TW201617482A - 金屬之生物腐蝕抑制劑 - Google Patents
金屬之生物腐蝕抑制劑 Download PDFInfo
- Publication number
- TW201617482A TW201617482A TW104130714A TW104130714A TW201617482A TW 201617482 A TW201617482 A TW 201617482A TW 104130714 A TW104130714 A TW 104130714A TW 104130714 A TW104130714 A TW 104130714A TW 201617482 A TW201617482 A TW 201617482A
- Authority
- TW
- Taiwan
- Prior art keywords
- present
- corrosion inhibitor
- agent
- methylglutaraldehyde
- metal
- Prior art date
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- 238000005260 corrosion Methods 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 230000007797 corrosion Effects 0.000 title claims abstract description 31
- 239000003112 inhibitor Substances 0.000 title claims abstract description 27
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- 230000006866 deterioration Effects 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
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- 239000003755 preservative agent Substances 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940047208 pyridoxine 10 mg Drugs 0.000 description 1
- ZUFQODAHGAHPFQ-UHFFFAOYSA-N pyridoxine hydrochloride Chemical compound Cl.CC1=NC=C(CO)C(CO)=C1O ZUFQODAHGAHPFQ-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 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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- 235000019698 starch Nutrition 0.000 description 1
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- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 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
- 238000010998 test method Methods 0.000 description 1
- 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
- 229940086388 thiamine hydrochloride 5 mg Drugs 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- AKUNSPZHHSNFFX-UHFFFAOYSA-M tributyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC AKUNSPZHHSNFFX-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- 239000010455 vermiculite Substances 0.000 description 1
