There is a theory that 2+ is oxidized to MnO 2 by chlorination and adhered in the tube. There is also the theory that it is due to manganese-oxidizing bacteria (Satoshi Kawamata, 3 authors, “Condenser Engineering Handbook”, first edition, Aichi Publishing Co., Ltd., March 30, 1994, p.107) : Non-patent document 2).
そのメカニズムがいずれであったとしても、アルミニウム黄銅管の孔食や異常潰食を防止するためには、海水中に鉄イオンを注入して水酸化鉄の防食皮膜を形成することが不可欠であると考えられていた（非特許文献１、p.90-93参照）。 Whatever the mechanism, in order to prevent pitting corrosion and abnormal erosion of the aluminum brass tube, it is essential to inject iron ions into seawater to form an anticorrosion film of iron hydroxide. (See Non-Patent Document 1, pages 90-93).
また、特開２００９−６３２３９号公報（特許文献１）には、熱交換器の伝導管内の冷却水を、マンガン酸化細菌が死滅可能な最低温度×時間に加熱維持する殺菌処理を、マンガン酸化細菌の酸化能回復期間経過毎に行う熱交換器のスケール対策法が記載されている。 JP 2009-63239 A (Patent Document 1) discloses a sterilization treatment in which the cooling water in the conduction tube of the heat exchanger is maintained at a minimum temperature x time at which manganese oxidizing bacteria can be killed. The scale countermeasure method of the heat exchanger which is performed every time the oxidation capacity recovery period elapses is described.
非特許文献１では、マンガンスケールの防止対策として、海水への鉄イオンの注入が有効であるとされているが、水産用水基準（社団法人 日本水産資源保護協会 ２００５年版）では、海生生物の生息環境として維持することが望ましい海域の鉄濃度の基準値を０．２ｍｇ／リットルとしている。また、近年、海水の着色などの影響が懸念され、海水冷却水などへの鉄注入が忌避される傾向が強まっている（非特許文献１、p.85参照）。 In Non-Patent Document 1, it is said that iron ion injection into seawater is effective as a measure to prevent manganese scales, but in the marine water standards (Japan Fisheries Resource Conservation Society 2005 edition) The standard value of iron concentration in the marine area that is desirably maintained as a habitat is set to 0.2 mg / liter. In recent years, there is a concern about the influence of seawater coloring and the like, and there is an increasing tendency to avoid iron injection into seawater cooling water (see Non-Patent Document 1, p.85).
また、特許文献１のスケール対策法は、海生生物付着抑制などのために海水を塩素処理する条件下では、一般細菌と同様にマンガン酸化細菌も殺菌されるため、加熱による殺菌処理は意味をなさないものと考えられる。さらに、この対策法では、一過性の海水冷却水を加熱することになり、エネルギー損失の問題も懸念される。 In addition, the scale countermeasure method of Patent Document 1 has a meaning that sterilization treatment by heating is significant because manganese-oxidizing bacteria are sterilized as well as general bacteria under the condition that seawater is chlorinated to suppress adhesion of marine organisms. It is thought that it does not do. Furthermore, with this countermeasure, transient seawater cooling water is heated, and there is a concern about the problem of energy loss.
そこで、本発明は、高濃度の溶解マンガンを含有する海水を冷却水として使用する装置における、マンガンスケールの付着およびその付着したスケールの剥離に起因する装置の構成材料の異常潰食などの障害防止に有用な海水中でのマンガンスケール形成阻害剤およびそれを用いるマンガンスケールの障害防止方法を提供することを課題とする。 Therefore, the present invention prevents failures such as abnormal erosion of the constituent materials of the apparatus due to adhesion of manganese scale and peeling of the adhered scale in an apparatus that uses seawater containing high-concentration dissolved manganese as cooling water. It is an object of the present invention to provide a manganese scale formation inhibitor useful in water and a method for preventing damage of manganese scale using the same.
