石化、火电工业用换热管的腐蚀失效分析及其性能评价
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摘要
换热器是石化、火电、核电等工业领域中用量很大的重要设备之一,换热管则是换热器实现热量交换与传递的核心部件。然而,由于工艺介质的可变性和操作工况的复杂性,例如复合腐蚀、腐蚀与结垢、腐蚀与磨损、腐蚀与冲蚀,以及高温与高压等的交互作用,换热管常会发生过早失效的现象,导致设备整体寿命缩短,经济损失很大,甚至还引发严重的安全事故。基于此,为确保相关换热器的运行安全、防止同类事故的再发生,本文从两个方面展开了一系列的分析和研究：一是结合几个典型的失效案例,对石化装置中重要换热管所发生的过早失效现象开展深入的分析,研究相关的失效机制,提出针对性的预防措施,从而为避免相似工况下在役换热器的过早失效起到借鉴作用；二是针对新一代超超临界及超临界火电机组中用于过热器、再热器等换热管的新型耐热钢材料,特别是最容易产生失效的焊接接头部位,进行了系统的性能评价和分析,从而为在建机组及其换热器的安全可靠性提供实用的实验数据。本论文已开展的研究内容及其成果概述如下：
1.PTA装置干燥机换热管的失效分析
某PTA装置中用于提纯的两台干燥机,使用不久就发现其不锈钢换热列管频繁受到局部腐蚀的影响,部分管子甚至还同时发生管壁减薄加速、以至爆管开裂等过早失效现象。为此,特从列管材质、工艺介质、操作工况以及维护管理等四个方面,对造成以上多种失效行为的主要因素进行了全面分析与界定。根据实验结果,明确了在设备维护时因碱洗操作不当引入的超标氯离子是造成这一系列严重局部腐蚀的根本原因,并深入探讨了相关的腐蚀失效机理。最后,针对各不同失效起因,提出了相应的、行之有效的解决方案和预防措施。通过此案例分析,掌握了相似工况下在役换热管可能引起失效的潜在因素及其对应的失效预防方法,对确保换热器整体的安全稳定运行具有重要的工程应用价值。
2.乙烯装置急冷油／稀释蒸汽换热器管的失效分析
某石化公司乙烯生产装置中,提供高温急冷油与低温工艺水进行热交换以产生稀释蒸汽供热的换热器,运行仅数月就发现大量碳钢换热管表面出现局部腐蚀凹坑,甚至穿孔破裂等失效缺陷。为迅速判明这一过早失效的真正起因,采用包括三维体式显微镜、SEM、EDS、离子色谱仪、ICP-AES、pH值监测仪等多种先进的表征测试仪器,重点对缺陷的宏微观形貌以及工艺介质的化学特性进行了全面的观察与检测分析。结果表明,设备日常操作时因不恰当的投料行为引起的工艺水pH值剧烈波动,进而使得换热管频繁受到点蚀、酸腐蚀、应力腐蚀开裂等失效机制的交互作用,是导致换热管表面产生局部腐蚀缺陷的根本原因。最后,为清晰阐述这一在复杂运行工况下,由各不同腐蚀原理间的复合效应形成的失效机制,特创新地提出了酸／碱交替腐蚀机理,并明确了其失效缺陷形貌、特征尺寸、以及失效机制间一一对应的关系。
3.高压聚乙烯装置循环气体冷却器换热管的失效分析
某高压聚乙烯装置中,为提高乙烯利用率,采用常温工艺水冷却、分离熔融状的乙烯低聚物及其单体。然而由于该循环冷却水系统为敞开式结构,使得水中含有大量从环境中引入的杂质元素,造成水质严重不合格,并由此对循环气体冷却器的正常运行产生影响。据现场调研发现,位于壳程的冷却水已使该夹套式换热器的碳钢内管受到了明显的腐蚀作用,管壁厚度也因此显著减薄,甚至在出口三通处发生了爆管破裂现象。在基本明确了这一由冷却水水质问题引起的失效原因基础上,深入探讨了相关的吸氧腐蚀、缝隙腐蚀、高速水流冲刷磨损等失效原理,及其对换热管造成的动态复合损伤机制。该成果对于在常见的腐蚀与磨损复合环境下服役的换热钢管进行失效机理研究,具有重要的理论参考价值。
4.T91同种钢焊接接头性能研究
对某国产T91铁素体耐热钢焊接接头展开了全面的常、高温性能评价以及微观结构分析,论证了其整体性能完全符合超临界火电机组与核电机组的服役要求。该研究成果对推广国产T91钢具有重要的实际意义与经济价值,也为研究与其成分和组织结构相近的T92钢的同、异种钢焊接接头作了试验基础准备。
5.T92/HR3C异种钢焊接接头结构与性能研究
对主要面向于超超临界火电机组的新型铁素体耐热钢T92与奥氏体耐热钢HR3C的异种钢焊接接头,进行了结构性能综合评定,包括显微组织、常温力学性能、高温持久强度、焊后残余应力分布等,并讨论了它们间的相互关系。其中,在国内外首次报道了该异种接头的高温蠕变断裂数据及其线性拟合方程,且以此大致推算出其在625℃时的最大许用应力σ105625℃约为40MPa,满足在超超临界蒸汽条件下服役的性能要求。本研究成果对普及新型耐热钢管材料,甚至新一代超超临界火电机组都具有极大的科研与经济价值。
Heat exchangers are one of the significant and substantially-used equipments in engineering areas like petrochemical, fossil power, nuclear power, and so on, and the tubes inside them are the most key parts for heat exchanging and transferring. However, owing to the variability of the process media and the complexity of the service conditions, e.g., the interactions between different corrosion mechanisms, corrosion and scaling, corrosion and abrasion, corrosion and erosion, as well as high temperature and high pressure, such heat exchanger tubes are always encountered with premature failures. As a result, the lifetime of the whole equipments would be shortened, great economic losses would be sufferred, and even safety accidents would be engendered. Thus, in order to ensure safe operation of those heat exchangers and avoid recurrence of similar accidents, this thesis will carry out a series of analyses and researches into two aspects. Based on several typical failure incidents, the first part will deeply investigate the premature failure behaviors of the heat exchanger tubes in some important petrochemical plants, and will also study the relevant failure mechanisms and propose the pertinent prevention methods. Achievements of this research will have a reference value for failure prevention of the in-service heat exchangers that operate under similar service