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- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
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- 239000001993 wax Substances 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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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- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
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- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
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- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
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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
- 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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Abstract
本發明之課題係提供一種以低濃度發揮效果且在生物分解性上亦優良的金屬之生物腐蝕抑制劑。
本發明解決課題之手段係一種金屬之生物腐蝕抑制劑,其係以3-甲基戊二醛作為有效成分。
Description
本發明係關於金屬的生物腐蝕之抑制劑。
生物腐蝕係指藉由存在於環境中的微生物的作用而直接或間接的誘發之腐蝕現象,雖然許多研究案例已被報告(例如非專利文獻1等),但關於產生的機制仍留有原因不明的部分。在最近的研究中報告,於生物腐蝕係由2種以上的微生物(例如硫酸還原菌及產甲烷菌等)所造成之情形,這些微生物的作用會有相乘地促進腐蝕之情形。
近年來,於石化燃料(例如,石油、天然氣、頁岩油、頁岩氣等)的採掘中,以高壓水進行岩盤的破碎等,在此高壓水的流路之鐵配管等看到生物腐蝕。為了抑制此生物腐蝕而使用了戊二醛(參照專利文獻1)。一般而言,戊二醛及其類似物已知具有殺菌性,其中戊二醛已知具有優良的殺菌性(非專利文獻2)。
非專利文獻1 Journal of Bioscience and Bioengineering VOL. 110, No. 4, pp. 426-430 (2010)
非專利文獻2 Journal of applied bacteriology Vol.30, No.1, 78-87(1967)
專利文獻1 美國專利第2801216號說明書
另一方面,具有殺菌性的化合物經常顯示高毒性。在此種化合物被使用於釋放在環境中之用途的情形,由於有可能對工作者與生態系產生影響,因此期望使用量極可能的少,另外期望在環境中快速地被分解。亦即,期望在具有殺菌性的化合物中以低濃度發揮所期望的效果的同時,還具有生物分解性。於石化燃料的採掘上被頻繁使用作為生物腐蝕抑制劑之戊二醛已知具有致癌性,生物分解性不充分,有可能比較長期的殘存在環境中,而被擔心有上述影響。
因此,本發明之目的係提供:以低濃度發揮效果且生物分解性亦優良的金屬之生物腐蝕抑制劑、該生物腐蝕抑制劑之製造方法、使用該生物腐蝕抑制劑的金屬的生物腐蝕之抑制方法。
本案發明人們詳細研究的結果,發現:與戊二醛相比,3-甲基戊二醛具有更高的生物分解性,且以極低濃度展現金屬之生物腐蝕抑制效果,而完成本發明。
亦即,本發明提供下述[1]~[8]。
[1]一種金屬之生物腐蝕抑制劑,其係以3-甲基戊二醛作為有效成分。
