CN106686980B - 金属的生物腐蚀抑制剂 - Google Patents
金属的生物腐蚀抑制剂 Download PDFInfo
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- CN106686980B CN106686980B CN201580049962.9A CN201580049962A CN106686980B CN 106686980 B CN106686980 B CN 106686980B CN 201580049962 A CN201580049962 A CN 201580049962A CN 106686980 B CN106686980 B CN 106686980B
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- Prior art keywords
- biological corrosion
- metal
- corrosion inhibitor
- carbon atom
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
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- 239000011781 sodium selenite Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
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- 235000012222 talc Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
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- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
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- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
- C23F11/122—Alcohols; Aldehydes; Ketones
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
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- C09K2208/32—Anticorrosion additives
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
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Abstract
本发明的课题在于提供以低浓度发挥效果并且生物分解性也优异的金属的生物腐蚀抑制剂。一种金属的生物腐蚀抑制剂，其将3‑甲基戊二醛作为有效成分。
Description
技术领域
本发明涉及金属的生物腐蚀的抑制剂。
背景技术
所谓生物腐蚀是指通过环境中存在的微生物的作用而直接或间接地诱发的腐蚀现象，已报道了许多的研究例(例如非专利文献1等)，但关于发生的机制等还残留有未阐明的部分。在最近的研究中，报道了在生物腐蚀为基于2种以上的微生物(例如硫酸还原菌及甲烷生成菌等)而进行的腐蚀的情况下，有时这些微生物的作用协同地促进腐蚀。
近年来，在化石燃料(例如石油、天然气、页岩油、页岩气等)的采掘中利用高压水进行岩盘的破碎等，在作为该高压水的流路的铁配管等中见到了生物腐蚀。为了抑制该生物腐蚀，使用了戊二醛(参照专利文献1)。一般来说，已知戊二醛及其类似物具有杀菌性，其中，已知戊二醛具有优异的杀菌性(非专利文献2)。
现有技术文献
非专利文献
非专利文献1：Journal of Bioscience and Bioengineering VOL.110，No.4，pp.426-430(2010)
