CN1823182A - 流体体系的腐蚀抑制 - Google Patents

流体体系的腐蚀抑制 Download PDF

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CN1823182A
CN1823182A CNA2004800206460A CN200480020646A CN1823182A CN 1823182 A CN1823182 A CN 1823182A CN A2004800206460 A CNA2004800206460 A CN A2004800206460A CN 200480020646 A CN200480020646 A CN 200480020646A CN 1823182 A CN1823182 A CN 1823182A
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corrosion
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罗莎·克罗维托
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General Electric Co
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Abstract

本发明提供了抑制与工业体系中所含流体接触的金属表面腐蚀的有效方法，该方法包括向所述流体添加有效控制腐蚀量的磷酸甘油酯化合物或乳化豆油。

Description

流体体系的腐蚀抑制
技术领域
本发明一般性地涉及保护金属表面免受水性和非水性流体体系的蒸汽相和液相腐蚀。更具体地，本发明涉及腐蚀抑制组合物及使用其的方法。
背景技术
工厂中金属部件的腐蚀会引起体系失灵并且有时引起工厂停产。另外，积累在金属表面的腐蚀产物会降低金属表面和水或其它流体介质之间的传热速率，从而腐蚀将降低体系操作的效率。因此，腐蚀增加了维护成本和生产成本。
对付腐蚀最通常的方法是向这些体系的流体中添加防腐添加剂。然而，目前可用的防腐添加剂是非生物可降解的、有毒的，或两者都具备，这限制了这些添加剂的可应用性。
与锅炉冷凝物体系结合使用的最常见的防腐添加剂是中和胺(neutralizing amine)和膜胺(filming amine)。尽管胺和胺的组合一般对钢和其它含铁金属提供了有效保护，但目前在防腐添加剂中使用胺带来了几个问题。
首先，胺在高温下常常经历热分解并形成氨气，该氨气对铜和铜合金的腐蚀很强，特别在氧气存在下。因此，含有胺的缓蚀剂用于包含铜或铜合金冶金的体系常常不尽人意。
另外，在包括食品加工、饮料生产、废热电站(co-generation plant)和制药的大量应用中，胺的使用因政府法规或对味道和气味问题的关注而受到限制。从而，在许多这些应用中，根本不采用防腐处理步骤。因此，这些体系易遭受高腐蚀率、高维护成本和高设备失灵率。
美国专利5,368,775讨论了控制酸致腐蚀的方法。在一方法中，使用薄膜作为欲保护金属表面和酸性溶液之间的屏障。使用长链胺例如十八烷基胺或唑系形成薄膜。第二种方法需要添加中和胺以中和酸并提高水溶液的pH。用于该方法的最佳胺描述为具有高碱度和低分子量。引用环己胺、二甲胺、三甲胺、吗啉和甲氧基丙胺作为中和胺的实例。
美国专利4,915,934披露了可发泡的杀生物剂组合物来对付含醇chlorohexidine溶液的腐蚀本性，所述组合物包括含醇chlorohexidine溶液，快速灭泡剂、气溶胶推进剂和缓蚀剂。快速灭泡剂包含作为其成分之一的表面活性剂，优选为乙氧基化脱水山梨糖醇酯。该表面活性剂充当乳化剂。所给出的优选乳化剂的实例包括乙氧基化脱水山梨糖醇硬酯酸酯、棕榈酸酯和油酸酯；壬基苯酚乙氧基化物；以及脂肪醇乙氧基化物。
美国专利3,977,994披露了防锈组合物。该组合物是有机酸、N-烷基或环烷基取代的乙醇胺和水的混合物。在一些情况中，该组合物还可以包含至少一种乳化剂来使有机酸和乙醇胺乳化。所述乳化剂的实例包括脱水山梨糖醇的衍生物。
美国专利4,970,026教导了用于含铁水性体系和不含铁水性体系的缓蚀剂。其组合物包括选自以下的组分：三乙醇胺N-烷基硫酸二酰胺羧酸的环烷油基钠盐；三乙醇胺N-烷基硫酸二酰胺羧酸的石蜡油基钠盐；N-烷基硫酸二酰胺羧酸的钠盐；和包括两种选择的混合物，以及表面活性剂，该表面活性剂选自肌氨酸的长链脂肪酸衍生物和环氧乙烷与脂肪酸的缩合产物。
防腐效果归功于所述组分或所述组分的混合物，而不是添加的表面活性剂。事实上，该专利指出，分别测试了表面活性剂作为缓蚀剂的效果。发现表面活性剂作为缓蚀剂是无效的。
美国专利5,082,592披露了用于水溶液中含铁金属防腐的方法，所述水溶液包括非离子表面活性剂和含氧阴离子的基团，例如硼酸、钼酸和硝酸/亚硝酸的碱金属盐。优选的非离子表面活性剂是苯酚/聚环氧乙烷。
在该专利的说明书中假设非离子表面活性剂增加了阴离子的防腐性能。阴离子的防腐性能起因于它们在金属表面和溶液界面处的吸附。认为非离子表面活性剂的共吸附起到通过屏蔽阴离子的流体静压排斥力使阴离子表面浓度最大化的作用。
EPO专利申请0 108 536 B1披露了保护金属表面免受腐蚀的方法。该方法使用缓蚀剂和增稠剂的组合物。缓蚀剂可包括脱水山梨糖醇的羧酸酯。在与增稠剂的结合中，该缓蚀剂是假塑性和触变的。在静置时组合物形成凝胶。所述组合物形成软的柔性涂层，该涂层可以替代经常用于保护金属表面免受腐蚀的涂料、清漆、漆、塑料和金属涂层。