[2]如[1]之生物腐蝕抑制劑,其中前述生物腐蝕係由選自硫酸還原菌、硝酸還原菌、產甲烷菌、碘氧化菌、鐵氧化細菌及硫氧化細菌中之至少一種所造成。
[3]如[1]或[2]之生物腐蝕抑制劑,其進一步包含1種以上的以下述式(1)所表示之化合物或以下述式(2)所表示之化合物:
(R1、R2各自獨立地表示碳數1至6的烷基,或彼此連結而表示碳數2至7的亞烷基)
(R1、R2係如上述所定義,R3、R4各自獨立地表示碳數1至6的烷基,或彼此連結而表示碳數2至7的亞烷基)。
[4]如[1]至[3]中任一項之生物腐蝕抑制劑,其係有效成分的總濃度在0.01ppm~3000ppm之範圍的水性液的形態。
[5]如[1]至[4]中任一項之生物腐蝕抑制劑,其中前述金屬為鐵。
[6]一種如[1]至[5]中任一項之金屬腐蝕抑制劑之製造方法,其包含使1種以上的以式(1)所表示之化合物或
以式(2)所表示之化合物與水接觸而產生3-甲基戊二醛之步驟。
[7]如[6]之金屬腐蝕抑制劑之製造方法,其係共存有酸。
[8]一種金屬之生物腐蝕抑制方法,其係使用如[1]至[5]中任一項之生物腐蝕抑制劑。
依據本發明,能提供一種以低濃度發揮效果且生物分解性亦優良的金屬之生物腐蝕抑制劑。
第1圖為顯示實施例1中3-甲基戊二醛的生物腐蝕抑制試驗結果(鐵的析出濃度)之圖表。
第2圖為顯示比較例1中戊二醛的生物腐蝕抑制試驗結果(鐵的析出濃度)之圖表。
本發明的劑係含有3-甲基戊二醛作為有效成分。3-甲基戊二醛為已知物質,能藉由已知方法(例如記載於Organic Syntheses,Vol.34,p.29(1954),及Organic Syntheses,Vol.34,p.71(1954)等的方法)或參照其的方法來製造。
本發明的劑除了3-甲基戊二醛以外,只要不損害本發明之目的,也可進一步包含在生物腐蝕抑制劑領域慣用的成分。作為該成分可藉舉出例如:其他抗菌
劑、分散劑、懸浮劑、展著劑(spreader)、滲透劑、濕潤劑、黏漿劑、穩定劑、阻燃劑、著色劑、抗氧化劑、抗靜電劑、發泡劑、潤滑劑、膠凝劑、成膜助劑、防凍劑、黏度調整劑、pH調整劑、防腐劑、乳化劑、消泡劑、載體等。
作為其他抗菌劑,可列舉出例如:氧化劑(過乙酸、單過硫酸鉀、過硼酸鈉、過氧化氫、過碳酸鈉等)、鏻鹽(THPS、聚醚聚胺基亞甲基膦酸酯、氯化三丁基十四烷基鏻等)、烷基苯磺酸、四級銨鹽(氯化N-烷基二甲基苯甲基銨、氯化N-二烷基甲基苯甲基銨等)、異噻唑啉/噻唑啉/異噻唑酮系化合物(2-(硫氰甲基硫)苯并噻唑、異噻唑酮等)、硫胺甲酸酯系化合物、氫醌系化合物、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、氯化烷基二甲基苄基銨(benzalkonium chloride)、次氯酸、唑啶化合物、咪唑系化合物(1,2-二甲基-5-硝基-1H-咪唑等)、胺基醇、醚類、核糖體類、炔烷氧化物類、溴系殺生物劑(2,2-二溴-2-硝基乙醯胺)、酵素類(內-β-1,2-半乳聚糖酶(endo-β-1,2-galactanase)等)、金屬離子類、苯酚系化合物等。這些抗菌劑可以單獨使用,也可將2種以上併用。
作為分散劑,可列舉出例如:高級醇的硫酸酯、烷基磺酸、烷基芳基磺酸、氧烷基胺、脂肪酸酯、聚環氧烷系、脫水山梨醇系等界面活性劑;皂類、酪蛋白、明膠、澱粉、藻酸、洋菜、羧甲基纖維素(CMC)、聚乙烯醇、松根油(asbolin)、糖油、膨土、甲酚皂等。這些分散劑可以單獨使用,也可將2種以上併用。
作為載體,可列舉出例如:水、醇(甲醇、乙醇、異丙醇、乙二醇、丙三醇等)、酮(丙酮、甲乙酮等)、脂肪族烴(己烷、流動石蠟等)、芳香族烴(苯、二甲苯等)、鹵化烴、醯胺、酯、腈等液體載體;黏土類(高嶺土、膨土、酸性白土等)、滑石類(滑石粉、壽山石粉等)、矽石類(矽藻土、無水矽酸、雲母粉等)、氧化鋁、硫黃粉末、活性碳等固體載體;等等。這些載體可以單獨使用,也可將2種以上併用。
本發明的劑中前述有效成分的總含有比例,依照劑型與使用態樣等來適當設定即可,惟通常為1~100質量%,從成本效益的觀點來看,較佳為5~100質量%,更佳為5~95質量%。
本發明的劑的製造方法不特別限制,可使用本身已知的方法或參照其的方法。例如,可藉由在3-甲基戊二醛中,視期望添加生物腐蝕抑制劑之領域所慣用的成分並混合等而製造。
就本發明的劑型而言,可列舉出例如:乳劑、液劑、水溶性粉末、可濕性粉劑、粉劑、粒劑、微粒劑、錠劑、糊劑、懸浮劑、噴霧劑、塗布劑等。對各劑型製劑化的方法不特別限制,可依照本身已知的方法或與參照其的方法而製劑化。