非专利文献2：Journal of applied bacteriology V0l.30，No.1，78-87(1967)
专利文献
专利文献1：美国专利第2801216号说明书
发明内容
发明所要解决的课题
另一方面，具有杀菌性的化合物不少显示出高毒性。由于这样的化合物在被放出到环境中的用途中使用时，有可能对作业者、生态系统造成影响，所以希望使用量尽量少，此外希望在环境中迅速地被分解。即，在具有杀菌性的化合物中，希望以低浓度显示所期望的效果，同时具有高生物分解性。已知在化石燃料的采掘中作为生物腐蚀抑制剂而频繁使用的戊二醛具有致突变性，且生物分解性不充分，在比较长期的过程中有可能残存在环境中，上述的影响令人担忧。
于是，本发明的目的在于提供以低浓度发挥效果并且生物分解性也优异的金属的生物腐蚀抑制剂、该生物腐蚀抑制剂的制造方法、使用了该生物腐蚀抑制剂的金属的生物腐蚀的抑制方法。
用于解决课题的方案
本发明人们详细进行了研究，结果发现，3-甲基戊二醛与戊二醛相比具有较高的生物分解性，并且以极低浓度体现出金属的生物腐蚀抑制效果，从而完成了本发明。
即，本发明提供下述[1]～[8]。
[1]一种金属的生物腐蚀抑制剂，其将3-甲基戊二醛作为有效成分。
[2]根据[1]所述的生物腐蚀抑制剂，其中，上述生物腐蚀为基于选自硫酸还原菌、硝酸还原菌、甲烷生成菌、碘氧化菌、铁氧化细菌及硫氧化细菌中的至少1种而进行的腐蚀。
[3]根据[1]或[2]所述的生物腐蚀抑制剂，其还包含下述式(1)所表示的化合物或下述式(2)所表示的化合物中的1种以上，
[化学式1]
(R1、R2分别独立地表示碳原子数为1到6的烷基，或者彼此连结而表示碳原子数为2到7的亚烷基)
[化学式2]
(R1、R2如上述定义的那样，R3、R4分别独立地表示碳原子数为1到6的烷基，或者彼此连结而表示碳原子数为2到7的亚烷基)。
[4]根据[1]～[3]中任一项所述的生物腐蚀抑制剂，其为有效成分的总浓度为0.01ppm～3000ppm的范围的水性液的形态。
[5]根据[1]～[4]中任一项所述的生物腐蚀抑制剂，其中，上述金属为铁。
[6]根据[1]～[5]中任一项所述的金属的生物腐蚀抑制剂的制造方法，其包括：使式(1)所表示的化合物或式(2)所表示的化合物中的1种以上与水接触而产生3-甲基戊二醛的工序。
[7]根据[6]所述的金属腐蚀抑制剂的制造方法，其中，使酸共存。
[8]一种金属的生物腐蚀抑制方法，其使用[1]～[5]中任一项所述的生物腐蚀抑制剂。
发明效果
根据本发明，能够提供以低浓度发挥效果并且生物分解性也优异的金属的生物腐蚀抑制剂。
附图说明
图1是表示实施例1中3-甲基戊二醛的生物腐蚀抑制试验结果(铁的溶出浓度)的图表。
图2是表示比较例1中戊二醛的生物腐蚀抑制试验结果(铁的溶出浓度)的图表。
具体实施方式
本发明的制剂含有3-甲基戊二醛作为有效成分。3-甲基戊二醛为公知物质，可以通过公知的方法(例如Organic Syntheses，Vol.34，p.29(1954)、及Organic Syntheses，Vol.34，p.71(1954)等中记载的方法)、或依据其的方法来制造。
本发明的制剂除含有3-甲基戊二醛以外，只要不损害本发明的目的，还可以包含在生物腐蚀抑制剂的领域中惯用的成分。作为该成分，可列举出例如其他的抗菌剂、分散剂、悬浮剂、展开剂、渗透剂、湿润剂、粘浆剂、稳定剂、阻燃剂、着色剂、抗氧化剂、抗静电剂、发泡剂、润滑剂、凝胶化剂、造膜助剂、防冻剂、粘度调整剂、pH调整剂、防腐剂、乳化剂、消泡剂、载体等。
作为其他的抗菌剂，可列举出例如氧化剂(过乙酸、单过硫酸钾、过硼酸钠、过氧化氢、过碳酸钠等)、鏻盐(THPS、聚醚聚氨基亚甲基膦酸酯、三丁基十四烷基氯化鏻等)、烷基苯磺酸、季铵盐(N-烷基二甲基苄基氯化铵、N-二烷基甲基苄基氯化铵等)、异噻唑啉·噻唑啉·异噻唑酮系化合物(2-(硫氰基甲基硫代)苯并噻唑、异噻唑酮等)、硫代氨基甲酸酯系化合物、氢醌系化合物、除3-甲基戊二醛以外的醛化合物(戊二醛、氯乙醛、1，9-壬二醛、2-甲基-1，8-辛二醛等)、偶氮系化合物、苯扎氯铵、次氯酸、噁唑烷化合物、咪唑系化合物(1，2-二甲基-5-硝基-1H-咪唑等)、氨基醇、醚类、脂质体类、炔烃烷氧基化物类(alkynealkoxylates)、溴系杀生物剂(2，2-二溴-2-硝基乙酰胺等)、酶类(endo-β-1，2-galactanase(β-1，2-半乳糖内切酶)等)、金属离子类、酚系化合物等。这些抗菌剂可以单独使用，也可以将2种以上并用。
