CN100425735C - 抑制金属表面的晶间腐蚀的方法 - Google Patents
抑制金属表面的晶间腐蚀的方法 Download PDFInfo
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- CN100425735C CN100425735C CNB038256347A CN03825634A CN100425735C CN 100425735 C CN100425735 C CN 100425735C CN B038256347 A CNB038256347 A CN B038256347A CN 03825634 A CN03825634 A CN 03825634A CN 100425735 C CN100425735 C CN 100425735C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/12—Accessories for subsequent treating or working cast stock in situ
- B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
- B22D11/1245—Accessories for subsequent treating or working cast stock in situ for cooling using specific cooling agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/12—Accessories for subsequent treating or working cast stock in situ
- B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
-
- 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
- C23F11/14—Nitrogen-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明目的在于使用炔二醇和聚亚烷基多胺的反应产物以抑制工业加工系统中由喷淋水雾或凝聚引起的金属表面的晶间腐蚀。
Description
技术领域
本发明目的在于使用炔二醇和聚亚烷基多胺化合物的反应产物以抑制工业水和加工系统中的金属表面的晶间腐蚀,其中该表面与喷淋水或凝聚相接触。
背景技术
金属和合金的微观结构由晶粒组成,由晶界分离。晶间腐蚀可以解释为沿着晶界或紧邻于晶界的局部侵蚀。这种沉淀可以在紧邻的附近产生抗腐蚀性降低的区域。
晶间腐蚀的一个例子为不锈钢或焊接侵蚀的敏化。富铬晶界沉淀物导致与这些沉淀物相邻的Cr的局部贫化,留下这些易受腐蚀侵蚀的区域。
剥离腐蚀是晶间腐蚀的特殊形式。剥落或分层本身表现为层中金属的损失,这些层似乎是沿着沿表面的晶界。在连铸机中的剥落,例如,发生在不发生直接喷淋水接触的下段的未沾湿结构上。钢暴露于热、潮湿环境,其中表面仅由喷淋水雾或凝聚进行沾湿。腐蚀迅速地沿着钢表面传播,导致二级支承结构的结构完整性的损失。
剥离腐蚀的机理与喷淋水中氯化物的存在有关。当用于喷淋水系统时,雾(蒸汽)穿过蒸汽室并富集于钢表面。热和湿度使水分从钢表面蒸发,留下浓缩的氯化物离子。这个过程连续下去,将越来越多的氯化物离子浓缩到发生剥落的点上。
试样分析显示腐蚀机理如下进行:通过产生的腐蚀产物/沉淀物的脆性层,沉积在金属表面上的氯化物离子进行迁移。在沉淀物下,产生瞬间氯化铁盐。该盐具有吸湿性(吸收水分)并进行水解,形成酸性氯化物条件。留下附加的氧化铁腐蚀产物当酸性腐蚀前部更深入金属表面时。
由于上述原因,工业上正在寻找各种技术和抑制剂,以克服存在于工业加工系统中的剥离腐蚀。
具体实施方式
本发明目的在于提供用于抑制工业加工系统(例如,蒸汽和冷却水系统)中的金属表面晶间腐蚀的方法,其表面与喷淋水或凝聚相接触,其包括向喷淋水中加入足够的腐蚀抑制量的炔二醇和聚亚烷基多胺的反应产物。
反应产物的形成条件在美国专利No.3,211,667中进行了描述,其内容在此全部引入。
教导的可以有效生产反应产物的炔二醇和烯二醇为含有4-12个碳原子的那些。优选,炔二醇含有4个碳原子。示例性的炔二醇为丁炔二醇。
教导的可以有效生产反应产物的聚亚烷基多胺化合物为含有2-10个胺基的那些,且优选,3-7个胺基。这些胺基可以为取代或未取代,且每个胺基均由具有1-6个碳原子,优选2-4个碳原子的亚烷基进行分离。示例性的多胺包括乙二胺、二亚乙基三胺、五亚乙基六胺、五亚丙基六胺(pentapropylene hexamine)、三庚烯二胺等。
胺对二醇的重量比为4∶1-1∶1,优选3∶1,以这样的反应物的重量比获得各个配料之间的全部反应。铜的可电离化合物,例如乙酸铜,以催化的量用于该反应。
本发明的反应产物可以足以抑制金属表面腐蚀的量添加到喷淋水中。该反应产物可以添加到供应管线中,相对于每百万份存在于供应管线中的水,其加入量范围为0.5份-约500份。优选,以每百万份水约1-100份的量加入,特别优选每百万份水约5-10份。
本发明的反应产物或者以溶剂的形式或者以纯物质的形式加入到供应管线中。优选,将反应产物加到含水溶剂中,其中水是一个实例。该反应产物可以与其它适宜的配料(例如消泡剂、腐蚀抑制剂等)一起加入到喷淋水中。在将被处理的系统中,喷淋水一般温度为约110-180°F。
下列数据表明了通过使用本发明所得到的意想不到的结果。下列实施例仅用以说明本发明,而不应认为是对本发明范围的限定。
实施例
为了抑制发生腐蚀进程在金属表面上,要求加入镀膜材料以使表面与水和氯化物相隔离。2-丁炔-1,4-二醇-聚亚乙基多胺(产物A)的加入显著降低了钢的腐蚀速度(如表1和表2所示)。为了在喷雾室内放置各种腐蚀试样,在所有试验中,构造了试样树(coupons trees)。将溶液注入与铸造机喷雾器(casterspray)相连的供应管线中。这使得该物质分布遍及喷雾室。
表1-(用于SEM的试样)
铰线#1-未处理侧 | 铰线#2-已处理侧 |
151mpy | 20.9mpy |
沉淀物中的铁含量大大降低。
表2-(用于SEM的试样)
铰线#1-未处理侧 | 铰线#2-已处理侧 |
Fe-88% | Ca-52% |
