CN1669093A - 用来清洗压水反应器的蒸汽发生器的方法 - Google Patents
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- F28G9/00—Cleaning by flushing or washing, e.g. with chemical solvents
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- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
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Abstract
本发明涉及一种用来清洗压水反应器的蒸汽发生器的方法，在该法中蒸汽发生器双重地在提高的压力下和提高的温度下用水性的清洗溶液处理，该溶液含有EDTA、还原剂和碱化剂。本发明提出用吗啉作为碱化剂，在此吗啉的摩尔浓度选择为至少如EDTA的摩尔浓度那么大。
Description
本发明涉及一种用来清洗压水反应器的蒸汽发生器的方法。压水反应器的蒸汽发生器通常包括一个容器，在其下部设置有许多例如弯成U-形的、流过初级冷却剂的热交换管。在其上部有其他的构件，如蒸汽分离器和蒸汽干燥器。热交换管由耐腐蚀的合金构成，而容器、用来固定热交换管的辅助结构和流过次级冷却剂的次级循环的部件部分地由具有较小的耐腐蚀性的材料，如C-钢制备。所以上述的部件会在主要的操作温度下受到腐蚀。在操作过程中在次级循环中生成的腐蚀产物，主要是磁铁矿，到达蒸汽发生器中，在此其沉积在容器底部和管道之间的空间以及在热交换管的表面上生成沉淀层。为了保证蒸汽发生器的完整无损和可有效操作，特别是无阻碍的热传导，那么-如果必需-就要在每年的维修维护中进行清洁净化操作，以化学的方法去除沉积所形成的淀积物和热交换管的沉淀层。
出于这个目的，蒸汽发生器分步骤地这样用清洁净化液填注，使交换管完全被浸没。一种常用的、例如由US 4,632,705已知的清洗溶液含有形成络合物的酸，如乙二胺四乙酸(EDTA)、还原剂，如肼、和作为碱化剂的氨。碱性的条件是必需的，以保持在由C-钢或低合金钢构成的次级循环部件中尽可能少的材料侵蚀量。此外，出于这个目的还添加腐蚀阻止剂。在从DE 198 57 342中获知的、同样用肼作为还原剂操作的方法中用吗啉(四氢-1，4-噁嗪)作为碱化剂。吗啉比氨要难挥发得多，以致于只有相应的较少的份额进入蒸汽相。在上述种类的清洗方法中通常是这样进行的，即在一定的时间内通过在蒸汽发生器后面设置的新蒸汽系统的阀而进行突然的降压，其导致强烈的沸腾和导致在清洗液中的强烈的涡流。以这种方式混合清洗溶液，以致于络合物形成剂在还原以后可以溶解磁铁矿。因为吗啉在蒸汽相中的份额比氨要少得多，所以在降压时到达环境周围的对环境有害的碱化剂的量比用氨操作的方法时要少得多。对于本清洗方法，碱化剂的较少的损失具有这个重要的优点，即直到清洗结束其pH-值基本保持恒定。这样相对于用氨的方法就减少了母体金属的去除量，在用氨的方法中，由于氨的排出，pH-值在清洗结束时降至几乎是中性点的值。
本发明的任务是，给出一种用于压水反应器的蒸汽发生器的清洗方法，用这种方法不用添加腐蚀阻止剂在还可进一步减少母体金属去除量的情况下进行有效的清洗是可能的。
这一任务根据权利要求1而解决。令人惊奇地显示出，通过用一种清洗溶液，在该清洗溶液中吗啉的摩尔浓度至少如EDTA的摩尔浓度那么大，一种比氨法温和的、也即对母体金属更小腐蚀性的清洗是可能的。
在清洗溶液中的上述成分的绝对浓度当然与每次所要去除的沉积物的量相关，以致于其在可能的情况下以较高的浓度存在。尽管如此，当吗啉以与EDTA相比相同的或过量的摩尔浓度存在时，还是可观察到上述的温和作用。
吗啉与EDTA的摩尔比优选为1∶1-6∶1。当比例为4∶1时，得到最佳的结果。最后提到的摩尔比相当于1.2的质量比。当肼与EDTA的摩尔比值为1∶6-1∶1时得到特别好的清洗效果。优选的摩尔比是1∶3，其相当于0.04的质量比。除了特别优选的肼外还可用其他的还原剂，特别是甲醛。
实施例：
一种合适用于清洗蒸汽发生器的清洗溶液含有60g/l EDTA(＝0.205Mol/l)、71.5g/l吗啉(＝0.821Mol/l)和2.2g/l肼(＝0.068Mol/l)。这种溶液具有约9的pH-值。吗啉与EDTA的摩尔比也是4∶1，肼与EDTA的摩尔比为1∶3。
优选的方法实施方案为，清洗在反应器关闭时进行。一旦在蒸汽发器中的温度为约160℃时，就将溶液的各成分以浓缩的形式以这样的量加入，即在加入水后调节至上述的浓度。在蒸汽发生器中根据清洗温度具有约6-10bar的压力。通过分布于整个清洗过程中的、突然的压力降低而使得清洗溶液沸腾，这样还没有用过的化学试剂与沉积物接触。在约140℃以下时清洗不再是可有效进行的。
为了试验用吗啉操作的清洗溶液与氨比较在同样的方法中的效果，进行以下更清楚的描述的试验：
在一个由不锈钢制成的实验室高压釜中11.5g来自压水装置的蒸汽发生器的磁铁矿沉积物，具有约72.5重量％的铁含量，用约1L的上述的清洗溶液在160℃下处理8小时，在此进行多次的突然降压，以达到密切混合的目的。在排汽过程中失去的水量和用来从高压釜中取出试样而失去的清洗溶液的量被再次补给。用在高压釜中设置的、用特氟隆涂层的悬挂装置而在液面下设置由C-钢构成的取样管。
