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Article(id=1236321544151027759, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236321537146540956, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202412260, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1733328000000, receivedDateStr=2024-12-05, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772691625868, onlineDateStr=2026-03-05, pubDate=1761321600000, pubDateStr=2025-10-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772691625868, onlineIssueDateStr=2026-03-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772691625868, creator=13701087609, updateTime=1772691625868, updator=13701087609, issue=Issue{id=1236321537146540956, tenantId=1146029695717560320, journalId=1210938733613449225, year='2025', volume='54', issue='10', pageStart='1', pageEnd='174', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1772691624199, creator=13701087609, updateTime=1772691865526, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1236322549404070348, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236321537146540956, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1236322549408264653, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236321537146540956, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=126, endPage=132, ext={EN=ArticleExt(id=1236321544444629059, articleId=1236321544151027759, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Effect of dissolved oxygen on deposition rules of corrosion products in orifice of steam generators, columnId=1211002409397129992, journalTitle=Thermal Power Generation, columnName=Power generation technology forum, runingTitle=null, highlight=null, articleAbstract=

The deposition of corrosion products in orifice of the steam generator of high temperature gas cooled reactor (HTGR) in nuclear power units threats to safe operation of the unit seriously. To effectively inhibit the deposition of corrosion products in the orifice, the influence of dissolved oxygen in water on the orifice deposition rate was studied under the simulated water condition in the secondary loop of the HTGR. Moreover, the variation law of ZETA potential with dissolved oxygen in iron solution was also studied. It is found that the deposition rate of corrosion products in the orifice area is extremely sensitive to the dissolved oxygen, it decreases with the increase of dissolved oxygen concentration in water. Secondly, over high pH value is not conducive to the inhibition of orifice deposition, which is mainly due to the effect of dissolved oxygen and pH value on the ZETA potential. The wall current electrokinetic effect plays an important role in the orifice deposition, and increasing the concentration of dissolved oxygen in feed water is an effective method to restrain the orifice deposition and clogging in the steam generator of HTGR.

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高温气冷堆核电机组蒸汽发生器节流孔腐蚀产物沉积严重会威胁机组安全运行，为此，在模拟高温气冷堆二回路水工况条件下，研究了水中溶解氧对节流孔沉积速率的影响，以及水中胶体铁ZETA电位随溶解氧的变化规律。实验结果表明：节流孔区域腐蚀产物的沉积速率对溶解氧非常敏感，其随水中溶解氧质量浓度的增加而降低；其次，过高的pH值不利于节流孔沉积现象的抑制，这主要归因于溶解氧和pH值对胶体铁ZETA电位的影响；壁电流电动效应在节流孔沉积中发挥重要作用，提高给水中溶解氧质量浓度是抑制高温气冷堆蒸汽发生器节流孔沉积和堵塞的有效方法。

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张贵泉（1985），男，博士，高级工程师，主要研究方向为核电机组二回路水化学腐蚀控制技术，。

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张贵泉（1985），男，博士，高级工程师，主要研究方向为核电机组二回路水化学腐蚀控制技术，。

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张贵泉（1985），男，博士，高级工程师，主要研究方向为核电机组二回路水化学腐蚀控制技术，。

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溶解氧对蒸汽发生器节流孔腐蚀产物沉积规律的影响
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张贵泉 1 , 王威 2 , 姚建涛 1 , 龙国军 1 , 吴志军 2 , 贾晶晶 3
热力发电 | 发电技术论坛 2025,54(10): 126-132
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热力发电 | 发电技术论坛 2025, 54(10): 126-132
溶解氧对蒸汽发生器节流孔腐蚀产物沉积规律的影响
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张贵泉1 , 王威2, 姚建涛1, 龙国军1, 吴志军2, 贾晶晶3
作者信息
  • 1.西安热工研究院有限公司，陕西　西安　710054
  • 2.华能核能技术研究院有限公司，上海　200126
  • 3.华能山东石岛湾核电有限公司，山东　荣成　264312

