CN1312865A - 抑制水系统中腐蚀的方法 - Google Patents
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Abstract
本发明提供一种用于控制金属腐蚀、特别是与水系统接触的铁基金属腐蚀的方法,其包括用通式(Ⅰ)的四唑盐(包括上述结构的单体或低聚物)处理工业用水,其中R1、R2和R3可以是各种有机或无机取代基。
Description
发明领域
本发明涉及对水进行处理以抑制结垢和控制与水系统接触的金属腐蚀的方法。更具体地说，本发明涉及使用四唑盐以抑制结垢或防止与水系统接触的铁基金属腐蚀的方法。
发明的背景
在工业冷却系统中，将例如取自江河、湖泊、池塘等的水用作热交换器的冷却介质。来自热交换器的冷却水在排放出或再使用之前通常通过冷却塔、喷淋池或蒸发系统。在这些体系中，冷却效应是通过蒸发流过系统的一部分水而实现。由于在冷却过程中发生蒸发，在水中溶解的材料变得浓缩，使得该种水更具腐蚀性。
在冷却系统中，腐蚀引发两个基本问题。第一个和最明显的问题是设备失效，导致维修成本和装置停工。而且，由于传热损失，引起装置效率降低。腐蚀产物的累积引起热交换器结垢，从而导致传热损失。铁基金属，例如铁金属和含铁的金属合金(低碳钢)是通常用在冷却系统的构建中，因为它们的成本低和容易买到。当系统的水从这些含铁基金属的装置上或之中通过时，它们经受了腐蚀过程。通常加入腐蚀抑制剂作为冷却系统中的水处理步骤的一部分以防止和抑制含铁基金属的装置的腐蚀。
曾经将钼酸盐、锌、磷酸盐或多磷酸盐用于抑制与冷却系统的系统水接触的铁基金属的腐蚀。然而，每种处理均表现出一些缺点。
因此需要一种用于与水系统接触的铁基金属的更具环境可接受性的腐蚀抑制剂。
防止工业传热设备的腐蚀和结垢对冷却水系统的有效和经济操作是十分重要的。金属表面的过度腐蚀可引起工艺设备的早期失效，必然导致用于更换或维修设备的停工时间。另外，在传热表面的腐蚀产物的堆积降低了效率，由此限制了生产或要求用于清洗的停工时间。
发明概述
本发明提供一种用于控制金属腐蚀、特别是与水系统接触的铁基金属腐蚀的有效方法。
本发明的方法包括用下列通式的四唑盐处理工业用水：
其中R1、R2和R3可以是各种有机或无机取代基，例如是选自于低级烷基、芳基、芳烷基和杂环取代芳基，但R1、R2或R3均不能含有超过14个碳原子，和n可以是1或2。
为了平衡上述结构上的电荷，所述化合物可包含正或负反离子。这类化合物的化学或电化学还原产生容易吸附在金属表面和形成用于腐蚀保护的薄膜的四唑基和甲。
在水系统中，金属例如钢发生下列腐蚀反应：
当使用具有高于受腐蚀的金属或合金的氧化还原电势的四唑化合物时，在钢表面上容易发生四唑分子的还原以形成不溶材料且因此防止钢进一步腐蚀。
优选实施方案的详细描述
本发明的处理方法的成膜和腐蚀抑制活性是用烧杯腐蚀测试装置(BCTA)进行评估的。该BCTA包括配备有空气/CO2喷射器的烧杯，低碳钢试样片、电化学探针和磁搅拌器。将烧杯浸入至用于控制温度的水浴中。使用线性极化电阻工艺测得电化学腐蚀数据。所有的测试均是在120°F,400RPM下进行18小时。
测试的化合物
NBT:3,3’-二甲氧基-4,4’-亚联苯基)-双-[2-(对硝基苯基)-5-苯基-2H-氯化四唑]INT:2-(4-碘苯基)-3-(4-硝基苯基)-5-苯基-氯化四唑TZV:2,5-二苯基-3-(1-萘基)-2H-氯化四唑TTC:2,3,5-三苯基-2H-氯化四唑
| 化合物 | R1 | R2 | R3 | n |
| NBT | CH3OC6H3 | NO2C6H4 | C6H5 | 2 |
| INT | IC6H4 | NO2C6H4 | C6H5 | 1 |
| TZV | C10H7 | C6H5 | C6H5 | 1 |
| TTC | C6H5 | C6H5 | C6H5 | 1 |
实施例1
试验用水：250ppm Ca(以CaCO3形式)，125ppm Mg(以CaCO3形式)，10ppm SiO2(以SiO2形式)，300ppm Cl,200ppm SO4,7.5ppm聚乙氧基琥珀酸(PESA),7.5ppm丙烯酸和烯丙基羟丙基磺化醚钠盐的共聚物(AA/AHPSE)
对于在空白试验水和在含有抑制剂氯化氮蓝四唑单水合物(NBT)和2-(4-碘苯基)-3-(4-硝基苯基)-5-苯基-氯化四唑(INT)的试验水中低碳钢的腐蚀率的结果是总结在表1中。
表1
实施例2
| 处理物 | 活性ppm | PH | m-Alk(作为CaCO3形式的ppm) | 平均腐蚀率(密耳/年) |
| 空白 | - | 8.4 | 90 | 38.4 |
| NBT | 20 | 8.4 | 90 | 2.06 |
| INT | 20 | 8.4 | 90 | 8.00 |
试验用水：100ppm Ca(以CaCO3形式),50ppm Mg(以CaCO3形式)，100ppm Cl,100ppm SO4,5ppm PESA