作为分散剂，可列举出例如高级醇的硫酸酯、烷基磺酸、烷基芳基磺酸、羟基烷基胺、脂肪酸酯、聚环氧烷烃系、脱水山梨醇系等表面活性剂；皂类、酪蛋白、明胶、淀粉、海藻酸、琼脂、羧甲基纤维素(CMC)、聚乙烯基醇、松焦油、糖油、膨润土、甲酚皂等。这些分散剂可以单独使用，也可以将2种以上并用。
作为载体，可列举出例如水、醇(甲醇、乙醇、异丙醇、二醇、甘油等)、酮(丙酮、甲基乙基酮等)、脂肪族烃(己烷、液体石蜡等)、芳香族烃(苯、二甲苯等)、卤代烃、酸酰胺、酯、腈等液体载体；粘土类(高岭土、膨润土、酸性白土等)、滑石类(滑石粉、叶腊石粉等)、二氧化硅类(硅藻土、无水硅酸、云母粉等)、氧化铝、硫粉末、活性炭等固体载体等。这些载体可以单独使用，也可以将2种以上并用。
本发明的制剂中的上述有效成分的总含有比例只要根据剂型、使用方式等来适当设定即可，通常为1～100质量％，从费用相对于效果的观点出发，优选为5～100质量％，更优选为5～95质量％。
本发明的制剂的制造方法没有特别限制，可以使用自身公知的方法或依据其的方法。例如可以通过在3-甲基戊二醛中根据期望添加生物腐蚀抑制剂的领域中惯用的成分并混合等来制造。
作为本发明的剂型，可列举出例如乳剂、液剂、水溶剂、水合剂、粉剂、粒剂、微粒剂、片剂、糊剂、悬浮剂、喷雾剂、涂布剂等。制剂化成各剂型的方法没有特别限制，可以通过自身公知的方法或依据其的方法来进行制剂化。
本发明的制剂的有效成分即3-甲基戊二醛相对于引起生物腐蚀的微生物具有戊二醛以上的杀菌作用，并且生物分解性高。因此，本发明的制剂适宜用于抑制金属的生物腐蚀。作为引起生物腐蚀的微生物，可列举出例如硫酸还原菌、硝酸还原菌、甲烷生成菌、碘氧化菌、铁氧化细菌及硫氧化细菌等，但并不限定于这些。另外，本发明中所谓生物腐蚀的“抑制”是包含将生物腐蚀的发生防患于未然、及抑制生物腐蚀的进展(恶化)的概念。
本发明中所谓“硫酸还原菌”是具有将硫酸盐还原的能力的微生物的总称。作为硫酸还原菌的具体例子，可列举出Desulfovibrio属(脱硫弧菌属)的微生物、Desulfobacter属(脱硫菌属)的微生物、Desulfotomaculum属(脱硫肠状菌属)的微生物等。
本发明中所谓“硝酸还原菌”是具有将硝酸盐还原的能力的微生物的总称。
本发明中所谓“甲烷生成菌”是具有在厌氧的环境下生成甲烷的能力的微生物的总称。作为甲烷生成菌的具体例子，可列举出Methanobacterium属(甲烷杆菌属)的微生物、Methanococcus属(甲烷球菌属)的微生物、Methanosarcina属(甲烷八叠球菌属)的微生物等。
本发明中所谓“碘氧化菌”是具有将碘化物离子(I-)氧化成分子状碘(I2)的能力的微生物的总称。作为碘氧化菌的具体例子，可列举出Roseovarius sp.2S-5、Iodideoxidizing bacterium MAT3株等。
本发明中所谓“铁氧化细菌”是具有将2价的铁离子(Fe2+)氧化成3价的铁离子(Fe3 +)的能力的微生物的总称。作为铁氧化细菌的具体例子，可列举出Mariprofundusferrooxydans、Acidithiobacillus ferrooxidans等。
本发明中所谓“硫氧化细菌”是具有将硫或无机硫化合物氧化的能力的微生物的总称。作为硫氧化细菌的具体例子，可列举出Thiobacillus属(硫杆菌属)细菌、Acidithiobacillu s属(嗜酸硫杆菌属)细菌、Sulfolobus属(硫化叶菌属)古细菌、Acidianus属(嗜酸两面菌属)古细菌等。
本发明的制剂优选用于抑制基于选自硫酸还原菌、硝酸还原菌、甲烷生成菌、碘氧化菌、铁氧化细菌及硫氧化细菌中的至少1种；更优选基于选自硫酸还原菌、硝酸还原菌及甲烷生成菌中的至少1种；进一步优选基于选自硫酸还原菌及甲烷生成菌中的至少1种；特别优选基于甲烷生成菌而进行的生物腐蚀。