本發明的劑的有效成分之3-甲基戊二醛,對於引起生物腐蝕的微生物具有戊二醛以上的殺菌作用,且生物分解性高。因此,本發明的劑能適當用於抑制金屬的生物腐蝕。作為引起生物腐蝕的微生物,可列舉出
例如:硫酸還原菌、硝酸還原菌、產甲烷菌、碘氧化菌、鐵氧化細菌及硫氧化細菌等,但不限定於這些細菌。其中,本發明中生物腐蝕之「抑制」係包含將生物腐蝕的發生防範於未然,及抑制生物腐蝕的進展(惡化)之概念。
本發明中「硫酸還原菌」係指具有將硫酸鹽還原之能力的微生物的總稱。就硫酸還原菌的具體例而言,可列舉出:脫硫弧菌(Desulfovibrio)屬的微生物、脫硫菌(Desulfobacter)屬的微生物、脫硫腸狀菌(Desulfotomaculum)屬的微生物等。
本發明中「硝酸還原菌」係指具有將硝酸鹽還原之能力的微生物的總稱。
本發明中「產甲烷菌」係指具有在厭氧的環境下生成甲烷之能力的微生物的總稱。就產甲烷菌的具體例而言,可列舉出:甲烷桿菌(Methanobacterium)屬的微生物、甲烷球菌(Methanococcus)屬的微生物、甲烷八聯球菌(Methanosarcina)屬的微生物等。
本發明中「碘氧化菌」係指具有將碘化物離子(I-)氧化為分子狀碘(I2)之能力的微生物的總稱。碘氧化菌的具體例可列舉出:玫瑰變色菌屬(Roseovarius sp.)2S-5、碘氧化細菌(Iodide oxidizing bacterium)MAT3株等。
本發明中「鐵氧化細菌」係指具有將2價鐵離子(Fe2+)氧化為3價鐵離子(Fe3+)之能力的微生物的總稱。就鐵氧化細菌的具體例而言,可列舉出:嗜中性鐵氧化菌(Mariprofundus ferrooxydans)、氧化亞鐵硫桿菌(Acidithiobacillus ferrooxidans)等。
本發明中「硫氧化細菌」係指具有將硫或無機硫化合物氧化之能力的微生物的總稱。就硫氧化細菌的具體例而言,可列舉出:硫桿菌(Thiobacillus)屬細菌、酸硫桿狀菌(Acidithiobacillus)屬細菌、硫化葉菌(Sulfolobus)屬古細菌、嗜酸菌(Acidianus)屬古細菌等。
本發明的劑較佳使用來抑制從硫酸還原菌、硝酸還原菌、產甲烷菌、碘氧化菌、鐵氧化細菌及硫氧化細菌中所選出的至少一種;更佳為從硫酸還原菌、硝酸還原菌及產甲烷菌中所選出的至少一種;再較佳為從硫酸還原菌及產甲烷菌中所選出之至少一種;特佳為產甲烷菌所造成的生物腐蝕。
產甲烷菌喜歡厭氧的環境,存在於水田、另外還有沼地、池塘、湖泊、河川、海及石化燃料的採掘現場等。
硫酸還原菌喜歡厭氧的環境,只要是在含有水分的環境大多能生存,例如在森林土壤、田地、沼地、池塘、湖泊、河川及海等隨處都能生存。
硝酸還原菌喜歡厭氧的環境,與產甲烷菌或硫酸還原菌相比,由於在氧化的環境中也能生長,故生存於上述環境中。
鐵氧化細菌存在於礦山汙水等中。另外也生存在河川等積存著些許茶色的堆積物等之場所等。
硫氧化細菌係生存在與鐵氧化細菌相同的環境下,且因還生存在生活汙水中,而也與下水道的混凝土腐蝕等相關。另外也存存在含有硫磺的溫泉。
碘氧化菌比較多存在的場所為地下鹹水,另外亦廣泛存在於海洋環境中。
因此,本發明的劑適合使用來抑制存在或設置於上述微生物的生存環境之金屬的生物腐蝕。
本發明的劑所使用之金屬只要是暴露於存在有會引起生物腐蝕之微生物的環境者即不特別限制,可舉出例如鐵、銅、鋅、錫、鋁、鎂、鈦、鎳、鉻、錳、鉬及包含由其中所選出的至少一種之合金等。其中,從工業利用的觀點來看,較佳為鐵及包含鐵之合金,更佳為鐵。
本發明的劑之使用方法只要不損害本發明之目的即無特別限制,惟,作為其一態樣,可舉出例如:在金屬暴露於存在有會引起生物腐蝕之微生物的環境中的情形,在那之前預先讓本發明之劑存在於該環境中之方法等。若要舉出該態樣的具體例,在藉由水力壓裂法進行的石化燃料(例如石油、天然氣、頁岩油、頁岩氣等)之採掘中,藉由將本發明之劑預先添加進以高壓注入岩盤等的液體(高壓水)中並使其溶解,能抑制高壓水接觸的金屬(例如高壓水的流路之金屬配管等)產生的生物腐蝕。或者,在金屬暴露於存在有引起生物腐蝕之微生物的環境中時,讓本發明的劑存在於該環境中也可。作為另一態樣,可舉出例如:將本發明的劑照原樣,或使其溶解或分散於水或有機溶媒等而成之物,塗布或噴霧於需要抑制生物腐蝕的金屬之表面上之方法等。
作為本發明的劑的使用形態,較佳為前述有效成分的總濃度在特定範圍之水性液的形態。