在这些条件下进行2个试验，在此，在一种情况下用氨/EDTA和在另一种情况下用吗啉/EDTA操作和每种碱化剂这样加入，即将pH-值调节到9。通过再次补充所取出的清洗液而保持这个数值几乎恒定直至清洗结束，以使阻止上述的由于pH-值的下降而提高的母体金属受腐蚀的效应。在试验的最后测定从取样管和从沉积物中已溶解的铁份额。在两种情况下测得已溶解的沉积物与所用的沉积物的比例为95％。根据磁铁矿沉积物的溶解，两种清洗溶液也显示出可比较的作用效果。然而在用氨的试验中从由C-钢构成的取样管已溶解的铁份额为20％，而这个份额在吗啉试验中只为15％。从而对于具有吗啉的清洗溶液其对C-钢的腐蚀影响是更小。在用氨清洗时平均材料去除为27μm，这相当于平均去除速率为34g/l*h*m2。在吗啉试验中观察到平均材料去除为21μm，或平均去除速率为20g/l*h*m2。因为在种种情况下pH-值几乎是保持恒定的，所以氨试验的较差的试验结果不能归因于pH-值下降。在此显示更多的是由EDTA/吗啉联合所给出的作用效果。
由申请人进行的氨/EDTA和吗啉/EDTA的差热分析表明吗啉/EDTA系统有更高的热稳定性，假如保持上述的摩尔比的话。已知EDTA在较高的温度下分解，在此生成促进腐蚀的分解产物，如亚氨二乙酸。迄今为止在缩短的清洗时间内或降低的清洗温度下遇到了这问题。由此引起的缺点是显而易见的。与此相反对于本发明所提出的方法可利用较大的时间范围。此外由于吗啉/EDTA的较高的热稳定性而使得在比180℃更高的温度下进行清洗也是可能的。
Claims (8)
1.一种用来清洗压水反应器的蒸汽发生器的方法，在该方法中蒸汽发生器双重地在提高的压力下和提高的温度下用水性的清洗溶液处理，该溶液含有EDTA、还原剂和作为碱化剂的吗啉，其特征在于，使用一种清洗溶液，在该清洗溶液中吗啉的摩尔浓度至少如EDTA的摩尔浓度那么大。
2.根据权利要求1的方法，其特征在于，使用一种清洗溶液，在该清洗溶液中吗啉和EDTA以1∶1-6∶1的摩尔比存在。
3.根据权利要求2的方法，其特征在于，吗啉与EDTA的摩尔比为4∶1。
4.根据权利要求1、2或3的方法，其特征在于，肼用作为还原剂。
5.根据权利要求1、2或3的方法，其特征在于，甲醛用作为还原剂。
6.根据权利要求4和5中至少一项的方法，其特征在于，使用一种清洗溶液，其具有肼和/或甲醛与EDTA的摩尔比为1∶6-1∶1。
7.根据权利要求6的方法，其特征在于，肼和/或甲醛与EDTA的摩尔比为1∶3。
8.根据权利要求1-7中至少一项的方法，其特征在于，在清洗过程中温度保持在140-200℃。
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| Application Number | Priority Date | Filing Date | Title |
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| DE10238730.3 | 2002-08-23 | ||
| DE10238730A DE10238730A1 (de) | 2002-08-23 | 2002-08-23 | Verfahren zur Reinigung des Dampferzeugers eines Druckwasserreaktors |
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| CN1669093A true CN1669093A (zh) | 2005-09-14 |
| CN1270835C CN1270835C (zh) | 2006-08-23 |
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| US (1) | US20050126587A1 (zh) |
| EP (1) | EP1532638B1 (zh) |
| JP (1) | JP4309346B2 (zh) |
| KR (1) | KR100689569B1 (zh) |
| CN (1) | CN1270835C (zh) |
| AT (1) | ATE390691T1 (zh) |
| AU (1) | AU2003266996A1 (zh) |
| CA (1) | CA2496682C (zh) |
| DE (2) | DE10238730A1 (zh) |
| ES (1) | ES2301812T3 (zh) |
| RU (1) | RU2316069C2 (zh) |
| UA (1) | UA76650C2 (zh) |
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| CN108780669A (zh) * | 2016-03-16 | 2018-11-09 | 法玛通有限公司 | 用于处理来自金属表面的净化的废水的方法、废水处理装置和废水处理装置的用途 |
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| US7857911B2 (en) * | 2004-04-01 | 2010-12-28 | Asml Netherlands B.V. | Scale conditioning agents and treatment method |
| DE102004054471B3 (de) * | 2004-11-11 | 2006-04-27 | Framatome Anp Gmbh | Reinigungsverfahren zur Entfernung von Magnetit enthaltenden Ablagerungen aus einem Druckbehälter eines Kraftwerks |