甲烷生成菌嗜好厌氧的环境，在水田、以及沼泽、池、湖、河川、海及化石燃料的采掘现场等中栖息。
硫酸还原菌嗜好厌氧的环境，只要是包含水分的环境，则大都栖息，例如在森林土壤、农田、沼泽、池、湖、河川及海等所有场所栖息。
硝酸还原菌嗜好厌氧的环境，由于与甲烷生成菌、硫酸还原菌相比，即使是氧化的环境也能够生育，所以在上述环境中栖息。
铁氧化细菌存在于矿山废水等中。此外在河川等中在少量茶色的堆积物等积存的场所等中栖息。
硫氧化细菌在与铁氧化细菌同样的环境中栖息，此外由于在生活排水中也栖息，所以也参与污水管的混凝土腐蚀等。进而在含有硫的温泉中也栖息。
碘氧化细菌存在比较多的场所是地下碱水，此外在海洋环境中也广泛存在。
因此，本发明的制剂适宜用于抑制在上述的微生物的栖息环境中存在的或设置的金属的生物腐蚀。
使用本发明的制剂的金属只要是暴露于存在引起生物腐蚀的微生物的环境中则没有特别限制，例如可列举出铁、铜、锌、锡、铝、镁、钛、镍、铬、锰、钼及包含选自它们中的至少1种的合金等。其中，从工业利用的观点出发，优选为铁及包含铁的合金，更优选为铁。
本发明的制剂的使用方法只要不损害本发明的目的则没有特别限制，作为其一个方式，可列举出例如在金属被暴露于存在引起生物腐蚀的微生物的环境中时，在这之前预先使本发明的制剂存在于该环境中的方法等。若列举出该方式的具体例子，则在利用水压破碎法的化石燃料(例如石油、天然气、页岩油、页岩气等)的采掘中，通过在以高压注入到岩盘等中的液体(高压水)中预先添加本发明的制剂并使其溶解，从而能够抑制在高压水所接触的金属(例如高压水的流路即金属配管等)中产生的生物腐蚀。或者，也可以在金属被暴露于存在引起生物腐蚀的微生物的环境中的期间，使该环境中存在本发明的制剂。作为另一方式，例如可列举出对需要抑制生物腐蚀的金属的表面直接涂布或喷雾本发明的制剂、或将本发明的制剂溶解或分散到水、有机溶剂等中而得到的溶液的方法等。
作为本发明的制剂的使用形态，优选上述有效成分的总浓度为特定的范围的水性液的形态。
所述水性液中的有效成分的总浓度通常为10000ppm以下，从费用相对于效果的观点出发，优选为0.01ppm～3000ppm，更优选为0.1ppm～1000ppm。若该浓度低于0.01ppm，则存在生物腐蚀抑制效果变小的倾向，若超过10000ppm则变得大过剩而存在在价格方面难以利用的倾向。本说明书中，“ppm”只要没有特别说明，则是指“质量ppm”。
水性液的制造方法没有特别限制，可以使用自身公知的方法或依据其的方法。例如可以通过将上述有效成分添加到适当的液体载体中并搅拌而使其溶解或分散来制造。作为该液体载体，可列举出例如作为本发明的制剂可以包含的成分之一而在上述中例示出的液体载体等。
水性液例如可以作为在水压破碎法中使用的高压水等而利用。将水性液作为该高压水使用时，水性液也可以包含在高压水中惯用的成分(例如支撑剂、粘度调整剂、表面活性剂、酸等)。
此外，水性液也可以涂布或喷雾于需要抑制生物腐蚀的金属的表面。
对于本发明的制剂中的作为有效成分的3-甲基戊二醛来说，从保存稳定性的观点出发，也可以作为包含下述式(1)所表示的缩醛化合物(以下，称为化合物(1))或下述式(2)所表示的二缩醛化合物(以下，称为化合物(2))中的1种以上的形态而使其在本发明的制剂中进一步含有而进行保存及运输。
[化学式3]
(R1、R2分别表示碳原子数为1到6的烷基、或者彼此连结而表示碳原子数为2到7的亚烷基)
[化学式4]
(R1、R2、R3、R4分别表示碳原子数为1到6的烷基、或者R1与R2、R3与R4彼此连结而表示碳原子数为2到7的亚烷基)
即，化合物(1)或化合物(2)中的1种以上可以作为3-甲基戊二醛的等价体而使其在本发明的制剂中进一步含有。对含有化合物(1)或化合物(2)中的1种以上时的含量，并没有特别限制。另外，不含有3-甲基戊二醛而仅含有化合物(1)或化合物(2)中的1种以上的制剂也可以与本发明的制剂同等地处置。