    • 张贵泉（1985），男，博士，高级工程师，主要研究方向为核电机组二回路水化学腐蚀控制技术，。

Effect of dissolved oxygen on deposition rules of corrosion products in orifice of steam generators
Guiquan ZHANG1 , Wei WANG2, Jiantao YAO1, Guojun LONG1, Zhijun WU2, Jingjing JIA3
Affiliations
  • 1.Xi’an Thermal Power Research Institute Co., Ltd., Xi’an 710054, China
  • 2.Huaneng Nuclear Energy Technology Research Institute Co., Ltd., Shanghai 200126, China
  • 3.Huaneng Shandong Shidao Bay Nuclear Power Co., Ltd., Rongcheng 264312, China
出版时间: 2025-10-25 doi: 10.19666/j.rlfd.202412260
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摘要
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高温气冷堆核电机组蒸汽发生器节流孔腐蚀产物沉积严重会威胁机组安全运行，为此，在模拟高温气冷堆二回路水工况条件下，研究了水中溶解氧对节流孔沉积速率的影响，以及水中胶体铁ZETA电位随溶解氧的变化规律。实验结果表明：节流孔区域腐蚀产物的沉积速率对溶解氧非常敏感，其随水中溶解氧质量浓度的增加而降低；其次，过高的pH值不利于节流孔沉积现象的抑制，这主要归因于溶解氧和pH值对胶体铁ZETA电位的影响；壁电流电动效应在节流孔沉积中发挥重要作用，提高给水中溶解氧质量浓度是抑制高温气冷堆蒸汽发生器节流孔沉积和堵塞的有效方法。

高温气冷堆  /  节流孔  /  沉积速率  /  溶解氧  /  电动效应

The deposition of corrosion products in orifice of the steam generator of high temperature gas cooled reactor (HTGR) in nuclear power units threats to safe operation of the unit seriously. To effectively inhibit the deposition of corrosion products in the orifice, the influence of dissolved oxygen in water on the orifice deposition rate was studied under the simulated water condition in the secondary loop of the HTGR. Moreover, the variation law of ZETA potential with dissolved oxygen in iron solution was also studied. It is found that the deposition rate of corrosion products in the orifice area is extremely sensitive to the dissolved oxygen, it decreases with the increase of dissolved oxygen concentration in water. Secondly, over high pH value is not conducive to the inhibition of orifice deposition, which is mainly due to the effect of dissolved oxygen and pH value on the ZETA potential. The wall current electrokinetic effect plays an important role in the orifice deposition, and increasing the concentration of dissolved oxygen in feed water is an effective method to restrain the orifice deposition and clogging in the steam generator of HTGR.