对于在含有抑制剂2,5-二苯基-3-(1-萘基)-2H-氯化四唑(四唑紫或TZV)氯化氮蓝四唑单水合物(NBT)和2-(4-碘苯基)-3-(4-硝基苯基)-5-苯基-氯化四唑(INT)试验水中低碳钢的腐蚀率的结果是总结在表2中。
表2
实施例3
| 处理物 | 活性ppm | PH | m-Alk(作为CaCO3形式的ppm) | 平均腐蚀率(密耳/年) |
| 空白 | - | 8.6 | 375 | 35.5 |
| TZV | 2 | 8.6 | 375 | 18.7 |
| TZV | 20 | 8.6 | 375 | 3.68 |
| NBT | 20 | 8.6 | 375 | 2.64 |
| INT | 20 | 8.6 | 375 | 3.19 |
试验用水：100ppm Ca(以CaCO3形式)，50ppm Mg(以CaCO3形式)，100ppm Cl,100ppm SO4,5ppm PESA,5ppm AA/AHPSE
对于在含有抑制剂2,5-二苯基-3-(1-萘基)-2H-氯化四唑(四唑紫或TZV)2,3,5-三苯基-2H-氯化四唑(TTC)的试验水中低碳钢的腐蚀率的结果是总结在表3中。
表3
*LCS是在不含TZV的这个水中测试之前用20ppmTZV处理18小时。
| 处理物 | 活性ppm | PH | m-Alk(作为CaCO3形式的ppm) | 平均腐蚀率(密耳/年) |
| 空白 | - | 8.6 | 375 | 23.1 |
| TZV | 20 | 8.6 | 375 | 3.48 |
| TZV | 0 | 8.6 | 375 | 1.48* |
| TTC | 20 | 8.6 | 375 | 12.1 |
| TTC | 50 | 8.6 | 375 | 8.2 |
| 空白 | - | 7.6 | 32 | 45.5 |
| TZV | 50 | 7.6 | 32 | 22.2 |
| TTC | 20 | 7.6 | 32 | 42.6 |
| TTC | 50 | 7.6 | 32 | 40.1 |
| 空白 | - | 6.8 | 4 | 85.3 |
| TZV | 50 | 6.8 | 4 | 33.2 |
| TTC | 20 | 6.8 | 4 | 58.5 |
| TTC | 50 | 6.8 | 4 | 62.3 |
本发明的处理物可连续地或间断地添加。在选择的具体用途之前，所述化合物可用作活化金属表面的预处理物。
实施例4
试验用水：100ppm Cl,100ppm SO4
对于在含有抑制剂2,5-二苯基-3-(1-萘基)-2H-氯化四唑(四唑紫或TZV)氯化氮蓝四唑单水合物(NBT)和2-(4-碘苯基)-3-(4-硝基苯基)-5-苯基-氯化四唑(INT)的试验水中低碳钢的腐蚀率的结果是总结在表4中。
表4
| 处理物 | 活性ppm | PH | m-Alk(作为CaCO3形式的ppm) | 平均腐蚀率(密耳/年) |
| 空白 | - | 8.6 | 342 | 83 |
| TZV | 2 | 8.6 | 342 | 20.9 |
| TZV | 20 | 8.6 | 342 | 4.92 |
| NBT | 20 | 8.6 | 342 | 9.18 |
| INT | 20 | 8.6 | 342 | 6.95 |
| 空白 | - | 7.6 | 31 | 126 |
| TZV | 2 | 7.6 | 31 | 116 |
| TZV | 20 | 7.6 | 31 | 16.3 |
在长凳工作台面循环装置(BTU)测试中，设计BTU装置以测量处理物防止腐蚀和结垢形成的能力。经处理的水是通过其中插入有试样片和探针的旁路支管进行循环并通过一个热交换管。通过装置的水的速度可控制在约0至4.5英尺/秒。使用LCS探针的线性极化测试得到腐蚀率。不锈钢探针被用作反电极和参比电极。
在下列条件下为期7天的测试中LCS腐蚀速率的结果是总结在表5中。
试验用水：100ppm Ca(以CaCO3形式)，50ppm Mg(以CaCO3形式)，100ppm Cl,100ppm SO4,5ppm PESA,5ppm AA/AHPSE主体水温：120°F流动速率：4英尺/秒
表5
| 处理物 | 剂量(活性ppm)间断/连续 | PH | m-Alk(作为CaCO3形式的ppm) | 平均腐蚀率(密耳/年) |
| NBT | 50/10 | 7.6 | 32 | 0.57 |
| NBT | 25/5 | 8.6 | 375 | 1.90 |
在本发明的优选实施方案中，将化合物以约0.1-50ppm的活性处理物量添加至水系统中，特别优选以约1-25ppm的处理物量。
能够得益于本发明的处理物的体系包括冷却水系统、蒸汽产生系统、气体洗涤系统和制浆及造纸系统。待处理的水系统的PH是约6或更大。
虽然以上参照特定的实施方案对本发明进行了描述，但本发明的许多其它形式和改进对本领域熟练人员将是十分明显的。所附的权利要求书和本发明总体上应包括属于本发明的实质精神和范围内的所有此种明显形式和改进。
Claims (12)
1、控制与水系统接触的金属腐蚀的方法，其包括将下列通式的化合物引入至所述水系统中：