在使用前使进一步含有化合物(1)或化合物(2)中的1种以上的本发明的制剂与水接触而能够产生3-甲基戊二醛。此外，也可以通过使化合物(1)或化合物(2)中的1种以上与在作为生物腐蚀抑制的对象的环境中存在的水直接接触而产生3-甲基戊二醛。包含如上所述地通过与水接触而能够产生3-甲基戊二醛的化合物(1)或化合物(2)中的1种以上的制剂也为本发明的制剂的一个方式。
使还包含化合物(1)或化合物(2)中的1种以上的本发明的制剂与水接触而产生3-甲基戊二醛时，根据需要也可以使用酸。作为所使用的酸，没有特别限定，可列举出例如硫酸、磷酸、硝酸、盐酸、硼酸等无机酸；甲酸、醋酸、丙酸、草酸等有机酸。使还包含化合物(1)或化合物(2)中的1种以上的本发明的制剂与水接触的方法没有特别限定，可以使水与将还包含化合物(1)或化合物(2)中的1种以上的本发明的制剂与酸预先混合而成的组合物接触，也可以使还包含化合物(1)或化合物(2)中的1种以上的本发明的制剂与预先将酸与水混合而成的溶液接触。
对使用的水的量没有特别限制，通常，优选与化合物(1)或化合物(2)中的1种以上的合计量等量以上。对接触时间没有特别限制，但通常为5秒以上，优选为1分钟以上，更优选为10分钟以上。对接触温度没有特别限制，但通常为-20℃到200℃，优选为0℃到120℃，更优选为10℃到100℃。对酸的使用量没有特别限制，但通常为将酸与水混合时的pH成为6.0以下的量，优选成为1.0到5.6的量，更优选成为2.0到5.0的量。
化合物(1)、化合物(2)中，作为R1～R6分别独立地表示的碳原子数为1到6的烷基，可列举出例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、环己基。其中，优选甲基、乙基、正丙基，更优选甲基、乙基。此外，作为R1与R2、R3与R4彼此连结而表示的亚烷基，可列举出例如亚乙基、正亚丙基、正亚丁基、正亚戊基、正亚己基、2-甲基-亚乙基、1，2-二甲基亚乙基、2-甲基-正亚丙基、2，2-二甲基-正亚丙基、3-甲基-正亚戊基。其中，优选亚乙基、正亚丙基、2-甲基-正亚丙基、2，2-二甲基-正亚丙基、2-甲基-亚乙基、1，2-二甲基亚乙基，更优选亚乙基、正亚丙基、2-甲基-正亚丙基、2，2-二甲基-正亚丙基。
化合物(1)、化合物(2)为公知化合物，可以通过公知的方法(例如日本特开平11-228566号公报)、或依据其的方法来制造。
使用还包含化合物(1)或化合物(2)中的1种以上的本发明的制剂时，上述“有效成分的总含有比例”及“有效成分的总浓度”分别表示3-甲基戊二醛、化合物(1)、化合物(2)的含有比例的合计及浓度的合计。
使用本发明的制剂时，只要不损害本发明的目的，也可以将自身公知的杀菌方法或依据其的方法并用。
例如，也可以并用公知的抗菌剂，也可以并用基于pH控制的杀菌方法(例如参照WO2010/056114、WO2008/134778等)、利用超声波照射的杀菌方法(例如参照WO2000/024679等)等。作为可以与本发明的制剂并用的公知的抗菌剂，可列举出例如作为本发明的制剂可以包含的成分之一而在上述中例示出的其他的抗菌剂等。
实施例
以下列举出实施例对本发明更详细地进行说明，但本发明并不限定于以下的实施例。
实施例1
对于3-甲基戊二醛，如上所述地进行生物腐蚀抑制试验。
[无机盐海水培养基(A液)的制备]
将Milli-Q水970ml、NaCl 19.0g、MgCl2·6H2O 2.6g、CaCl2·2H2O 0.15g、Na2SO44.0g、NH4Cl 0.25g、KH2PO4 4.0g、KCl 0.5g、HEPES(2-[4-(2-羟基乙基)-1-哌嗪基]乙烷磺酸)23.8g在厌氧性腔室内混合溶解，制备了无机盐海水培养基(A液)。
另外，Milli-Q水是使用Merk Millipore公司制装置(例如、Milli-Q Integral10)而制造的超纯水。
[碳酸氢钠溶液(C液)的制备]
在Milli-Q水30ml中溶解NaHCO3 2.52g后，进行过滤器除菌，制备了碳酸氢钠溶液(C液)。
[微量元素溶液(E液)的制备]