因此，强烈需要防腐的非胺的、毒性较小的添加剂，该添加剂是更加可被环境接受的替代物。在本发明中，磷酸甘油酯化合物出乎意料地提供了在水性和非水性溶液中保护金属表面不受腐蚀。
发明内容
本发明提供了抑制与工业流体体系中所含流体接触的金属表面腐蚀(例如，二氧化碳腐蚀)的有效方法，该方法包括向所述流体中加入有效控制腐蚀量的磷酸甘油酯化合物。
磷酸甘油酯化合物可以为，例如通常称为卵磷酯的磷酯酰胆碱(PC)，磷酯酰乙醇胺(PE)或磷酯酰丝氨酸(PS)。在本发明的优选实施方案中，磷酸甘油酯化合物为卵磷酯。卵磷酯化合物具有以下结构：
CH2(R)CH(R1)CH2OPO(OH)O(CH2)2N(OH)(CH3)3
其中R、R1可以为脂肪酸基团，例如亚油酸、硬脂酸、油酸和/或棕榈酸的基团。
为此应该向流体体系添加有效量的本发明的组合物，对于所述流体体系，与流体体系接触的金属部件的防腐活性是必需的。添加量根据需要处理的具体体系而改变，并受到例如腐蚀面积、pH、温度、水量和水中腐蚀物质各自浓度等因素的影响。在极大程度上，当以约0.025-50份/百万(ppm)的待处理体系中的流体，且优选以0.025-10ppm的待处理体系中的流体使用时，本发明将是有效的。可以连续或间歇地以固定量和以水溶液态将本发明的组合物直接加入所需流体体系中。所述流体体系可以是，例如冷却水、锅炉水、锅炉蒸汽、气体洗涤或者纸浆和造纸体系。可受益于本发明处理的流体体系的其它实例包括传热体系、精炼体系、食品和饮料体系、制药应用体系(pharmaceutical utility system)和机械冷却体系。
具体实施方式
现参考多种具体实施例来进一步描述本发明，这些实施例应仅仅看作是说明性的，而不是限制本发明的范围。
在实验室的腐蚀测试装置中进行测试。该设备包括去离子和去氧水源、高压泵、一系列输送材料的计量泵和相关的传感器。
用于本发明的测试装置包括充当腐蚀金属的16英尺低碳钢卷(OD：0.25″，ID：0.135″)。详细的实验条件如下：1.使用去离子碳酸水作为流体；2.进口氧浓度为10ppb；3.低碳钢卷内的流速为180ml/min；4.保持钢卷和流动溶液的温度为104℃±3℃。
为了得到更好的热稳定性，将钢卷容纳在填充了沙的加热罐内。两个内部热电偶监测钢卷进口/出口温度。保持CO2的浓度恒定并用碳分析器Sievers TOC 800测量。溶液的pH估计为5.15±0.10。
在装置出口流体中的总铁浓度表示低碳钢卷的腐蚀。在实验室用1，10-菲咯啉作为反应剂(reactive)以比色法粗略估计铁的浓度，通过感应耦合等离子体(ICP)确定总铁含量。
计算腐蚀抑制百分数，其为运行条件下未处理钢卷出口处的总铁浓度(Fe ppm UT)和在相同实验条件下离开化学处理钢卷的总铁浓度(Fe ppm T)之间的差异：腐蚀抑制％＝((Fe ppm UT)-Fe ppm T))×100)/(Fe ppm UT)。
对于未处理卷和一些处理运行，探索(following)铁释放的动力学。未处理的铁卷在4至8小时内快速达到平滑。以下是每种浓度平衡时间为20-26小时的结果。在该时间期间，为了探索铁释放动力学，对出口流体取样并分析总铁含量。在设定的平衡时间(20-26小时)结束时使用测量的总铁浓度计算由化学物质产生的腐蚀百分数。
在每次运行之前和之后，将铁卷从装置中分离、活化、再接合，并使其在开始处理之前的总铁浓度中达到平衡。测量的总铁浓度为上式中的(Feppm UT)。
根据上述程序，在测试装置中测试得自Fluka GmbH的大豆卵磷酯作为腐蚀抑制剂。该化学物质称为得自大豆的3-sn磷酯酰胆碱、磷酯酰胆碱、L-a-卵磷酯；L-a-磷酯酰胆碱。注意到，该化学物质不是水溶性的，但易于在水中乳化。
表1表示在测试装置中将卵磷酯输入铁卷时得到的腐蚀抑制百分数。使用由ICP测量的总铁浓度计算腐蚀百分数。结果表明该化学物质起着金属缓蚀剂的作用。
表1
当输入卵磷酯时的腐蚀抑制％
  运行   卵磷脂(ppm)   腐蚀抑制％
  1   0   0.0
  1   1   44.8
  1   2   43.5
  2   0   0.0
  2   1   43.2
  2   2   51.1
还使用上述相同的程序在腐蚀测试装置中测试精制大豆油和粗大豆油作为缓蚀剂。注意到，使用的油不是水溶性的。依次将它们输入测试水中，将材料进行乳化。为此使用占油约10％重量的蔗糖脂肪酸酯(蔗糖酯：非离子的水溶性表面活性剂)。为了形成乳状液。在60-65℃在水中向酯溶液中添加少量油，同时剧烈搅拌。表2和表3显示了获得的金属腐蚀抑制百分数的结果。结果表明乳状液起着金属缓蚀剂的作用。
表2
用精制大豆油得到的腐蚀抑制％
  运行   精制大豆油(ppm)   Fe腐蚀抑制％
  1   0   0
  1   0.34   8.0
  1   0.86   21
  1   1.1   28
  2   0   0
  2   1   7
  2   2.2   65
  3   0   0
  3   1.05   10
  3   3.19   16
  4   0   0
  4   0.99   32
  4   2.01   83
表3
用乳化的粗大豆油得到的腐蚀抑制％
  运行   原料大豆油(ppm)   Fe腐蚀抑制％
  1   0   0
  1   0.96   64
  1   2.54   63
  2   0   0
  2   0.99   21
  2   2.5   45
尽管根据本发明的具体实施方案描述了本发明，但显然对于本领域的技术人员来说，本发明的大量其它形式和修改都将是显而易见的。本发明所附的权利要求书通常认为涵盖了在本发明的实质和范围内的所有这些明显的形式和修改。