発明者らは、上記課題を解決するために、アルミニウム黄銅管を並列に連結した試験装置に高濃度の溶解マンガンを含有する海水を通水し各種薬剤を添加して、マンガンスケールの発生と抑制ならびに異常潰食の防止の観点から、アルミニウム黄銅管内の表面の挙動を観察した結果、特定濃度の過酸化水素を特定時間添加することにより、マンガンスケールの付着が防止され、その結果、鉄イオンを供給しなくともアルミニウム黄銅管内の異常潰食が防止できる事実を見出し、本発明を完成するに到った。 In order to solve the above-mentioned problems, the inventors passed seawater containing high-concentration dissolved manganese into a test apparatus in which aluminum brass pipes were connected in parallel, and added various chemicals to generate and suppress manganese scale. As a result of observing the behavior of the surface in the aluminum brass tube from the viewpoint of preventing abnormal erosion, adhesion of manganese scale was prevented by adding a specific concentration of hydrogen peroxide for a specific time, and as a result, iron ions were The present inventors have found the fact that abnormal erosion in an aluminum brass tube can be prevented without supply, and have completed the present invention.
すなわち、そのメカニズムは明らかではないが、一般細菌が殺菌されない程度の低濃度の過酸化水素を海水に添加することにより、海水中の溶解マンガン濃度がそのスケールを発生しない濃度にまで低下するか、あるいは溶解マンガンがそのスケールを形成しない状態に変化するものと考えられ、このような知見は意外な事実である。
また、海生生物の付着抑制に用いられる次亜塩素酸ナトリウムは、過酸化水素に比較して酸化力が弱いものの酸化剤であり、次亜塩素酸ナトリウムの添加による残留塩素がマンガンスケールの付着を防止できず、さらに異常潰食を惹起することからみても、本発明の知見は意外な事実である。
In other words, the mechanism is not clear, but by adding a low concentration of hydrogen peroxide to seawater that does not kill general bacteria, the concentration of dissolved manganese in seawater is reduced to a concentration that does not cause the scale, Or it is thought that melted manganese changes to the state which does not form the scale, and such knowledge is an unexpected fact.
In addition, sodium hypochlorite, which is used to suppress marine organisms, is an oxidizing agent that has weaker oxidizing power than hydrogen peroxide, and residual chlorine due to the addition of sodium hypochlorite adheres to manganese scale. The findings of the present invention are surprising even in view of the fact that it is impossible to prevent the occurrence of abnormal erosion.
さらに、本発明者らは、海水生物の付着抑制に、次亜塩素酸ナトリウムのような塩素系酸化剤を添加した、溶解マンガンを含有する海水であっても、特定濃度の過酸化水素を特定時間添加することにより、マンガンスケールの付着が防止され、その結果、鉄イオンを供給しなくともアルミニウム黄銅管内の異常潰食が防止できる事実も確認している。 Furthermore, the present inventors specified a specific concentration of hydrogen peroxide even in seawater containing dissolved manganese, to which adhesion of marine organisms was suppressed by adding a chlorinated oxidant such as sodium hypochlorite. By adding for a long time, the adhesion of manganese scale is prevented, and as a result, it has been confirmed that abnormal erosion in the aluminum brass tube can be prevented without supplying iron ions.
かくして、本発明によれば、溶解マンガンを含有する海水を冷却水として使用する水系において、前記海水に過酸化水素または過酸化水素供給化合物を含むマンガンスケール形成阻害剤を過酸化水素として０．１〜２．０ｍｇ／リットルの濃度になるように１日１２〜２４時間添加して、前記水系の装置内で発生するマンガンスケールの付着に起因する障害を防止することを特徴とするマンガンスケールの障害防止方法が提供される。 Thus, according to the present invention, in an aqueous system using seawater containing dissolved manganese as cooling water, the manganese scale formation inhibitor containing hydrogen peroxide or a hydrogen peroxide supply compound in the seawater is 0.1% as hydrogen peroxide. Addition of 12 to 24 hours a day to a concentration of ˜2.0 mg / liter to prevent damage caused by adhesion of manganese scale generated in the aqueous system A prevention method is provided.
また、本発明によれば、上記のマンガンスケールの障害防止方法に使用される、過酸化水素または過酸化水素供給化合物を含むことを特徴とする海水中でのマンガンスケール形成阻害剤が提供される。 In addition, according to the present invention, there is provided a manganese scale formation inhibitor in seawater characterized by containing hydrogen peroxide or a hydrogen peroxide supply compound used in the above-described method for preventing damage of manganese scale. .