Cl-5% | Fe-23% |
Ca-1% | Na-6% |
Na-1% | C1-6% |
Mg-痕量(<1%) | Al-2% |
Al-痕量(<1%)) | Si-2% |
Si-痕量(<1%) | S-2% |
S-痕量(<1%) | K-<l% |
结果显示,虽然对于未处理(5%)和已处理侧(6%)来说,氯化物浓度相似,但其它组分有极大不同。在未处理侧上的铁含量为88%;剥落水平也很显著。在已处理侧上,铁含量仅为23%且不出现剥落。已处理侧具有52%的钙,这说明存在腐蚀抑制。
在附加试验中,在已处理和未处理铰线中,均将腐蚀试样浸入产物A中和置于未处理的试样的旁边。在未处理铰线中,浸入的试样显示了极小的腐蚀,而未处理试样被剥落。在已处理铰线中,比较未浸入的试样,在腐蚀控制上存在显著的改善。
在本发明的其他试验中,构造了可选择的试样树。试验的试样包括:低碳钢、不锈钢、铜和涂覆低碳钢。
八日后,将一单套低碳钢试样移出作为初步检查。试样结果列于下表3中。来自铰线#2的试样显示了剥落的迹象,而来自铰线#1的试样仅显示了一般腐蚀进程。
表3-八日后试样结果(mpy)
如进一步在下表4中所示,在铰线#1中,腐蚀试样树上的腐蚀速度存在显著降低,其中注入了产物A。以15ppm供给产物A通过该系统。在大多数位置上,低碳钢的腐蚀速度降低了大约50-80%。与上面相同,来自铰线#2的试样显示了剥落的迹象,而来自铰线#1的试样仅显示了一般腐蚀进程(没有出现剥落)。
表4-试样的腐蚀结果(mpy)
注意到,所有剩余的试样是不锈钢或者涂覆试样;在这些试样的任何一个上都没有观察到显著的腐蚀。另外,在喷淋水体系中,本发明的处理没有不利的冲击喷嘴性能。
虽然参照本发明的特定具体实施方式,已经对本发明进行描述,但对本领域技术人员而言,本发明的许多其它形式和改进是显而易见的。通常,应认为附属权利要求和本发明覆盖所有这些在本发明实际精神和范围内的显而易见的形式和改进。
Claims (14)
1.一种抑制工业加工系统中与喷淋水相接触的金属表面的晶间腐蚀的方法,其包括向喷淋水中加入每百万份水0.5份-500份量的炔二醇和聚亚烷基多胺的反应产物。
2.权利要求1的方法,其中所述晶间腐蚀为剥离腐蚀。
3.权利要求1的方法,其中所述金属表面包括连续铸造机表面。
4.权利要求2的方法,其中所述剥离腐蚀发生在由喷淋水雾或凝聚所沾湿的金属表面上。
5.权利要求1的方法,其中所述炔二醇包含具有4-12个碳原子的炔基。
6.权利要求1的方法,其中所述炔二醇为丁炔二醇。
7.权利要求1的方法,其中所述聚亚烷基多胺包含2-10个胺基,每个胺基相互之间由具有1-6个碳原子的亚烷基分开。
8.权利要求1的方法,其中所述聚亚烷基多胺为五亚乙基六胺。
9.权利要求1的方法,其中所述喷淋水温度范围为110°F-180°F。
10.权利要求1的方法,其中所述反应产物以含水溶剂加到所述喷淋水中。
11.权利要求1的方法,其中所述金属表面为含铁金属表面。
12.权利要求1的方法,其中所述反应产物以每百万份水1份-100份的量加到所述喷淋水中。
13.权利要求12的方法,其中所述反应产物以每百万份水5份-10份的量加到所述喷淋水中。
14.权利要求1的方法,其中所述工业加工系统包括蒸汽和冷却水系统。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/283,457 | 2002-10-30 | ||
US10/283,457 US20040086419A1 (en) | 2002-10-30 | 2002-10-30 | Methods for inhibiting intergranular corrosion of metal surfaces |
Publications (2)
Publication Number | Publication Date |
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CN1714173A CN1714173A (zh) | 2005-12-28 |
CN100425735C true CN100425735C (zh) | 2008-10-15 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CNB038256347A Expired - Lifetime CN100425735C (zh) | 2002-10-30 | 2003-09-10 | 抑制金属表面的晶间腐蚀的方法 |
Country Status (17)
Country | Link |
---|---|
US (1) | US20040086419A1 (zh) |
EP (1) | EP1558787B1 (zh) |
JP (1) | JP4424671B2 (zh) |
KR (1) | KR101058965B1 (zh) |
CN (1) | CN100425735C (zh) |
AT (1) | ATE355402T1 (zh) |
AU (1) | AU2003267075B2 (zh) |
BR (1) | BR0315190B1 (zh) |
CA (1) | CA2504421A1 (zh) |
DE (1) | DE60312202T2 (zh) |
ES (1) | ES2282654T3 (zh) |
NZ (1) | NZ540134A (zh) |
PL (1) | PL376482A1 (zh) |
RU (1) | RU2320778C2 (zh) |
UA (1) | UA80451C2 (zh) |
WO (1) | WO2004042115A1 (zh) |
ZA (1) | ZA200503934B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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MD307Z (ro) * | 2010-04-27 | 2011-07-31 | Институт Прикладной Физики Академии Наук Молдовы | Inhibitor de coroziune a oţelului în apă |