conditions. The second part will conduct systematic performance evaluation and analysis on the welded joints, the most-prone-to-failure components, of the novel heat resistant steels that are mainly applied for the heat exchanger tubes like superheater, reheater, etc, in new-generation ultra-supercritical (USC) and supercritical fossil power plants. Results of it will provide practical experimental data for safety and reliability of the under-construction power plants and their heat exchangers. Detailed research contents and results are summarized as follows:
1. Failure analysis of heat exchanger tubes in PTA dryers
The stainless steel heat exchanger tubes of the two dryers that were used for purification in one PTA plant were frequently encountered with localized corrosions not long after beginning of service, and some of them were also detected other failure modes involving accelerated thinning of their wall thickness and even bursting. Consequently, in order to ascertain the main causes of these premature failure behaviors, comprehensive investigations into four aspects were then carried out, including matrix materials, process media, service conditions, and maintenance management. According to the analysis results, the overproof chloride ions introduced by the inappropriate operation in alkali washing procedure during routine maintenance were determined as the root cause of those serious localized corrosions as pitting and crevice corrosion. Subsequently, the relevant corrosion failure mechanisms were deeply discussed, and both the effective pertinent countermeasures and the prevention measures were put forward as well. Based on this incident analysis, the initiating factors and prevention methods of potential failures of the heat exchanger steel tubes operating under similar service conditions were commanded, which would play an important role in safe and smooth operation of the whole heat exchangers in engineering applications.
2. Failure analysis of quench oil/diluted steam heat exchanger tubes in ethylene plant
In the ethylene manufacturing plant of one petrochemical works, failure defects like localized concaves and even perforation were detected just after several months' service on the surfaces of most carbon steel tubes of the quench oil/diluted steam heat exchangers that were used for generating diluted steam to supply heat. So as to immediately determine the actual causes of this premature failure, a series of advanced characterization apparatus including3D stereo microscope, SEM, EDS, ion chromatograph, ICP-AES, and pH inspection device, etc were utilized to observe the macro/microscopic morphologies of the defects and analyze the chemical features of the process media. The results showed that the interaction among pitting corrosion, acidic corrosion, stress corrosion cracking because of the frequent sharp fluctuations of the process water pH values that were led by the inappropriate feeding methods during routine operation, was the root cause of the localized defects on tubes'surfaces. Furthermore, aiming to clearly illustrate the combined effects by such complicated corrosion modes, a novel 'acidic/caustic alternating corrosion' mechanism was innovatedly put forward, and its concrete relationships among defect morphologies, featured sizes, and detailed mechanisms were established.