本発明によれば、高濃度の溶解マンガンを含有する海水を冷却水として使用する装置における、マンガンスケールの付着およびその付着したスケールの剥離に起因する装置の構成材料の異常潰食などの障害防止に有用な海水中でのマンガンスケール形成阻害剤およびそれを用いるマンガンスケールの障害防止方法を提供することができる。 According to the present invention, in an apparatus that uses seawater containing high-concentration dissolved manganese as cooling water, prevention of troubles such as abnormal erosion of constituent materials of the apparatus due to adhesion of manganese scale and peeling of the attached scale. It is possible to provide a manganese scale formation inhibitor in seawater that is useful for water and a method for preventing damage to manganese scale using the same.
本発明のマンガンスケールの障害防止方法は、水系の装置がアルミニウム黄銅管からなる熱交換器である場合、海水が２０〜１００μｇ／リットルの濃度で溶解マンガンを含有する海水であり、上記の海水中でのマンガンスケール形成阻害剤が過酸化水素として０．１〜２．０ｍｇ／リットルの濃度になるように１日１２〜２４時間添加される場合に、上記の効果がさらに発揮される。
また、本発明のマンガンスケールの障害防止方法は、海水は、海生生物の付着を抑制するための塩素系酸化剤が残留塩素として０．１〜０．３ｍｇ/リットルの濃度になるように所定時間添加された海水である場合でも、上記の効果が発揮される。
When the water-based apparatus is a heat exchanger composed of an aluminum brass tube, the manganese scale failure prevention method of the present invention is seawater containing dissolved manganese at a concentration of 20 to 100 μg / liter. The above effect is further exhibited when the manganese scale formation inhibitor in is added for 12 to 24 hours a day as a hydrogen peroxide concentration of 0.1 to 2.0 mg / liter.
In addition, the manganese scale failure prevention method according to the present invention is configured so that the chlorine-based oxidizing agent for suppressing the adhesion of marine organisms has a concentration of 0.1 to 0.3 mg / liter as residual chlorine. Even in the case of seawater added for a long time, the above-described effects are exhibited.
（海水中でのマンガンスケール形成阻害剤）
本発明の海水中でのマンガンスケール形成阻害剤は、過酸化水素または過酸化水素供給化合物を含むことを特徴とする。
(Manganese scale formation inhibitor in seawater)
The manganese scale formation inhibitor in seawater of the present invention is characterized by containing hydrogen peroxide or a hydrogen peroxide supplying compound.
本発明において、マンガンスケールとは、スケール全体の重量に対してマンガン（ＭｎＯ2）を５重量％以上含有するものをいう。このマンガンスケールは、溶解マンガンとして２０μｇ／リットル以上の濃度で含有する海水を冷却水として使用する場合に、熱交換器（復水器管）のアルミニウム黄銅管の細管に付着成長する蓋然性が高い。 In the present invention, the manganese scale means one containing 5% by weight or more of manganese (MnO 2 ) with respect to the weight of the entire scale. This manganese scale has a high probability of adhering and growing on a thin tube of an aluminum brass tube of a heat exchanger (condenser tube) when seawater containing dissolved manganese at a concentration of 20 μg / liter or more is used as cooling water.
海水中の溶解マンガンの濃度は、海域や気象条件などによりバラツキがある。溶解マンガンの高濃度化の原因は、地殻活動の活発化などにより海底のマンガンが巻き上げられること、海水汚染などの還元性雰囲気下における不溶性酸化マンガン（ＭｎＯ2）が還元溶出されることなどが考えられる。 The concentration of dissolved manganese in seawater varies depending on the sea area and weather conditions. The reason for the high concentration of dissolved manganese is that the bottom layer of manganese is rolled up due to the activation of crustal activity, and that insoluble manganese oxide (MnO 2 ) is reduced and eluted under reducing atmosphere such as seawater contamination. It is done.