Claims (10)

1.抑制与工业流体体系所含流体接触的金属表面腐蚀的方法，该方法包括向所述流体添加有效控制腐蚀量的处理剂，该处理剂选自磷酸甘油酯化合物和豆油。
2.权利要求1的方法，其中所述磷酸甘油酯化合物选自磷酯酰胆碱、磷酯酰乙醇胺和磷酯酰丝氨酸。
3.权利要求1的方法，其中所述流体体系选自传热体系、精炼体系、食品和饮料体系、制药应用体系和机械冷却体系。
4.权利要求1的方法，其中所述化合物是以约0.025至约50ppm的有效处理剂量(active treatment level)添加至流体体系的。
5.权利要求4的方法，其中所述化合物是以约0.025至约10ppm的有效处理量添加至流体体系的。
6.抑制与工业流体体系中所含流体接触的金属表面上二氧化碳腐蚀的方法，该方法包括向所述流体添加有效控制腐蚀量的处理剂，该处理剂选自磷酯酰胆碱化合物和豆油。
7.权利要求6的方法，其中所述流体体系选自传热体系、精炼体系、食品和饮料体系、制药应用体系和机械冷却体系。
8.权利要求6的方法，其中所述磷酯酰胆碱化合物得自豆油。
9.权利要求6的方法，其中所述化合物是以约0.025至约50ppm的有效处理剂量添加至流体体系的。
10.权利要求9的方法，其中所述化合物是以约0.025至约10ppm的有效处理剂量添加至流体体系的。
CNA2004800206460A 2003-07-31 2004-06-21 流体体系的腐蚀抑制 Pending CN1823182A (zh)

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