3. Failure analysis of heat exchanger tubes of circulating cooler in high-pressure polyethylene plant
For the sake of enhancing the utilization rate of ethylene, circulating coolers that cooled and separated the melted ethylene oligomers and monomers by using room-temperature process water were applied in one high-pressure polyethylene plant. However, since the circulating cooling water, i.e. the process water system was exposed to the environment, it was inevitably polluted and its quality was seriously decreased, which would consequently affect the normal operation of these coolers. Indeed, the carbon steel inner tubes of one circulating cooler with jacket structure were detected severely corroded by such cooling water in the shell side, and their wall thicknesses were also thinned, and one of them even burst at the tee tube near the outlet. Then, on the basis that these failures were undoubtedly induced by the unqualified process water, the dynamic damaging effects combined by dissolved oxygen corrosion, crevice corrosion, and high-speed erosion that were all engendered by the water was discussed in detail. Achievements of this research would have important reference values for studying failure mechanisms of heat exchanger steel tubes that operate under both corrosive and abrasive conditions.
4. Properties research of T91welded joints
The properties at both room and elevated temperatures, and the microscopic structures of the welded joints of one China-made T91ferritic heat resistant steels were comprehensively evaluated, demonstrating that their overall performances were qualified enough for being applied in supercritical fossil power plants and nuclear power plants nowadays. The results would have both practical and economic values in popularizing the domestically-made T91steels, and had also paved the way for studying the similar and/or dissimilar welded joints of T92steels, which have similar chemical compositions and microstructures as T91.
5. Research on structures and properties of T92/HR3C dissimilar steels welded joints
Comprehensive structural performance evaluation was conducted on the dissimilar steels welded joints between novel T92ferritic and HR3C austenitic heat resistant steels that were mainly applied in the USC fossil power plants, including mirostructures, mechanical properties, creep rupture properties, and residual stresses distribution, etc, and the relationships between them were discussed as well. Among them, the creep rupture data and their linearly fitted equation were the first to be reported at home and abroad. Then, the maximum allowable stress at625℃was accordingly calculated, and the resultant value40MPa was sufficient for serving under current USC conditions. From both the scientific and the economic points of view, results of this study would have significant values in popularizing not only such novel heat resistant steels but also the new-generation USC fossil power plants.
1.PTA装置干燥机换热管的失效分析
某PTA装置中用于提纯的两台干燥机,使用不久就发现其不锈钢换热列管频繁受到局部腐蚀的影响,部分管子甚至还同时发生管壁减薄加速、以至爆管开裂等过早失效现象。为此,特从列管材质、工艺介质、操作工况以及维护管理等四个方面,对造成以上多种失效行为的主要因素进行了全面分析与界定。根据实验结果,明确了在设备维护时因碱洗操作不当引入的超标氯离子是造成这一系列严重局部腐蚀的根本原因,并深入探讨了相关的腐蚀失效机理。最后,针对各不同失效起因,提出了相应的、行之有效的解决方案和预防措施。通过此案例分析,掌握了相似工况下在役换热管可能引起失效的潜在因素及其对应的失效预防方法,对确保换热器整体的安全稳定运行具有重要的工程应用价值。
2.乙烯装置急冷油／稀释蒸汽换热器管的失效分析
某石化公司乙烯生产装置中,提供高温急冷油与低温工艺水进行热交换以产生稀释蒸汽供热的换热器,运行仅数月就发现大量碳钢换热管表面出现局部腐蚀凹坑,甚至穿孔破裂等失效缺陷。为迅速判明这一过早失效的真正起因,采用包括三维体式显微镜、SEM、EDS、离子色谱仪、ICP-AES、pH值监测仪等多种先进的表征测试仪器,重点对缺陷的宏微观形貌以及工艺介质的化学特性进行了全面的观察与检测分析。结果表明,设备日常操作时因不恰当的投料行为引起的工艺水pH值剧烈波动,进而使得换热管频繁受到点蚀、酸腐蚀、应力腐蚀开裂等失效机制的交互作用,是导致换热管表面产生局部腐蚀缺陷的根本原因。最后,为清晰阐述这一在复杂运行工况下,由各不同腐蚀原理间的复合效应形成的失效机制,特创新地提出了酸／碱交替腐蚀机理,并明确了其失效缺陷形貌、特征尺寸、以及失效机制间一一对应的关系。
3.高压聚乙烯装置循环气体冷却器换热管的失效分析
某高压聚乙烯装置中,为提高乙烯利用率,采用常温工艺水冷却、分离熔融状的乙烯低聚物及其单体。然而由于该循环冷却水系统为敞开式结构,使得水中含有大量从环境中引入的杂质元素,造成水质严重不合格,并由此对循环气体冷却器的正常运行产生影响。据现场调研发现,位于壳程的冷却水已使该夹套式换热器的碳钢内管受到了明显的腐蚀作用,管壁厚度也因此显著减薄,甚至在出口三通处发生了爆管破裂现象。在基本明确了这一由冷却水水质问题引起的失效原因基础上,深入探讨了相关的吸氧腐蚀、缝隙腐蚀、高速水流冲刷磨损等失效原理,及其对换热管造成的动态复合损伤机制。该成果对于在常见的腐蚀与磨损复合环境下服役的换热钢管进行失效机理研究,具有重要的理论参考价值。