将HCI(35％)8.3ml、FeSO4·7H2O 2100mg、H3BO4 30mg、MnCl2·4H2O 100mg、CoCl2·6H2O 190mg、NiCl2·6H2O 24mg、CuCl2·2H2O 2mg、ZnSO4·7H2O 144mg、Na2MoO4·2H2O 36mg混合，利用Milli-Q水定容成100ml后，进行过滤器除菌，制备了微量元素溶液(E液)。
[硒钨溶液(S液)的制备]
将NaOH 400mg、Na2SeO34mg、Na2WO4·2H2O8mg混合，利用Milli-Q水定容成100ml后，进行过滤器除菌，制备了硒钨溶液(S液)。
[维生素溶液(V液)的制备]
将4-氨基苯甲酸4mg、D-生物素1mg、烟酸10mg、D-泛酸钙5mg、吡哆素盐酸盐15mg、硫胺素盐酸盐10mg、维生素B125mg混合，利用Milli-Q水定容成100ml后，进行过滤器除菌，制备了维生素溶液(V液)。
<生物腐蚀抑制试验>
将A液进行10分钟左右气体置换，利用高压釜进行121℃、20分钟加热后，添加C液、E液、S液及V液，将所得到的混合液各20ml地分注到装有经灭菌的铁薄片(0.08g Iron foil(纵10mm×横10mm×厚度0.1mm：Sigma-Aldrich356808-G))的小瓶中。将各小瓶进行5分钟气体置换(在N2气中按照最终成为20％CO2气的方式混合CO2气)后，迅速地塞上丁基橡胶塞，以铝密封垫可靠地固定。之后，使用注射器添加0.5ml(106～109cells/ml)的Methanococcusmaripaludis KA-1株，进一步按照成为图1中所示的浓度的方式添加3-甲基戊二醛。将各小瓶在37℃下静置，为了确认铁薄片中的生物腐蚀的进行度，在7天后、14天后、21天后、28天后测定铁的溶出浓度。关于铁的溶出浓度的测定，分取各小瓶中的溶液(1.0ml)，向其中添加0.5ml的6M HCl而将不溶性的铁溶解，添加1.0ml的1M L-抗坏血酸而将三价铁还原成二价铁后，通过邻菲绕啉法(o-phenanthroline method)进行比色测定。将结果示于图1中。
比较例1
除了使用戊二醛来代替3-甲基戊二醛以外，与实施例1同样地进行生物腐蚀抑制试验。将结果示于图2中。
由图1及图2的结果获知，就3-甲基戊二醛而言，添加浓度为1ppm时铁的溶出浓度被抑制得充分低。另一方面，就戊二醛而言，为了将铁的溶出浓度抑制为相同程度，添加浓度必须为100ppm。因此，显示3-甲基戊二醛与戊二醛相比，以极低浓度具有良好的生物腐蚀抑制作用。
实施例2
对于3-甲基戊二醛及戊二醛，如下所述地进行生物分解性试验。
<生物分解性试验>
参考OECD测试指引301C(OECD test guideline 301C)、JIS K 6950(ISO 14851)的试验方法，实施待测物质的分解度试验。即，在培养瓶中加入无机培养基液300ml、从日本冈山县仓敷市水岛地区的水岛污水处理场在试验开始当天获得的活性污泥9mg(30ppm)，由于待测物质均具有杀菌作用，再加上对污泥的影响，因此以高浓度组：待测物质30mg(100ppm)、及低浓度组：9mg(30ppm)这2个浓度实施生物分解性试验。
使用库仑计(大仓电气3001A型)在25℃下培养28天，使用被待测物质的分解所消耗的氧量和由待测物质的结构式求得的理论需氧量而算出生物分解率。作为生物分解标准物质，使用苯胺30mg(100ppm)。生物分解率为60％以上时，判定为良好分解性物质。
在以上的条件下测定的结果是，作为生物分解标准物质的苯胺在试验期间显示60％以上的生物分解率，判定为良好分解性。由此，判断为本试验系统正常地工作。
3-甲基戊二醛高浓度组(100ppm)的28天的生物分解率为64.8％，判断为“良好分解性”。
3-甲基戊二醛低浓度组(30ppm)的28天的生物分解率为97.2％，判断为“良好分解性”。
比较例2
除了使用戊二醛来代替3-甲基戊二醛以外，与实施例2同样地进行生物分解性试验。
戊二醛高浓度组(100ppm)的28天的生物分解率为52.6％，判断为“部分的生物分解性(难分解性)”。
戊二醛低浓度组(30ppm)的28天的生物分解率为78.0％，判断为“良好分解性”。由以上的结果显示，3-甲基戊二醛与戊二醛相比，生物分解性高。