RU2754319C1 (ru) * | 2020-12-14 | 2021-09-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Способ получения ингибиторов коррозии на основе тетрапропиленпентаминов для нефтепромыслового оборудования и трубопроводов |
RU2754326C1 (ru) * | 2020-12-14 | 2021-09-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Способ получения бис-имидазолинов и их производных на основе пентаэтиленгексаминов для коррозионной защиты нефтепромыслового оборудования и трубопроводов |
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GB894386A (en) * | 1959-04-20 | 1962-04-18 | Continental Oil Co | Polyamine-diol reaction products and corrosion inhibiting compositions containing same |
US3113113A (en) * | 1958-11-07 | 1963-12-03 | Armour & Co | Corrosion inhibitor compositions |
US3152187A (en) * | 1960-04-13 | 1964-10-06 | Continental Oil Co | Condensation product of unsaturated diols and polyalkylene polyamines and method of preparation thereof |
US3211667A (en) * | 1960-04-13 | 1965-10-12 | Continental Oil Co | Corrosion inhibition |
FR2477923A1 (fr) * | 1980-03-11 | 1981-09-18 | Compiegne Universite Technolog | Procede de refroidissement par pulverisation d'eau en coulee continue ou dans des domaines techniques voisins |
DE3317126A1 (de) * | 1983-05-06 | 1984-11-08 | Mannesmann AG, 4000 Düsseldorf | Verfahren zur vermeidung von saeurekorrosion an stranggiessanlagen |
US5173213A (en) * | 1991-11-08 | 1992-12-22 | Baker Hughes Incorporated | Corrosion and anti-foulant composition and method of use |
US5311925A (en) * | 1993-11-12 | 1994-05-17 | Nalco Chemical Company | Magnesium hydroxide to prevent corrosion caused by water spray in continuous casting |
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US2923599A (en) * | 1958-03-26 | 1960-02-02 | Universal Oil Prod Co | Water-soluble corrosion inhibitors |
US3320318A (en) | 1963-08-19 | 1967-05-16 | Continental Oil Co | Thiobenzene-diol-polyamine corrosion inhibiting composition |
CA2123936C (en) * | 1994-04-06 | 2005-12-27 | Bruno E. Morin | Methods of inhibiting water corrosion in crude oil pipelines |
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2002
- 2002-10-30 US US10/283,457 patent/US20040086419A1/en not_active Abandoned
-
2003
- 2003-09-10 WO PCT/US2003/028266 patent/WO2004042115A1/en active IP Right Grant
- 2003-09-10 BR BRPI0315190-5A patent/BR0315190B1/pt active IP Right Grant
- 2003-09-10 CA CA002504421A patent/CA2504421A1/en not_active Abandoned
- 2003-09-10 RU RU2005116268/02A patent/RU2320778C2/ru not_active IP Right Cessation
- 2003-09-10 EP EP03749550A patent/EP1558787B1/en not_active Expired - Lifetime
- 2003-09-10 JP JP2004549947A patent/JP4424671B2/ja not_active Expired - Fee Related
- 2003-09-10 KR KR1020057007590A patent/KR101058965B1/ko active IP Right Grant