其中R1、R2和R3是选自于低级烷基、芳基、芳烷基和杂环取代芳基，但R1、R2或R3均不能含有超过14个碳原子，且n是1或2。
2、如权利要求1所述的方法，其中所述化合物是选自于：3,3’-二甲氧基-4,4’-亚联苯基)-双-[2-(对硝基苯基)-5-苯基-2H-氯化四唑]；2-(4-碘苯基)-3-(4-硝基苯基)-5-苯基氯化四唑；2,5-二苯基-3-(1-萘基)-2H-氯化四唑；2,3,5-三苯基-2H-氯化四唑。
3、如权利要求2所述的方法，其中所述水系统是冷却水系统。
4、如权利要求1所述的方法，其中将所述化合物以约0.1-50ppm的活性处理物量添加至水系统中。
5、如权利要求4所述的方法，其中将所述化合物以约1-25ppm的活性处理物量添加至水系统中。
6、如权利要求1所述的方法，其中所述水系统是蒸汽产生系统。
7、如权利要求1所述的方法，其中所述水系统是气体洗涤系统。
8、如权利要求1所述的方法，其中所述水系统是制浆和造纸系统。
9、如权利要求1所述的方法，其中所述金属是铁基金属。
10、如权利要求1所述的方法，其中所述水系统的PH是约6或更大。
11、如权利要求1所述的方法，其中所述化合物是连续地添加至所述水系统中。
12、如权利要求1所述的方法，其中所述化合物是间断地添加至所述水系统中。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/136,884 | 1998-08-19 | ||
| US09/136,884 US6187262B1 (en) | 1998-08-19 | 1998-08-19 | Inhibition of corrosion in aqueous systems |
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| Country | Link |
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| US (1) | US6187262B1 (zh) |
| EP (1) | EP1115907A1 (zh) |
| JP (1) | JP2002523624A (zh) |
| KR (1) | KR20010072752A (zh) |
| CN (1) | CN1312865A (zh) |
| AR (1) | AR024829A1 (zh) |
| AU (1) | AU764313B2 (zh) |
| BR (1) | BR9913099A (zh) |
| CA (1) | CA2339982A1 (zh) |
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| HK (1) | HK1041028A1 (zh) |
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| ID (1) | ID28730A (zh) |
| NO (1) | NO20010722D0 (zh) |
| PL (1) | PL346039A1 (zh) |
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| CN110117791A (zh) * | 2019-05-23 | 2019-08-13 | 电子科技大学 | 一种用于高密度互联印制电路板棕化液的结合力促进剂 |
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| US6379587B1 (en) * | 1999-05-03 | 2002-04-30 | Betzdearborn Inc. | Inhibition of corrosion in aqueous systems |
| MXPA01011087A (es) * | 1999-05-03 | 2002-06-04 | Betzdearborn Inc | Metodo y composicion para inhibir la corrosion en sistemas acuosos. |
| US8361952B2 (en) | 2010-07-28 | 2013-01-29 | Ecolab Usa Inc. | Stability enhancement agent for solid detergent compositions |
| EP2702891B1 (fr) | 2012-09-04 | 2015-11-18 | Omega SA | Fermoir pour bracelet de montre ou ceinture vestimentaire |