本発明の海水中でのマンガンスケール形成阻害剤における有効成分の過酸化水素または過酸化水素供給化合物としては、工業用として市販されている濃度３〜６０％の過酸化水素水溶液や水中で過酸化水素を放出し得る化合物が挙げられる。
また、水中で過酸化水素を放出し得る化合物としては、過炭酸などのような無機過酸、過酢酸のような有機過酸、またはこれらの塩類が挙げられる。
これらの過酸化水素または過酸化水素供給化合物は、用時、例えば、海水冷却水の流路となるアルミニウム黄銅管の海水に供給する際に、海水や淡水で適宜希釈してもよい。
また、過酸化水素として、当該水系または別水系において電気化学分解により発生させた過酸化水素を用いることもできる。
As an active ingredient hydrogen peroxide or a hydrogen peroxide supplying compound in the manganese scale formation inhibitor in seawater of the present invention, hydrogen peroxide aqueous solution having a concentration of 3 to 60% commercially available for industrial use or peroxidation in water Examples include compounds capable of releasing hydrogen.
Examples of the compound capable of releasing hydrogen peroxide in water include inorganic peracids such as percarbonate, organic peracids such as peracetic acid, and salts thereof.
These hydrogen peroxides or hydrogen peroxide supply compounds may be appropriately diluted with seawater or fresh water when in use, for example, when supplied to seawater in an aluminum brass tube serving as a flow path for seawater cooling water.
Further, as hydrogen peroxide, hydrogen peroxide generated by electrochemical decomposition in the aqueous system or another aqueous system can also be used.
（マンガンスケールの障害防止方法）
本発明のマンガンスケールの障害防止方法は、溶解マンガンを含有する海水を冷却水として使用する水系において、本発明の海水中でのマンガンスケール形成阻害剤を添加して、水系の装置内で発生するマンガンスケールの付着に起因する障害を防止することを特徴とする。
すなわち、本発明の海水中でのマンガンスケール形成阻害剤を海水に添加することにより、海水中の溶解マンガン濃度が低下し、マンガンスケールの付着が発生せず、それによる障害を防止できるものと考えられる。
(Manganese scale failure prevention method)
The manganese scale failure prevention method of the present invention is generated in an aqueous system by adding the manganese scale formation inhibitor in seawater of the present invention in an aqueous system using seawater containing dissolved manganese as cooling water. It is characterized by preventing damage caused by adhesion of manganese scale.
That is, by adding the manganese scale formation inhibitor in the seawater of the present invention to seawater, the concentration of dissolved manganese in the seawater is reduced, manganese scale adhesion does not occur, and it is possible to prevent damage caused thereby. It is done.
溶解マンガンを含有する海水を冷却水として使用する水系の装置としては、特に限定されないが、例えば、アルミニウム黄銅管、キュプロニッケル（白銅）管、チタン管、ステンレススチール管などからなる熱交換器や復水器などが挙げられる。
本発明のマンガンスケールの障害防止方法は、水系の装置がアルミニウム黄銅管からなる熱交換器である場合に、特にその優れた効果を発揮する。
There are no particular limitations on the water-based device that uses seawater containing dissolved manganese as cooling water, but for example, heat exchangers and condensers made of aluminum brass tubes, cupronickel (brass) tubes, titanium tubes, stainless steel tubes, etc. Water bottles are listed.
The manganese scale failure prevention method of the present invention exhibits particularly excellent effects when the water-based apparatus is a heat exchanger made of an aluminum brass tube.
本発明のマンガンスケールの障害防止方法では、海水が２０〜１００μｇ／リットルの濃度で溶解マンガンを含有する海水であり、本発明の海水中でのマンガンスケール形成阻害剤が過酸化水素として０．１〜２．０ｍｇ／リットルの濃度になるように１日１２〜２４時間添加されるのが好ましい。 In the method for preventing failure of the manganese scale of the present invention, the seawater is seawater containing dissolved manganese at a concentration of 20 to 100 μg / liter, and the manganese scale formation inhibitor in the seawater of the present invention is 0.1% as hydrogen peroxide. It is preferably added for 12 to 24 hours a day so as to have a concentration of -2.0 mg / liter.
海水中の溶解マンガンの濃度が２０μｇ／リットル未満では、マンガンスケールの発生が起こり難いので、本発明の海水中でのマンガンスケール形成阻害剤を添加しなくてもよい場合がある。
一方、海水中の溶解マンガンの濃度が１００μｇ／リットルを超えても、本発明の海水中でのマンガンスケール形成阻害剤における添加濃度や添加量を高くまたは増量することで対応できるが、通常、海水中の溶解マンガンの濃度における上限は１００μｇ／リットル程度である。
When the concentration of dissolved manganese in seawater is less than 20 μg / liter, manganese scale is unlikely to occur, and therefore the manganese scale formation inhibitor in seawater of the present invention may not be added.