此種水性液中的有效成分的總濃度,通常為10000ppm以下,從成本效益的觀點來看,較佳為0.01ppm~3000ppm,更佳為0.1ppm~1000ppm。若該濃度小於0.01ppm,則生物腐蝕抑制效果會有變小的傾向;若超過10000ppm,則會大幅過剩而會有價格上變得難以利用的傾向。本說明書中「ppm」只要沒有特別說明,即是意指「質量ppm」。
水性液的製造方法不特別限制,可使用本身已知的方法或參照其的方法。例如:可藉由將前述有效成分添加進適當的液體載體並攪拌,使其溶解或分散來製造。作為該液體載體,可舉出例如作為本發明的劑可包含的成分之一的上述例示之液體載體等。
水性液可利用作為例如於水力壓裂法所使用之高壓水等。在將水性液使用作為該高壓水的情形,水性液可包含於高壓水中慣用的成分(例如支撐劑、黏度調整劑、界面活性劑、酸等)。
又,水性液也可塗布或噴霧於需要抑制生物腐蝕之金屬的表面上。
本發明的劑中的有效成分之3-甲基戊二醛,從保存穩定性的觀點來看,也能夠以包含1種以上的以下述式(1)所表示之縮醛化合物(以下稱為化合物(1))或以下述式(2)所表示之雙縮醛化合物(以下稱為化合物(2))之形態,進一步含有於本發明之劑中來保存及搬運:
(R1、R2分別表示碳數1至6的烷基,或彼此連結而表示碳數2至7的亞烷基)
(R1、R2、R3、R4係分別表示碳數1至6的烷基,或R1與R2、R3與R4彼此連結而表示碳數2至7的亞烷基)。
亦即,1種以上的化合物(1)或化合物(2)可作為3-甲基戊二醛的等價物而進一步含有於本發明的劑中。在含有1種以上的化合物(1)或化合物(2)之情形的含量無特別限制。其中,不含3-甲基戊二醛而僅含有1種以上的化合物(1)或化合物(2)之物也能與本發明之劑同等地操作。
能在使用前使進一步含有1種以上的化合物(1)或化合物(2)之本發明的劑與水接觸而產生3-甲基戊二醛。又,也能藉由使1種以上的化合物(1)或化合物(2)與生物腐蝕抑制的對象之存在於環境的水直接接觸來產生3-甲基戊二醛。像這樣,能藉由與水接觸來產生3-甲基戊二醛之包含1種以上化合物(1)或化合物(2)的劑,也是本發明之劑的一種態樣。
使進一步包含1種以上的化合物(1)或化合物(2)之本發明的劑與水接觸而產生3-甲基戊二醛時,視需
要也可使用酸。作為使用的酸不特別限定,可列舉出例如:硫酸、磷酸、硝酸、鹽酸、硼酸等無機酸;甲酸、乙酸、丙酸、草酸等有機酸。使進一步包含1種以上的化合物(1)或化合物(2)之本發明的劑與水接觸之方法不特別限定,可以使水與將進一步包含1種以上的化合物(1)或化合物(2)之本發明的劑與酸預先混合而成的組成物接觸,也可以使進一步包含1種以上的化合物(1)或化合物(2)之本發明劑與預先將酸與水混合而成的溶液接觸。
使用的水的量無特別限制,通常較佳為1種以上的化合物(1)或化合物(2)的合計量與當量以上。接觸時間無特別限制,惟通常為5秒以上,較佳為1分鐘以上,更佳為10分鐘以上。對接觸溫度無特別限制,通常為-20℃至200℃,較佳為0℃至120℃,更佳為10℃至100℃。酸的使用量無特別限制,通常為使酸與水混合時的pH成為6.0以下的量,較佳為成為1.0至5.6的量,更佳為成為2.0至5.0的量。
在化合物(1)、化合物(2)中,就R1~R6各自獨立表示的碳數1至6之烷基而言,可列舉出例如:甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基、環己基。其中較佳為甲基、乙基、正丙基,更佳為甲基、乙基。又,就R1與R2、R3與R4相互連結表示的亞烷基而言,可列舉出例如:伸乙基、伸正丙基、伸正丁基、伸正戊基、伸正己基、2-甲基-伸乙基、1,2-二甲基伸乙基、2-甲基-伸正丙基、2,2-二甲基-伸正丙
基、3-甲基-伸正戊基。其中較佳為:伸乙基、伸正丙基、2-甲基-伸正丙基、2,2-二甲基-伸正丙基、2-甲基-伸乙基、1,2-二甲基伸乙基,更佳為伸乙基、伸正丙基、2-甲基-伸正丙基、2,2-二甲基-伸正丙基。
化合物(1)、化合物(2)為已知化合物,能依照已知方法(例如特開平11-228566號公報)或參照其的方法來製造。
在使用進一步包含1種以上的化合物(1)或化合物(2)之本發明劑之情形,前述「有效成分的總含有比例」及「有效成分的總濃度」係表示3-甲基戊二醛、化合物(1)、化合物(2)各別的含有比例之合計及濃度之合計。
使用本發明之劑時,只要不損害本發明之目的,也可併用本身已知的殺菌方法或參照其的方法。
例如可併用已知的抗菌劑,也可併用藉由控制pH之殺菌方法(參照例如WO2010/056114、WO2008/134778等)、或藉由超音波照射之殺菌方法(參照例如WO2000/024679等)等。作為能與本發明的劑併用的已知抗菌劑,可舉出例如作為本發明的劑可包含的成分之一的上述例示之其他抗菌劑等。