HTGR  /  orifice  /  deposition rate  /  dissolved oxygen  /  electrokinetic effect
张贵泉, 王威, 姚建涛, 龙国军, 吴志军, 贾晶晶. 溶解氧对蒸汽发生器节流孔腐蚀产物沉积规律的影响. 热力发电, 2025 , 54 (10) : 126 -132 . DOI: 10.19666/j.rlfd.202412260
Guiquan ZHANG, Wei WANG, Jiantao YAO, Guojun LONG, Zhijun WU, Jingjing JIA. Effect of dissolved oxygen on deposition rules of corrosion products in orifice of steam generators[J]. Thermal Power Generation, 2025 , 54 (10) : 126 -132 . DOI: 10.19666/j.rlfd.202412260
正文
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根据火电机组运行经验，采用全挥发给水处理的火电机组，极易发生节流孔沉积堵塞从而导致水冷壁爆管事故。华能玉环电厂4台1 000 MW超超临界机组直流炉、国电泰州电厂2台1 000 MW超超临界机组直流炉、华电西塞山电厂2台680 MW国产超超临界机组、淮南平圩电厂2台亚临界机组等，投运初期均陆续发生水冷壁超温导致机组调停消缺和非停事件，这些机组均在水冷壁入口布置了节流孔板[1-4]。节流孔沉积现象主要发生于全挥发给水处理条件下，沉积物主要成分为Fe3O4，研究认为机组运行过程中形成的磁性氧化铁在给水系统中随着温度、压力的变化引起迁移，由于炉水经过水冷壁入口节流孔后流速突然降低，在出口处存在紊流导致铁氧化物沉积。另一部分研究人员则认为，在节流孔板处流速加快导致微小铁离子碰撞吸附，长大后的颗粒铁沉积于节流孔板附件。
在压水堆的特定区域，如堆芯和蒸汽发生器，经常发生节流孔沉积现象。压水堆一回路设备表面沉积的有害腐蚀产物被国外学者称为未识别沉积物（chalk river unidentified deposit，CRUD）。在反应堆堆芯中，燃料棒上的CRUD沉积会导致堆芯轴向偏移异常，从而影响反应堆运行安全；其次，在蒸汽发生器的加速流动区域，如管道支撑板和文丘里流量计上的CRUD沉积，会导致支撑板或文丘里区域堵塞，进而引起热交换器水力性能的整体降低。研究发现[5-8]，在低电导率的高纯度冷却剂条件下，电动效应可能是节流孔腐蚀产物沉积的驱动力。McGrady[9-10]和Cassineri[11-13]等人针对一回路节流孔沉积问题开展了广泛研究，旨在阐明流速、氧化物溶解度和节流孔材料对腐蚀产物沉积的影响。研究发现，在节流孔入口侧和微孔内都有明显的腐蚀产物沉积现象，在接近中性pH值水溶液中，节流孔的径向积聚沉积与金属材料无关，是由腐蚀产物向金属表面的质量传输过程控制的。Cioncolini[14]和Turner[15]等人提出了通过流体动力引起局部压降去除节流孔沉积物的方法，发现通过流动动力诱导产生的局部压降对降低节流孔沉积量有一定作用。
高温气冷堆蒸汽发生器采用直流螺旋管式结构设计，为了有效调节给水流量分配，使二次侧给水流量与换热管束的换热量匹配，在换热管束的入口处加装了节流组件。节流组件材质为Inconel-718镍基合金，设有三级不同孔径节流孔，内径最大不超过3 mm。根据设计规范，高温气冷堆蒸汽发生器入口水温203 ℃，节流组件局部流速达到20 m/s，且二回路给水处理采用还原性全挥发工艺，存在严重的节流孔沉积风险。随着高温气冷堆核电机组投运和运行时间的延长，节流组件发生了严重的腐蚀产物沉积现象，增加了蒸汽发生器进出口压差，导致传热管换热性能降低。
为了从运行控制角度解决高温气冷堆蒸汽发生器节流孔沉积问题，本文在模拟高温气冷堆运行阶段蒸汽发生器二回路水化学环境下，研究了溶解氧质量浓度变化对节流孔腐蚀产物沉积速率的影响规律，为机组水化学参数选择奠定了基础。
1　实验部分
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1.1　实验材料
为了保证实验准确性，实验材料采用与高温气冷堆蒸汽发生器节流组件相同的Inconel-718材质。Inconel-718材质按Φ 9 mm×2 mm尺寸加工成圆盘试样，中心位置加工直径400 μm圆孔，用于模拟节流孔，分别采用200、800、1500号水磨砂纸逐级打磨后抛光，用丙酮擦洗试样表面油污后备用。
1.2　实验方法
节流孔腐蚀产物沉积模拟实验在图1所示实验装置上开展。节流孔模拟试样按照图2所示夹持方式固定，并安装在节流孔腐蚀产物沉积模拟实验装置循环回路上。由加压泵提供给水系统所需的驱动力，使得循环系统达到最大30 L/h的流量，水经过换热中升温至203 ℃后注入节流孔夹持装置内，通过圆盘试样后进行换热、冷却、降压，再回流至储水罐，通过背压阀调节实验压力。节流孔腐蚀产物沉积模拟实验装置设置了pH值、溶解氧、联氨等在线仪表，可实现对水化学参数的实时监测。