On the other hand, even if the concentration of dissolved manganese in seawater exceeds 100 μg / liter, it can be dealt with by increasing or increasing the concentration or amount of manganese scale formation inhibitor in seawater of the present invention. The upper limit of the concentration of dissolved manganese is about 100 μg / liter.
過酸化水素の濃度が０．１ｍｇ／リットル未満または１日当たりの添加時間が１２時間未満では、本発明の効果が十分に発揮されないことがある。
一方、過酸化水素の濃度が２．０ｍｇ／リットルを超えると、本発明の効果が十分に得られるものの、薬剤の供給過多になることがあり好ましくない。
しかしながら、過酸化水素の濃度や添加時間は、使用場面により適宜設定することができる。実際の現場における過酸化水素の濃度と添加時間は、試験例で用いているようなアルミニウム黄銅管の試験装置を用いて、決定することができる。
また、アルミニウム黄銅管カラムの腐食電位や分極抵抗値をモニタリングすることにより、過酸化水素の濃度や添加時間をコントロールすることもできる。
When the concentration of hydrogen peroxide is less than 0.1 mg / liter or the addition time per day is less than 12 hours, the effects of the present invention may not be sufficiently exhibited.
On the other hand, if the concentration of hydrogen peroxide exceeds the 2.0 mg / l, although the effect of the present invention is sufficiently obtained, may result in excessive supply of the drug is not preferable.
However, the concentration and addition time of hydrogen peroxide can be appropriately set depending on the usage scene. The actual hydrogen peroxide concentration and addition time can be determined by using an aluminum brass tube test apparatus as used in the test examples.
Further, by monitoring the corrosion potential and polarization resistance value of the aluminum brass tube column, the concentration and addition time of hydrogen peroxide can be controlled.
本発明のマンガンスケールの障害防止方法では、海生生物の付着を抑制するための塩素系酸化剤が残留塩素として０．１〜０．３ｍｇ/リットルの濃度になるように添加された海水であっても、本発明の効果が発揮される。 In the method for preventing damage of a manganese scale according to the present invention, the chlorinated oxidant for suppressing the adhesion of marine organisms is seawater added to a residual chlorine concentration of 0.1 to 0.3 mg / liter. However, the effect of the present invention is exhibited.
本発明の方法は、鉄イオンの添加（注入）なしにマンガンスケール付着に起因する異常潰食の発生などの障害を防止できるという効果を有するが、本発明の効果を阻害しない範囲で鉄イオンや他の公知の添加剤を添加してもよい。 The method of the present invention has the effect of preventing troubles such as the occurrence of abnormal erosion due to manganese scale adhesion without the addition (injection) of iron ions, but it does not impair the effects of the present invention. Other known additives may be added.
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 thereto.
（試験例１）
蒸留水１リットルに「ダイゴ人工海水ＳＰ」（日本製薬株式会社製）３６ｇを撹拌下に加えて人工海水を調製した。得られた人工海水７００ｍｌに５０％塩化マンガン（ＭｎＣｌ2・４Ｈ2Ｏ）をＭｎとして１ｍｇ／リットル（１０００μｇ／リットル）になるように添加し、供試海水とした。
次いで、得られた供試海水に、それぞれ酸化剤として過酸化水素および次亜塩素酸ナトリウムを表１に示す濃度になるように添加し、２５℃で１時間撹拌した。その後、孔径０．４５μｍのメンブランフィルターでろ過し、得られたろ液の溶解マンガン濃度を、ＩＰＣ発光分光分析法（ＪＩＳ Ｋ０１０２「工場排水試験方法」５６．マンガン（Ｍｎ）、５６．４ ＩＰＣ発光分光分析法）に準拠して、ＩＰＣ発光分光分析装置（セイコーインスツル株式会社（現 株式会社日立ハイテクサイエンス）製、型式：ＳＰＳ５１００）を用いて測定した。
なお、次亜塩素酸ナトリウムの添加量は、残留塩素濃度を意味する。
(Test Example 1)
Artificial seawater was prepared by adding 36 g of “Daigo Artificial Seawater SP” (manufactured by Nippon Pharmaceutical Co., Ltd.) to 1 liter of distilled water with stirring. To 700 ml of the obtained artificial seawater, 50% manganese chloride (MnCl 2 .4H 2 O) was added as Mn so as to be 1 mg / liter (1000 μg / liter) to obtain test seawater.