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| US3619347A (en) * | 1969-03-13 | 1971-11-09 | Salvox Mfg Co | Recovery of wastepaper treated with urea or the like resins to impart wet strength |
| US3860464A (en) | 1973-10-11 | 1975-01-14 | Bell Telephone Labor Inc | Oxide etchant |
| US4683035A (en) | 1986-02-03 | 1987-07-28 | Nalco Chemical Company | Method for in situ corrosion detection using electrochemically active compounds |
| US5073339A (en) * | 1990-08-23 | 1991-12-17 | W. R. Grace & Co. - Conn | Method of inhibiting corrosion and scale formation in aqueous systems |
| US5141675A (en) * | 1990-10-15 | 1992-08-25 | Calgon Corporation | Novel polyphosphate/azole compositions and the use thereof as copper and copper alloy corrosion inhibitors |
| US5425914A (en) * | 1994-03-22 | 1995-06-20 | Betz Laboratories, Inc. | Methods for inhibiting corrosion in cooling water systems |
| US5610068A (en) | 1995-07-28 | 1997-03-11 | Nalco Chemical Company | Field method for determining if adequate corrosion inhibition has been applied to thermally processed cans |
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1998
- 1998-08-19 US US09/136,884 patent/US6187262B1/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110117791A (zh) * | 2019-05-23 | 2019-08-13 | 电子科技大学 | 一种用于高密度互联印制电路板棕化液的结合力促进剂 |
| CN110117791B (zh) * | 2019-05-23 | 2023-11-10 | 电子科技大学 | 一种用于高密度互联印制电路板棕化液的结合力促进剂 |
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| Publication number | Publication date |
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| ID28730A (id) | 2001-06-28 |
| KR20010072752A (ko) | 2001-07-31 |
| AR024829A1 (es) | 2002-10-30 |
| NO20010722L (no) | 2001-02-12 |
| JP2002523624A (ja) | 2002-07-30 |
| AU5465199A (en) | 2000-03-14 |
| NO20010722D0 (no) | 2001-02-12 |
| EP1115907A1 (en) | 2001-07-18 |
| HUP0300309A2 (en) | 2003-06-28 |
| PL346039A1 (en) | 2002-01-14 |
| US6187262B1 (en) | 2001-02-13 |
| BR9913099A (pt) | 2001-05-08 |
| TW475003B (en) | 2002-02-01 |
| HK1041028A1 (zh) | 2002-06-28 |
| AU764313B2 (en) | 2003-08-14 |
| ZA200102275B (en) | 2002-06-19 |
| CZ2001592A3 (cs) | 2001-09-12 |
| WO2000011239A1 (en) | 2000-03-02 |
| CA2339982A1 (en) | 2000-03-02 |
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