| JP4505815B2 (ja) | 2005-07-20 | 2010-07-21 | チカミミルテック株式会社 | 歯列矯正装置 |
| DE102008005199B4 (de) * | 2008-01-18 | 2014-01-23 | Areva Gmbh | Verfahren zur Reinigung eines Wärmetauschers |
| KR101014751B1 (ko) * | 2008-09-26 | 2011-02-15 | 한국전력공사 | 증기 발생기의 화학 세정 방법 |
| FR2950432B1 (fr) * | 2009-09-24 | 2015-06-05 | Electricite De France | Procedes et dispositifs de detection de depots dans les interstices d'une liaison entre un tube et une plaque |
| EP2426322A1 (de) * | 2010-09-06 | 2012-03-07 | Siemens Aktiengesellschaft | Fluid-Kreislauf für eine Kraftwerksanlage und Verfahren zum chemischen Reinigen eines Fluid-Kreislaufs |
| KR101181584B1 (ko) * | 2010-09-28 | 2012-09-10 | 순천향대학교 산학협력단 | 침적 슬러지의 물리화학적 세정방법 |
| CA3029788C (en) | 2015-07-23 | 2021-07-27 | Renmatix, Inc. | Method and apparatus for removing a fouling substance from a pressurized vessel |
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| US3422022A (en) * | 1966-10-27 | 1969-01-14 | Betz Laboratories | Reduced fouling of steam turbines by treatment with sulfur containing compounds |
| CH653466A5 (de) * | 1981-09-01 | 1985-12-31 | Industrieorientierte Forsch | Verfahren zur dekontamination von stahloberflaechen und entsorgung der radioaktiven stoffe. |
| US4632705A (en) * | 1984-03-20 | 1986-12-30 | Westinghouse Electric Corp. | Process for the accelerated cleaning of the restricted areas of the secondary side of a steam generator |
| EP0273182B1 (de) * | 1986-12-01 | 1991-07-31 | Siemens Aktiengesellschaft | Verfahren zum Reinigen eines Behälters |
| EP0355628B1 (de) * | 1988-08-24 | 1993-11-10 | Siemens Aktiengesellschaft | Verfahren zur chemischen Dekontamination der Oberfläche eines metallischen Bauteils einer Kernreaktoranlage |
| DE4114951A1 (de) * | 1991-05-08 | 1992-11-12 | Siemens Ag | Verfahren zum aufloesen von eisenoxiden und loesungssubstanz dafuer |
| DE4131766A1 (de) * | 1991-09-24 | 1993-03-25 | Siemens Ag | Verfahren zur dekontamination des primaerkreises eines kernkraftwerkes |
| EP0674024B1 (en) * | 1994-03-17 | 1998-12-16 | Calgon Corporation | Method for controlling and removing solid deposits from a surface of a component of a steam generating system |
| US5814204A (en) * | 1996-10-11 | 1998-09-29 | Corpex Technologies, Inc. | Electrolytic decontamination processes |
| FR2764364B1 (fr) * | 1997-06-05 | 1999-09-03 | Framatome Sa | Procede de nettoyage d'un generateur de vapeur d'un reacteur nucleaire refroidi par de l'eau sous pression |