Next, hydrogen peroxide and sodium hypochlorite were added to the obtained seawater as oxidizing agents so as to have concentrations shown in Table 1, respectively, and stirred at 25 ° C. for 1 hour. Thereafter, the solution was filtered through a membrane filter having a pore size of 0.45 μm, and the dissolved manganese concentration in the obtained filtrate was determined by IPC emission spectroscopic analysis (JIS K0102 “Factory drainage test method” 56. Manganese (Mn), 56.4 IPC emission spectroscopy). In accordance with the analysis method), the measurement was performed using an IPC emission spectroscopic analyzer (manufactured by Seiko Instruments Inc. (currently Hitachi High-Tech Science Co., Ltd., model: SPS5100)).
The amount of sodium hypochlorite added means the residual chlorine concentration.
酸化剤を添加しない場合（ブランク）についても同様に試験し、この酸化剤無添加のブランク試験における溶解マンガン濃度の測定値に対する、上記の酸化剤添加の試験における溶解マンガン濃度の測定値の割合を百分率で算出した。
ブランク試験の測定値に対する割合が１００％とは、マンガンが析出していないことを意味し、その割合が低くなるほどマンガンが析出していることを示す。
得られた結果を、添加した酸化剤およびその添加量と共に表１に示す。
When the oxidizing agent is not added (blank), the same test is performed, and the ratio of the measured value of the dissolved manganese concentration in the above-described oxidizing agent addition test to the measured value of the dissolved manganese concentration in the blank test without the addition of the oxidizing agent is Calculated as a percentage.
A ratio of 100% with respect to the measured value of the blank test means that manganese is not precipitated, and indicates that manganese is precipitated as the ratio decreases.
The obtained results are shown in Table 1 together with the added oxidizing agent and the amount added.
表１の結果、すなわち酸化剤の添加前後の溶解マンガン濃度の変化を見る限りにおいて、次亜塩素酸ナトリウムの添加ではマンガンの析出が促進される傾向があり、過酸化水素の添加ではそのような傾向がないこと、すなわちマンガンの析出が抑制されていることがわかる。 As far as the results of Table 1, that is, the change in dissolved manganese concentration before and after the addition of the oxidant are observed, the addition of sodium hypochlorite tends to promote the precipitation of manganese, and the addition of hydrogen peroxide has such a tendency. It can be seen that there is no tendency, that is, the precipitation of manganese is suppressed.
（試験例２）
大阪湾内の臨海コンビナートの海水冷却水系を保有する某社内に、同水系の現場の海水を一過式に通水するモデル水路を設けて試験を行った。
具体的には、アルミニウム黄銅管（ＪＩＳ Ｈ３３００−１９８１「銅及び銅合金の継目無管」復水器用黄銅継目無管 Ｃ６８７１、内径１６ｍｍ×長さ１００ｍｍ）の新管を、内面状況調査用に予め流れ方向に二分割し、これらの供試管を二分割前の状態でビニールホース内に挿入したモデル水路を複数作製した。
(Test Example 2)
A model waterway that allows the seawater of the same water system to pass through temporarily was installed in the Sakai company that owns the seawater cooling water system of the coastal complex in Osaka Bay.
Specifically, a new pipe made of aluminum brass pipe (JIS H3300-1981 “Copper and Copper Alloy Seamless Pipe” Condenser Brass Seamless Pipe C6871, Inner Diameter 16 mm × Length 100 mm) is preliminarily used for investigation of the inner surface condition. A plurality of model water channels were prepared by dividing the test tube into two in the flow direction and inserting these test tubes into the vinyl hose in the state before the split.