4.T91同种钢焊接接头性能研究
对某国产T91铁素体耐热钢焊接接头展开了全面的常、高温性能评价以及微观结构分析,论证了其整体性能完全符合超临界火电机组与核电机组的服役要求。该研究成果对推广国产T91钢具有重要的实际意义与经济价值,也为研究与其成分和组织结构相近的T92钢的同、异种钢焊接接头作了试验基础准备。
5.T92/HR3C异种钢焊接接头结构与性能研究
对主要面向于超超临界火电机组的新型铁素体耐热钢T92与奥氏体耐热钢HR3C的异种钢焊接接头,进行了结构性能综合评定,包括显微组织、常温力学性能、高温持久强度、焊后残余应力分布等,并讨论了它们间的相互关系。其中,在国内外首次报道了该异种接头的高温蠕变断裂数据及其线性拟合方程,且以此大致推算出其在625℃时的最大许用应力σ105625℃约为40MPa,满足在超超临界蒸汽条件下服役的性能要求。本研究成果对普及新型耐热钢管材料,甚至新一代超超临界火电机组都具有极大的科研与经济价值。
Heat exchangers are one of the significant and substantially-used equipments in engineering areas like petrochemical, fossil power, nuclear power, and so on, and the tubes inside them are the most key parts for heat exchanging and transferring. However, owing to the variability of the process media and the complexity of the service conditions, e.g., the interactions between different corrosion mechanisms, corrosion and scaling, corrosion and abrasion, corrosion and erosion, as well as high temperature and high pressure, such heat exchanger tubes are always encountered with premature failures. As a result, the lifetime of the whole equipments would be shortened, great economic losses would be sufferred, and even safety accidents would be engendered. Thus, in order to ensure safe operation of those heat exchangers and avoid recurrence of similar accidents, this thesis will carry out a series of analyses and researches into two aspects. Based on several typical failure incidents, the first part will deeply investigate the premature failure behaviors of the heat exchanger tubes in some important petrochemical plants, and will also study the relevant failure mechanisms and propose the pertinent prevention methods. Achievements of this research will have a reference value for failure prevention of the in-service heat exchangers that operate under similar service conditions. The second part will conduct systematic performance evaluation and analysis on the welded joints, the most-prone-to-failure components, of the novel heat resistant steels that are mainly applied for the heat exchanger tubes like superheater, reheater, etc, in new-generation ultra-supercritical (USC) and supercritical fossil power plants. Results of it will provide practical experimental data for safety and reliability of the under-construction power plants and their heat exchangers. Detailed research contents and results are summarized as follows:
1. Failure analysis of heat exchanger tubes in PTA dryers
The stainless steel heat exchanger tubes of the two dryers that were used for purification in one PTA plant were frequently encountered with localized corrosions not long after beginning of service, and some of them were also detected other failure modes involving accelerated thinning of their wall thickness and even bursting. Consequently, in order to ascertain the main causes of these premature failure behaviors, comprehensive investigations into four aspects were then carried out, including matrix materials, process media, service conditions, and maintenance management. According to the analysis results, the overproof chloride ions introduced by the inappropriate operation in alkali washing procedure during routine maintenance were determined as the root cause of those serious localized corrosions as pitting and crevice corrosion. Subsequently, the relevant corrosion failure mechanisms were deeply discussed, and both the effective pertinent countermeasures and the prevention measures were put forward as well. Based on this incident analysis, the initiating factors and prevention methods of potential failures of the heat exchanger steel tubes operating under similar service conditions were commanded, which would play an important role in safe and smooth operation of the whole heat exchangers in engineering applications.