实验铁源为自腐蚀生成，总铁质量浓度为50 μg/L。本实验控制节流孔试样中心流速20 m/s，温度203 ℃，压力14 MPa，时间24 h。实验后，采用Quanta400HV型扫描电子显微镜（SEM）对节流孔试样的表面微观形貌进行观察分析。采用D/max-3C型X射线衍射仪（XRD）对节流孔沉积物的物相进行分析，工作条件为Cu靶的Kα（λ=0.1540 6 μm）辐射，管电压为35 kV，管电流为40 mA。
采用动态光散射ZETA电位仪测量不同水质环境下含铁水溶液的ZETA电位，分别研究碱性环境下还原性工况、含氧工况下，胶体铁的ZETA电位值随水质pH值的变化规律，pH值变化范围为9.0~9.8。实验条件为，以自腐蚀铁水溶液为研究对象，总铁质量浓度50 μg/L，氨水调节pH值，还原性工况采用加入联氨进行除氧控制。
2　结果与讨论
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高温气冷堆核电机组投运约1年后，在蒸汽发生器节流组件发现节流孔沉积现象，图3为蒸汽发生器节流孔沉积物的SEM照片。由图3可见，节流孔沉积物整体呈规则的环状结构，半径约为0.8 mm，环状沉积物由细小颗粒堆叠而成，且疏松多孔，在沉积物表面可观察到不规整的径向沟壑，可能是由于环状沉积物受到径向水流的冲刷力，从而产生径向沟壑形貌。这与国内外资料报道的现象一致[16-17]。
图4为高温气冷堆蒸汽发生器节流孔沉积物的XRD谱图。由图4可见，谱图在2θ=18.2°、30.1°、35.8°、43.6°、53.8°衍射角附近检测到归属于Fe3O4的特征衍射峰，证明在还原性水化学工况下高温气冷堆蒸汽发生器节流孔快速生成环状Fe3O4沉积物[18]。其次，在XRD谱中未检测到归属于三氧化铁的衍射特征峰，证明了在还原性给水处理条件下，腐蚀产物主要为亚铁形态。
2.1　水质溶解氧质量浓度对节流孔沉积的影响
在模拟高温气冷堆二回路水化学运行参数基础上，采用圆盘节流孔试样研究了水质溶解氧含量对节流孔沉积的影响规律。实验条件为：温度203 ℃，压力14 MPa，pH值9.3，溶解氧质量浓度分别为2、10、20、30 μg/L，实验时间24 h。图5为不同溶解质量浓度下实验后节流孔试样SEM表征结果。由图5a)可见，在水质含氧量2 μg/L条件下实验24 h后，节流孔进水侧边缘区域发生腐蚀产物沉积现象，呈现半径约为105 μm的环状形貌，为纳米尺寸晶体颗粒堆叠而成，这与图3所示Fe3O4微观形貌基本一致。值得注意的是，沉积物并未与节流孔边缘紧密衔接，存在约5 μm的洁净区，这可能是由于孔口边缘流速急剧增加，导致在高流速下诱导金属氧化物的机械去除[19]。由图5b)可见，当水质溶解氧质量浓度提高至10 μg/L时，节流孔沉积程度显著降低，仅在节流孔周边稀疏分散少量氧化铁颗粒，表明给水中腐蚀产物在节流孔边缘的沉积作用力减弱。提高溶解氧质量浓度至20 μg/L以上时（图5c)），节流孔周边沉积进一步减少甚至未见明显沉积现象，此时节流孔沉积得到有效抑制。继续提高给水溶解氧质量浓度为30 μg/L时（图5d)），圆盘节流孔试样的孔边缘光洁平整。因此，通过调节给水中溶解氧质量浓度对抑制节流孔腐蚀产物沉积具有显著作用，为了有效抑制节流孔沉积现象，在pH值为9.3条件下溶解氧的最优控制质量浓度应不低于20 μg/L。
2.2　pH值对节流孔沉积的影响
pH值是控制给水系统化学腐蚀的重要指标，高温气冷堆二回路主给水pH值设计范围为9.5~9.8，其目的是防止二回路系统流动加速腐蚀引起的设备损坏，同时降低给水中总铁含量。Cassineri等人[20]模拟研究了核电一回路加氢水化学环境下Li质量浓度对节流孔沉积的影响，发现随着Li质量浓度的升高，节流孔沉积物形貌和生成速率显著变化，证明了pH值也是影响节流孔腐蚀产物沉积的重要影响因素。为了进一步探索高温气冷堆二回路水化学控制参数，需要对pH值控制范围进行优化研究。图6为不同pH值下实验后节流孔试样SEM表征结果。实验条件为：温度203 ℃，压力14 MPa，溶解氧质量浓度30 μg/L，实验时间24 h。由图6可见：当水质pH值为9.1~9.3时，节流孔边缘光洁，基体清晰可见，节流孔内壁及边缘区域均未见明显的腐蚀产物沉积现象；当水质pH值为9.5时，距节流孔边缘100 μm处再次出现沉积现象，沉积物呈现无形性形态，表明过高的pH值会促进节流孔沉积。可见，pH值是影响节流孔腐蚀产物沉积的重要影响因素之一，为了有效抑制节流孔沉积应选择合适的pH值范围。
为了深入研究溶解氧和pH值对节流孔沉积的影响，采用动态光散射ZETA电位仪分别对还原工况和含氧工况水环境下含铁水溶液的ZETA电位进行测量，测试曲线见图7。水中溶解态铁是节流组件沉积物的前驱体，在碱性水化学环境中溶解态铁以胶体铁形态分散于水相中。由图7可见，在pH值为8.8~9.8时，水中胶体铁的ZETA电位均为负值，表明胶体铁在该水化学工况下表面带有负电荷，这与文献[21]表征结果一致。在还原工况下，随着pH值的升高，ZETA电位向负电位方向线性偏移，从初始–36.6 mV降至–49.0 mV；对比还原工况和氧化工况ZETA电位变化曲线发现，在氧化工况下，水溶液中胶体铁的ZETA电位整体向正方向偏移，但仍为负电位，其变化范围为–14.8~–33.4 mV，这可能是节流孔沉积速率随着水质含氧量升高而降低的主要原因。