次いで、１つのモデル水路を１つの試験区として、複数のモデル水路を並列に接続し、水深１〜２ｍの位置から取水した海水（溶解マンガンとして２０〜１００μｇ／リットル含有）を約１ｍ3／時間（平均流速約１．４ｍ／秒）で６０日間通水し、定量ポンプを用いて、表２に示す薬剤添加条件で過酸化水素および塩素系酸化剤としての次亜塩素酸ナトリウムを添加した。 Then, using one model waterway as one test section, connecting a plurality of model waterways in parallel, seawater (containing 20-100 μg / liter dissolved manganese) taken from a position with a water depth of 1 to 2 m is about 1 m 3 / hour. Water was passed for 60 days at an average flow rate of about 1.4 m / sec, and hydrogen peroxide and sodium hypochlorite as a chlorine-based oxidizing agent were added using a metering pump under the chemical addition conditions shown in Table 2.
なお、海生生物の付着抑制に用いられる塩素系酸化剤としての次亜塩素酸ナトリウムなどは、通常、一定の残留塩素濃度を維持しながら間欠的または連続的に添加されるため、本発明の有効成分である過酸化水素とは、添加時期が重複する場合と重複しない場合が考えられる。そこで、表２の薬剤添加条件の項目「両者の共存」には、添加時期が重複する場合、すなわち過酸化水素と次亜塩素酸ナトリウムとの添加（注入）を同時に開始し、それぞれの所定時間添加する場合を「共存」、重複しない場合、すなわち過酸化水素を所定時間添加し終えた後で、次亜塩素酸ナトリウムの添加を開始し、所定時間添加する場合を「非共存」と記載する。 It should be noted that sodium hypochlorite as a chlorine-based oxidant used to suppress adhesion of marine organisms is usually added intermittently or continuously while maintaining a constant residual chlorine concentration. It is conceivable that hydrogen peroxide as an active ingredient may or may not overlap with the addition time. Therefore, in the item “coexistence of both” of the chemical addition conditions in Table 2, when the addition times overlap, that is, the addition (injection) of hydrogen peroxide and sodium hypochlorite is started at the same time for each predetermined time. The case of addition is described as “coexistence”, the case where there is no overlap, that is, after the addition of hydrogen peroxide for a predetermined time, the addition of sodium hypochlorite is started and the case of addition for a predetermined time is described as “non-coexistence” .
このようにして各試験区に海水の通水と薬剤の添加を６０日間継続し、その後、モデル水路のビニールホースからアルミニウム黄銅管を取り出し、水洗してスライムなどを除去した。
一片の供試管を乾燥させた後、通水面状況（色呈）を目視で観察し、線状孔食の長さ（ｍｍ）および最大深さ（ｍｍ）を、それぞれノギス（コーナン商事株式会社製、型式：ＥＫＭ−０２−００６６）およびポイントマイクロメータ（株式会社ミツトヨ製、型式：ＣＰＭ１５−２５ＭＪ）を用いて測定した。
線状孔食とは、供試管内面に流れ方向と平行に生じた線状の孔食をいい、観察された線状孔食の最大長さを、次の基準で区分した。
−：線状孔食が観察されない
±：＜１０ｍｍの線状孔食
＋：＜３０ｍｍの線状孔食
＋＋：＜５０ｍｍの線状孔食
＋＋＋：≧５０ｍｍの線状孔食
In this way, the passage of seawater and the addition of the chemicals were continued for 60 days in each test section, and then the aluminum brass tube was taken out from the vinyl hose of the model waterway and washed with water to remove slime and the like.
After drying a piece of the test tube, the condition of the water flow surface (coloration) was visually observed, and the length (mm) and maximum depth (mm) of the linear pitting corrosion were respectively determined by calipers (manufactured by Konan Corporation). , Model: EKM-02-0066) and point micrometer (manufactured by Mitutoyo Corporation, model: CPM15-25MJ).
Linear pitting refers to linear pitting that occurs parallel to the flow direction on the inner surface of the test tube, and the maximum length of observed linear pitting was classified according to the following criteria.