2. Failure analysis of quench oil/diluted steam heat exchanger tubes in ethylene plant
In the ethylene manufacturing plant of one petrochemical works, failure defects like localized concaves and even perforation were detected just after several months' service on the surfaces of most carbon steel tubes of the quench oil/diluted steam heat exchangers that were used for generating diluted steam to supply heat. So as to immediately determine the actual causes of this premature failure, a series of advanced characterization apparatus including3D stereo microscope, SEM, EDS, ion chromatograph, ICP-AES, and pH inspection device, etc were utilized to observe the macro/microscopic morphologies of the defects and analyze the chemical features of the process media. The results showed that the interaction among pitting corrosion, acidic corrosion, stress corrosion cracking because of the frequent sharp fluctuations of the process water pH values that were led by the inappropriate feeding methods during routine operation, was the root cause of the localized defects on tubes'surfaces. Furthermore, aiming to clearly illustrate the combined effects by such complicated corrosion modes, a novel 'acidic/caustic alternating corrosion' mechanism was innovatedly put forward, and its concrete relationships among defect morphologies, featured sizes, and detailed mechanisms were established.
3. Failure analysis of heat exchanger tubes of circulating cooler in high-pressure polyethylene plant
For the sake of enhancing the utilization rate of ethylene, circulating coolers that cooled and separated the melted ethylene oligomers and monomers by using room-temperature process water were applied in one high-pressure polyethylene plant. However, since the circulating cooling water, i.e. the process water system was exposed to the environment, it was inevitably polluted and its quality was seriously decreased, which would consequently affect the normal operation of these coolers. Indeed, the carbon steel inner tubes of one circulating cooler with jacket structure were detected severely corroded by such cooling water in the shell side, and their wall thicknesses were also thinned, and one of them even burst at the tee tube near the outlet. Then, on the basis that these failures were undoubtedly induced by the unqualified process water, the dynamic damaging effects combined by dissolved oxygen corrosion, crevice corrosion, and high-speed erosion that were all engendered by the water was discussed in detail. Achievements of this research would have important reference values for studying failure mechanisms of heat exchanger steel tubes that operate under both corrosive and abrasive conditions.
4. Properties research of T91welded joints
The properties at both room and elevated temperatures, and the microscopic structures of the welded joints of one China-made T91ferritic heat resistant steels were comprehensively evaluated, demonstrating that their overall performances were qualified enough for being applied in supercritical fossil power plants and nuclear power plants nowadays. The results would have both practical and economic values in popularizing the domestically-made T91steels, and had also paved the way for studying the similar and/or dissimilar welded joints of T92steels, which have similar chemical compositions and microstructures as T91.
5. Research on structures and properties of T92/HR3C dissimilar steels welded joints
Comprehensive structural performance evaluation was conducted on the dissimilar steels welded joints between novel T92ferritic and HR3C austenitic heat resistant steels that were mainly applied in the USC fossil power plants, including mirostructures, mechanical properties, creep rupture properties, and residual stresses distribution, etc, and the relationships between them were discussed as well. Among them, the creep rupture data and their linearly fitted equation were the first to be reported at home and abroad. Then, the maximum allowable stress at625℃was accordingly calculated, and the resultant value40MPa was sufficient for serving under current USC conditions. From both the scientific and the economic points of view, results of this study would have significant values in popularizing not only such novel heat resistant steels but also the new-generation USC fossil power plants.
引文
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