实施例3
将2.0g下述式所表示的缩醛化合物(以下，称为缩醛化合物A)加入到在蒸馏水中加入盐酸而将pH调整为4.0的盐酸水溶液100g中，在氮气氛下、80℃下进行搅拌。1小时后采集一部分而进行气相色谱分析，结果确认缩醛化合物A被消耗97.2％，生成82.6％的3-甲基戊二醛。
[化学式5]
[气相色谱分析条件]
分析设备：GC-2014(株式会社岛津制作所制)
检测器：FID(氢火焰离子化型检测器)
使用柱：DB-WAX(长度为30m、膜厚为0.25μm、内径为0.25mm)
(Agilent Technologies Japan，Ltd.制)
分析条件：气化室温度250℃、检测器温度250℃
升温条件：50℃(保持4分钟)→(以10℃/分钟升温)→250℃
内标物质：四乙二醇二甲基醚
实施例4
将2.0g缩醛化合物A加入到在蒸馏水中加入盐酸而将pH调整为4.0的盐酸水溶液100g中，在氮气氛下、30℃下进行搅拌。50小时后采集一部分与实施例3同样地进行气相色谱分析，结果确认缩醛化合物A被消耗52.5％，生成47.3％的3-甲基戊二醛。
产业上的可利用性
本发明的制剂以3-甲基戊二醛作为有效成分，生物分解性优异，少量时金属的生物腐蚀的抑制能力优异。即，在环境·劳动安全方面，安全性高。
本发明的制剂例如可以用于在水压破碎法中使用的高压水或金属流体的生物腐蚀抑制中。此外，本发明的制剂可以涂布或喷雾于需要抑制生物腐蚀的金属的表面而使用。
进而，本发明的制剂可以有效地用于抑制在诱发生物腐蚀的微生物的栖息环境中存在或设置的金属的生物腐蚀。
本申请基于在日本申请的特愿2014-191163(申请日：2014年9月19日)，其内容全部包含于本说明书中。
Claims (7)
1.一种金属的生物腐蚀抑制剂，其将3－甲基戊二醛作为有效成分，并且其还包含下述式(1)所表示的化合物或下述式(2)所表示的化合物中的1种以上，
式(1)中，R1、R2分别独立地表示碳原子数为1到6的烷基，或者彼此连结而表示碳原子数为2到7的亚烷基，
式(2)中，R1、R2如上述定义所述，R3、R4分别独立地表示碳原子数为1到6的烷基，或者彼此连结而表示碳原子数为2到7的亚烷基。
2.根据权利要求1所述的金属的生物腐蚀抑制剂，其中，所述生物腐蚀为基于选自硫酸还原菌、硝酸还原菌、甲烷生成菌、碘氧化菌、铁氧化细菌及硫氧化细菌中的至少1种而进行的腐蚀。
3.根据权利要求1或2所述的金属的生物腐蚀抑制剂，其为有效成分的总浓度为0.01ppm～3000ppm的范围的水性液的形态。
4.根据权利要求1或2所述的金属的生物腐蚀抑制剂，其中，所述金属为铁。
5.权利要求1～4中任一项所述的金属的生物腐蚀抑制剂的制造方法，其包括：使下述式(1)所表示的化合物或下述式(2)所表示的化合物中的1种以上与水接触而产生3－甲基戊二醛的工序，
式(1)中，R1、R2分别独立地表示碳原子数为1到6的烷基，或者彼此连结而表示碳原子数为2到7的亚烷基，
式(2)中，R1、R2如上述定义所述，R3、R4分别独立地表示碳原子数为1到6的烷基，或者彼此连结而表示碳原子数为2到7的亚烷基。
6.根据权利要求5所述的金属的生物腐蚀抑制剂的制造方法，其中，使酸共存。
7.一种金属的生物腐蚀抑制方法，其使用权利要求1～4中任一项所述的金属的生物腐蚀抑制剂。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-191163 | 2014-09-19 | ||
| JP2014191163 | 2014-09-19 | ||
| PCT/JP2015/075979 WO2016043148A1 (ja) | 2014-09-19 | 2015-09-14 | 金属の生物腐食抑制剤 |
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| CN106686980A CN106686980A (zh) | 2017-05-17 |
| CN106686980B true CN106686980B (zh) | 2019-09-24 |