-: No linear pitting corrosion is observed
±: <10 mm linear pitting corrosion
+: <30 mm linear pitting ++: <50 mm linear pitting +++: ≧ 50 mm linear pitting
また、アルミニウム黄銅管の内面の付着物を掻き取り、掻き取った内面付着物を、Ｘ線回折装置（株式会社リガク製、型式：Ｍｕｌｔｉｆｌｅｘ)および蛍光Ｘ線分析装置（エスアイアイ・ナノテクノロジー株式会社（現：株式会社日立ハイテクサイエンス）製、型式：ＳＥＡ２１１０）を測定・分析し、内面付着物中にマンガンが含まれ、かつその酸の形態が二酸化マンガンであることを確認した。
もう一片の供試管を温度１１０℃で１時間乾燥させた後、ＪＩＳ Ｋ０１００「工業用水腐食性試験方法」の酸洗浄法に準拠して、室温条件下、約１０％硫酸で約５分間浸漬し、ナイロンブラシを用いて腐蝕生成物を除去し、酸洗前後の重量差から内面付着物量（ｍｇ／ｃｍ2）を求め、さらに、５２５℃（３時間）で灰化させた残留重量も勘案し、内面付着物に占めるＭｎＯ2の割合（重量％）を求めた。
薬剤を添加しない場合（ブランク）についても同様に試験した。
得られた結果を、薬剤添加条件と共に表２および３に示す。
Also, scraping off the deposits on the inner surface of the aluminum brass tube, and scraping off the deposits on the inner surface, the X-ray diffractometer (manufactured by Rigaku Corporation, model: Multiflex) and the fluorescent X-ray analyzer (SII Nanotechnology Inc.) (Currently, Hitachi High-Tech Science Co., Ltd., Model: SEA2110) was measured and analyzed, and it was confirmed that manganese was contained in the inner surface deposit and that the acid form was manganese dioxide.
After another sample tube was dried at a temperature of 110 ° C. for 1 hour, it was immersed in about 10% sulfuric acid for about 5 minutes at room temperature in accordance with the acid cleaning method of JIS K0100 “Industrial Water Corrosion Test Method”. The corrosion product was removed using a nylon brush, and the amount of deposits on the inner surface (mg / cm 2 ) was determined from the weight difference before and after pickling, and the residual weight ashed at 525 ° C. (3 hours) was also taken into account. The ratio (% by weight) of MnO 2 in the inner surface deposit was determined.
The same test was performed when no drug was added (blank).
The obtained results are shown in Tables 2 and 3 together with the drug addition conditions.
表２および３の結果から、次のことがわかる。
（１）薬剤無添加の場合には、マンガンスケールの付着と線状孔食が認められること（ブランク参照）
（２）次亜塩素酸ナトリウムの単独添加では、マンガンスケールおよびスケールに占める酸化マンガン（ＭｎＯ2）の割合がブランクに比較して顕著に増加し、線状孔食も顕著であること（比較例１〜５参照）
（３）過酸化水素を０．１〜２．０ｍｇ／リットルの濃度になるように１日１２時間〜２４時間添加することにより、マンガンスケールの付着が防止され、線状孔食が認められないこと（実施例１〜２２参照）
（４）過酸化水素を０．１ｍｇ／リットルの濃度になるよう１日１０時間添加した場合では、僅かであるがやや酸化マンガンの含有割合が高いスケールと僅かであるが線状孔食が認められること（比較例６〜８参照）
（５）次亜塩素酸ナトリウムを添加した場合であっても、過酸化水素を０．１〜２．０ｍｇ／リットルの濃度になるように１日１２時間〜２４時間添加併用することにより、マンガンスケール付着が顕著に防止され線状孔食が認められないこと（実施例１〜１６参照）
From the results of Tables 2 and 3, the following can be understood.
(1) Manganese scale adherence and linear pitting corrosion are observed when no chemical is added (see blank)
(2) When sodium hypochlorite is added alone, the manganese scale and the proportion of manganese oxide (MnO 2 ) in the scale are significantly increased compared to the blank, and linear pitting corrosion is also significant (comparative example) 1-5)
(3) By adding hydrogen peroxide to a concentration of 0.1 to 2.0 mg / liter for 12 hours to 24 hours a day, adhesion of manganese scale is prevented and linear pitting corrosion is not observed. (See Examples 1-22)
(4) When hydrogen peroxide was added at a concentration of 0.1 mg / liter for 10 hours a day, a slight but slightly higher scale of manganese oxide content and a slight but linear pitting corrosion were observed. (See Comparative Examples 6-8 )
(5) Even when sodium hypochlorite is added, manganese can be added by adding hydrogen peroxide to a concentration of 0.1 to 2.0 mg / liter for 12 hours to 24 hours a day. Scale adhesion is remarkably prevented and no linear pitting is observed (see Examples 1 to 16).
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