| CA2333215C (en) * | 1998-05-22 | 2008-04-01 | Siemens Aktiengesellschaft | Method for cleaning a container |
| DE19857342A1 (de) * | 1998-12-11 | 2000-02-17 | Siemens Ag | Verfahren zum Reinigen eines Behälters |
-
2002
- 2002-08-23 DE DE10238730A patent/DE10238730A1/de not_active Withdrawn
-
2003
- 2003-08-19 ES ES03747911T patent/ES2301812T3/es not_active Expired - Lifetime
- 2003-08-19 CA CA2496682A patent/CA2496682C/en not_active Expired - Fee Related
- 2003-08-19 DE DE50309481T patent/DE50309481D1/de not_active Expired - Lifetime
- 2003-08-19 WO PCT/EP2003/009171 patent/WO2004019343A1/de active IP Right Grant
- 2003-08-19 UA UAA200501577A patent/UA76650C2/uk unknown
- 2003-08-19 JP JP2004530205A patent/JP4309346B2/ja not_active Expired - Fee Related
- 2003-08-19 RU RU2005108068/06A patent/RU2316069C2/ru not_active IP Right Cessation
- 2003-08-19 AU AU2003266996A patent/AU2003266996A1/en not_active Abandoned
- 2003-08-19 CN CNB038169649A patent/CN1270835C/zh not_active Expired - Fee Related
- 2003-08-19 AT AT03747911T patent/ATE390691T1/de not_active IP Right Cessation
- 2003-08-19 EP EP03747911A patent/EP1532638B1/de not_active Expired - Lifetime
- 2003-08-19 KR KR1020057003009A patent/KR100689569B1/ko not_active IP Right Cessation
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2004
- 2004-12-21 ZA ZA2004/10261A patent/ZA200410261B/en unknown
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108780669A (zh) * | 2016-03-16 | 2018-11-09 | 法玛通有限公司 | 用于处理来自金属表面的净化的废水的方法、废水处理装置和废水处理装置的用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2496682A1 (en) | 2004-03-04 |
| ZA200410261B (en) | 2005-09-28 |
| WO2004019343A1 (de) | 2004-03-04 |
| AU2003266996A1 (en) | 2004-03-11 |
| EP1532638A1 (de) | 2005-05-25 |
| ES2301812T3 (es) | 2008-07-01 |
| RU2316069C2 (ru) | 2008-01-27 |
| EP1532638B1 (de) | 2008-03-26 |
| CA2496682C (en) | 2011-08-23 |
| DE10238730A1 (de) | 2004-03-04 |
| DE50309481D1 (de) | 2008-05-08 |
| JP4309346B2 (ja) | 2009-08-05 |
| CN1270835C (zh) | 2006-08-23 |
| RU2005108068A (ru) | 2006-02-20 |
| KR100689569B1 (ko) | 2007-03-02 |
| UA76650C2 (uk) | 2006-08-15 |
| KR20050058447A (ko) | 2005-06-16 |
| ATE390691T1 (de) | 2008-04-15 |
| US20050126587A1 (en) | 2005-06-16 |
| JP2005536730A (ja) | 2005-12-02 |
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