- 2003-09-10 NZ NZ540134A patent/NZ540134A/en not_active IP Right Cessation
- 2003-09-10 ES ES03749550T patent/ES2282654T3/es not_active Expired - Lifetime
- 2003-09-10 CN CNB038256347A patent/CN100425735C/zh not_active Expired - Lifetime
- 2003-09-10 AU AU2003267075A patent/AU2003267075B2/en not_active Expired
- 2003-09-10 AT AT03749550T patent/ATE355402T1/de not_active IP Right Cessation
- 2003-09-10 PL PL03376482A patent/PL376482A1/xx unknown
- 2003-09-10 DE DE60312202T patent/DE60312202T2/de not_active Expired - Lifetime
- 2003-10-09 UA UAA200505034A patent/UA80451C2/uk unknown
-
2005
- 2005-05-16 ZA ZA200503934A patent/ZA200503934B/en unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US3113113A (en) * | 1958-11-07 | 1963-12-03 | Armour & Co | Corrosion inhibitor compositions |
GB894386A (en) * | 1959-04-20 | 1962-04-18 | Continental Oil Co | Polyamine-diol reaction products and corrosion inhibiting compositions containing same |
US3152187A (en) * | 1960-04-13 | 1964-10-06 | Continental Oil Co | Condensation product of unsaturated diols and polyalkylene polyamines and method of preparation thereof |
US3211667A (en) * | 1960-04-13 | 1965-10-12 | Continental Oil Co | Corrosion inhibition |
FR2477923A1 (fr) * | 1980-03-11 | 1981-09-18 | Compiegne Universite Technolog | Procede de refroidissement par pulverisation d'eau en coulee continue ou dans des domaines techniques voisins |
DE3317126A1 (de) * | 1983-05-06 | 1984-11-08 | Mannesmann AG, 4000 Düsseldorf | Verfahren zur vermeidung von saeurekorrosion an stranggiessanlagen |
US5173213A (en) * | 1991-11-08 | 1992-12-22 | Baker Hughes Incorporated | Corrosion and anti-foulant composition and method of use |
US5311925A (en) * | 1993-11-12 | 1994-05-17 | Nalco Chemical Company | Magnesium hydroxide to prevent corrosion caused by water spray in continuous casting |
Also Published As
Publication number | Publication date |
---|---|
ZA200503934B (en) | 2006-08-30 |
ES2282654T3 (es) | 2007-10-16 |
AU2003267075A1 (en) | 2004-06-07 |
EP1558787B1 (en) | 2007-02-28 |
EP1558787A1 (en) | 2005-08-03 |
PL376482A1 (en) | 2005-12-27 |
RU2005116268A (ru) | 2006-02-10 |
DE60312202D1 (de) | 2007-04-12 |
BR0315190A (pt) | 2005-08-23 |
WO2004042115A1 (en) | 2004-05-21 |
JP4424671B2 (ja) | 2010-03-03 |
KR20050083872A (ko) | 2005-08-26 |
ATE355402T1 (de) | 2006-03-15 |
KR101058965B1 (ko) | 2011-08-23 |
US20040086419A1 (en) | 2004-05-06 |
BR0315190B1 (pt) | 2013-02-05 |
RU2320778C2 (ru) | 2008-03-27 |
DE60312202T2 (de) | 2007-10-31 |
UA80451C2 (en) | 2007-09-25 |
NZ540134A (en) | 2006-10-27 |
AU2003267075B2 (en) | 2009-06-25 |
JP2006504870A (ja) | 2006-02-09 |
CA2504421A1 (en) | 2004-05-21 |
CN1714173A (zh) | 2005-12-28 |
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