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| US (1) | US10087404B2 (zh) |
| EP (1) | EP3202266B1 (zh) |
| JP (1) | JP6642873B2 (zh) |
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| BR (1) | BR112017005174A2 (zh) |
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| RU (1) | RU2694973C2 (zh) |
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| EP3239127A4 (en) * | 2014-12-24 | 2018-08-15 | Kuraray Co., Ltd. | Method for producing aldehyde compound, and acetal compound |
| JPWO2018062254A1 (ja) * | 2016-09-27 | 2019-08-15 | 株式会社クラレ | 金属腐食の抑制方法 |
| CN117903854A (zh) * | 2024-03-19 | 2024-04-19 | 成都南玉电力设备有限公司 | 一种醇氢发动机甲醇燃料催化剂 |
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- 2015-09-14 JP JP2016548874A patent/JP6642873B2/ja not_active Expired - Fee Related
- 2015-09-14 WO PCT/JP2015/075979 patent/WO2016043148A1/ja active Application Filing
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| Publication number | Publication date |
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| KR20170052594A (ko) | 2017-05-12 |
| US20170275575A1 (en) | 2017-09-28 |
| RU2017108571A (ru) | 2018-10-19 |
| RU2017108571A3 (zh) | 2019-02-19 |
| SG11201702102SA (en) | 2017-04-27 |
| US10087404B2 (en) | 2018-10-02 |
| DK3202266T3 (da) | 2020-02-03 |
| MX2017003609A (es) | 2017-09-19 |
| RU2694973C2 (ru) | 2019-07-18 |
| WO2016043148A1 (ja) | 2016-03-24 |
| TW201617482A (zh) | 2016-05-16 |
| EP3202266A4 (en) | 2018-04-25 |
| CA2961703A1 (en) | 2016-03-24 |
| EP3202266B1 (en) | 2019-11-27 |
| TWI663292B (zh) | 2019-06-21 |
| JP6642873B2 (ja) | 2020-02-12 |
| CN106686980A (zh) | 2017-05-17 |
| EP3202266A1 (en) | 2017-08-09 |
| BR112017005174A2 (pt) | 2017-12-05 |
| JPWO2016043148A1 (ja) | 2017-07-06 |
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