根据上述实验结果，结合国内外文献，推测节流孔腐蚀产物沉积可能遵循壁电流电动效应机理[22-24]。具体来说，在高速流体中金属表面存在双扩散层，节流孔区域产生局部高流速，促进双扩散层部分离子剪切并产生流体电流，随着速度的升高流体电流的大小增加，导致局部电荷不平衡，只能通过金属壁电流的产生来补偿平衡，进而在节流孔边缘和孔内壁分别形成了正极和负极区；水中Fe(OH)2胶体为壁电流提供了电子来源，进而诱导法拉第反应，将水中的Fe(OH)2氧化形成不溶性铁或混合氧化态铁（磁铁矿）。
值得注意的是，提高水质pH值会导致2种对流体电流产生相反影响的现象：一方面在高pH值下水的电导率显著增加，双扩散层厚度减少，从而降低了流体电流的大小[9-10]；另一方面，在高pH值还原性水质中，胶体铁的ZETA电位为负值，且随着pH值的增加电位值进一步向负方向移动，加重了胶体铁与节流孔阳极区的作用力。在含氧工况下胶体铁的ZETA电位明显向正电位方向偏移，这对降低胶体铁与节流孔阳极区的作用力具有积极作用，进而减小壁电流电动效应。这与本实验结论一致，再次验证了壁电流电动效应机理的合理性。在氧化性水质中，当pH值为9.5时再次出现节流孔腐蚀产物沉积现象，主要归因于提高pH值引起的电导率增加对流体电流的降低作用弱于胶体电荷ZETA电位向负方向移动引起的作用力。其次，本文研究发现节流孔道内部未发现沉积现象，沉积物主要集中于孔口边缘，且与节流孔间存在一定的洁净间隙，证明了腐蚀产物沉积不仅受到壁电流电动效应的作用力，同时存在流体诱导机械去除的作用力[19,25]。当壁电流电动沉积作用与机械去除作用力相当或小于后者时，可完全避免节流孔沉积现象。
研究结果表明，提高给水溶解氧质量浓度不低于20 μg/L，降低pH值至9.3，可抑制节流孔沉积，这为高温气冷堆蒸汽发生器节流组件的沉积堵塞问题提供了新的解决思路和技术路线。通过在除氧器下降管位置进行给水加氧，控制流经节流组件给水氧质量浓度，进而有效抑制节流组件腐蚀产物沉积。然而，由于高温气冷堆蒸汽发生器过热段采用Incoloy-800H镍合金传热管，其对溶解氧引起的应力腐蚀极其敏感，因此为了保障核电机组的运行安全，含氧水或含氧蒸汽对蒸汽发生器材质、焊缝等区域的腐蚀影响仍需进一步验证。
3　结论
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高温气冷堆蒸汽发生器节流孔沉积物主要由Fe3O4晶体颗粒沉积堆积形成，集中于节流孔进水侧孔口边缘。水中分散的胶态Fe(OH)2是节流孔沉积物的前驱体，在壁电流电动效应作用下节流孔的边缘氧化形成不溶性铁或混合氧化态铁（磁铁矿）。本文从运行控制角度研究了高温气冷堆蒸汽发生器节流孔沉积问题，通过模拟高温气冷堆运行阶段蒸汽发生器二回路水化学环境，研究了溶解氧质量浓度变化对节流孔腐蚀产物沉积速率的影响规律。
1）随着水质溶解氧质量浓度的变化，胶体铁溶液ZETA电位值发生变化，显著影响胶体铁与节流孔阳极区的作用力，提高水中溶解氧质量浓度对抑制节流孔沉积堵塞具有明显促进作用。
2）随着水质pH值的升高，胶体铁溶液的ZETA电位进一步向负方向偏移，不利于控制节流孔腐蚀产物沉积。控制给水溶解氧质量浓度不低于20 μg/L，降低pH值至9.3，可抑制节流孔沉积，这为解决高温气冷堆蒸汽发生器节流组件的沉积堵塞问题提供了新的解决思路和技术路线。
基金
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  • 中国华能集团有限公司总部科技项目(HNKJ22-H09)
文献
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参考文献 引证文献
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2025年第54卷第10期
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doi: 10.19666/j.rlfd.202412260
  • 接收时间：2024-12-05
  • 首发时间：2026-03-05
  • 出版时间：2025-10-25
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  • 收稿日期：2024-12-05
基金
Science and Technology Project of China Huaneng Group Co., Ltd.(HNKJ22-H09)
中国华能集团有限公司总部科技项目(HNKJ22-H09)
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    1.西安热工研究院有限公司，陕西　西安　710054
    2.华能核能技术研究院有限公司，上海　200126
    3.华能山东石岛湾核电有限公司，山东　荣成　264312
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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