以下舉出實施例更詳細說明本發明,但本發明不受以下實施例限定。
實施例1
對3-甲基戊二醛如下述般進行生物腐蝕抑制試驗。
[無機鹽海水培養基(A液)之調製]
在無氧操作箱(anaerobic chamber)中將970ml的Milli-Q水、19.0g的NaCl、2.6g的MgCl2.6H2O、0.15g的CaCl2.2H2O、4.0g的Na2SO4、0.25g的NH4Cl、4.0g的KH2PO4、0.5g的KCl、23.8g的HEPES(2-[4-(2-羥基乙基)-1-哌基]乙磺酸)混合溶解,調製成無機鹽海水培養基(A液)。
其中Milli-Q水係使用Merk Millipore公司製裝置(例如Milli-Q Integral 10)所製造成的超純水。
[碳酸氫鈉溶液(C液)之調製]
將2.52g的NaHCO3溶解於30ml的Milli-Q水後,過濾除菌,調製成碳酸氫鈉溶液(C液)。
[微量元素溶液(E液)之調製]
混合8.3ml的HCl(35%)、2100mg的FeSO4.7H2O、30mg的H3BO4、100mg的MnCl2.4H2O、190mg的CoCl2.6H2O、24mg的NiCl2.6H2O、2mg的CuCl2.2H2O、144mg的ZnSO4.7H2O、36mg的Na2MoO4.2H2O,以Milli-Q水於量筒中稀釋至100ml後,過濾除菌,調製成微量元素溶液(E液)。
[硒鎢溶液(S液)之調製]
將400mg的NaOH、4mg的Na2SeO3、8mg的Na2WO4.2H2O混合,以Milli-Q水於量筒中稀釋至100ml後,過濾除菌,調製成硒鎢溶液(S液)。
[維生素溶液(V液)之調製]
混合4mg的4-胺基苯甲酸、1mg的D-生物素、10mg的菸鹼酸、5mg的D-泛酸鈣、15mg的鹽酸吡哆醇(pyridoxine hydrochloride)、10mg的鹽酸噻胺(thiamine hydrochloride)、5mg的維生素B12,以Milli-Q水於量筒中稀釋至100ml後,過濾除菌,調製成維生素溶液(V液)。
<生物腐蝕抑制試驗>
將A液進行10分鐘左右氣體置換,於高壓蒸氣滅菌器以121℃加熱20分鐘後,添加C液、E液、S液及V液,在放入了經殺菌之鐵薄片(0.08g鐵箔(Iron foil)(縱10mm×橫10mm×厚0.1mm:Sigma-Aldrich356808-G))的小瓶中,各分注20ml的所得到之混合液。對各小瓶進行5分鐘氣體置換(對N2氣體混合CO2氣體,最終成為20%CO2氣體)後,很快地封閉丁基橡膠栓,並以鋁密封件確實地固定。然後,使用注射器,添加0.5ml(106~109細胞/ml)的海沼甲烷球菌(Methanococcus maripaludis)KA-1株,進一步添加3-甲基戊二醛至第1圖所示之濃度。將各小瓶靜置於37℃,為了確認鐵薄片的生物腐蝕的進行度,於7日後、14日後、21日後、28日後測定鐵的析出濃度。鐵的析出濃度之測定,係取出各小瓶中的溶液(1.0ml),對其添加0.5ml的6M HCl,將不溶性的鐵溶解,把添加1.0ml的1M L-抗壞血醛而將三價鐵還原為二價鐵而成之物,用鄰啡啉法(o-phenanthroline)進行比色測定。將結果示於第1圖。
比較例1
除了使用戊二醛來取代3-甲基戊二醛以外,與實施例1同樣地進行生物腐蝕抑制試驗。將結果示於第2圖。
由第1圖與第2圖的結果,3-甲基戊二醛以1ppm的添加濃度即將鐵的析出濃度充分地抑制在低值。另一方面發現,戊二醛為了將鐵的析出濃度抑制在相同程度需要100ppm的添加濃度。因此,相較於戊二醛,3-甲基戊二醛顯示以極低濃度即具有良好的生物腐蝕抑制作用。
實施例2
對3-甲基戊二醛及戊二醛,如下述般進行生物分解性試驗。
<生物分解性試驗>
參考OECD試驗準則301C、JIS K 6950(ISO 14851)的試驗方法,實施受測物質的分解度試驗。亦即,在培養瓶中,裝入300ml之無機培養基液、9mg(30ppm)之在試驗開始當日從日本國岡山縣倉敷市水島地區的水島汙水處理廠取得的活性汙泥,由於受測物質同時具有殺菌作用,所以加入對汙泥的影響,以高濃度群:受測物質30mg(100ppm)、及低濃度群:9mg(30ppm)等2濃度實施生物分解性試驗。
使用庫侖計(大倉電氣3001A型)在25℃下培養28日,使用分解受測物質所消耗的氧量與由受測物質的結構式所求得的理論氧需求量來算出生物分解率。作為生物分解標準物質,係使用苯胺30mg(100ppm)。生物分解率為60%以上時,判定為良分解性物質。
按照以上條件測定的結果,生物分解標準物質之苯胺在試驗期間中顯示60%以上的生物分解率,被判定為良分解性。依此判斷本試驗系統運作正常。
3-甲基戊二醛高濃度群(100ppm)於28日之生物分解率為64.8%,被判斷為『良分解性』。
3-甲基戊二醛低濃度群(30ppm)於28日之生物分解率為97.2%,被判斷為『良分解性』。
比較例2
除了使用戊二醛取代3-甲基戊二醛以外,與實施例2同樣地進行生物分解性試驗。
戊二醛高濃度群(100ppm)於28日的生物分解率為52.6%,被判斷為『部分生物分解性(難分解性)』。
戊二醛低濃度群(30ppm)於28日生物分解率為78.0%,被判斷為『良分解性』。依據以上結果,顯示:相較於戊二醛,3-甲基戊二醛具高生物分解性。
實施例3
在對蒸餾水添加鹽酸而調整至pH4.0之鹽酸水溶液100g中,加入2.0g的以下述式所表示之縮醛化合物(以下稱為縮醛化合物A)
於氮氣環境下於80℃攪拌。1小時後採取一部分進行氣相層析分析時,確認:消耗了97.2%的縮醛化合物A,產生了82.6%的3-甲基戊二醛。
分析機器:GC-2014(島津製作所股份有限公司製)
檢測器:FID(火焰離子化檢測器)
使用管柱:DB-WAX(長30m、膜厚0.25μm、內徑0.25mm)
(Agilent Technologies公司製)
分析條件:氣化室溫度250℃,檢測器溫度250℃
升溫條件:50℃(保持4分鐘)→(以10℃/分鐘升溫)→250℃
內部標準物質:四乙二醇二甲醚
實施例4
在對蒸餾水添加鹽酸而調整至pH4.0之鹽酸水溶液100g中,加入2.0g的縮醛化合物A,於氮氣環境下於30℃攪拌。50小時後採取一部分與實施例3同樣地進行氣相層析分析時,確認:消耗了52.5%的縮醛化合物A,產生了47.3%的3-甲基戊二醛。
本發明的劑係以3-甲基戊二醛作為有效成分,生物分解性優良,少量即具有優良的金屬的生物腐蝕之抑制能力。亦即在環境/勞動安全上具高安全性。
本發明的劑能使用在例如於水力壓裂法所使用的高壓水或金屬流體的生物腐蝕抑制上。又,本發明的劑能塗布或噴霧在需要抑制生物腐蝕的金屬的表面上使用。
此外,本發明的劑能有效使用來抑制存在或設置在會誘發生物腐蝕的微生物之生存環境的金屬之生物腐蝕。
本申請案係以於日本提出申請之特願2014-191163(申請日:2014年9月19日)為基礎,其內容全部包含於本說明書中。
Claims (8)
- 一種金屬之生物腐蝕抑制劑,其係以3-甲基戊二醛作為有效成分。
- 如請求項1之生物腐蝕抑制劑,其中前述生物腐蝕係由選自硫酸還原菌、硝酸還原菌、產甲烷菌、碘氧化菌、鐵氧化細菌及硫氧化細菌中之至少一種所造成。
- 如請求項1或2之生物腐蝕抑制劑,其進一步包含1種以上的以下述式(1)所表示之化合物或以下述式(2)所表示之化合物,
- 如請求項1至3中任一項之生物腐蝕抑制劑,其係有效成分的總濃度在0.01ppm~3000ppm之範圍的水性液的形態。
- 如請求項1至4中任一項之生物腐蝕抑制劑,其中前述金屬為鐵。
- 一種如請求項1至5中任一項之金屬腐蝕抑制劑之製造方法,其包含使1種以上的以下述式(1)所表示之化合物或以下述式(2)所表示之化合物、與水接觸而產生3-甲基戊二醛之步驟:
- 如請求項6之金屬腐蝕抑制劑之製造方法,其係共存有酸。
- 一種金屬之生物腐蝕抑制方法,其係使用如請求項1至5中任一項之生物腐蝕抑制劑。
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US2820821A (en) * | 1956-01-05 | 1958-01-21 | Union Carbide Corp | Process for oxidizing glutaraldehydes |
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US7833551B2 (en) * | 2004-04-26 | 2010-11-16 | Conocophillips Company | Inhibition of biogenic sulfide production via biocide and metabolic inhibitor combination |
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