Der wartungsfreie Heißwasser-Boiler. Korreferat zu: Korrosionsschutz an Warmwasserboilern mit duroplastischen Kunststoffen

The maintenance-free hot water boiler. Corrosion protection of hot water boilers with duroplastics The corrosion damage caused by water is different from that caused by air. As there are always, in a hot water boiles boundary areas exposed to these media, the only materials suitable for boiler protection are those meeting the following requirements:

• The protection effect must be independent of the composition of the water.
• The composition of the water must not change in the boiler.
• The boilers concerned must not require maintenance.

But corrosion damage on hot water tanks is not conditioned by the composition of the water alone. There is also a possibility of contact corrosion if, e.g., copper pipes or copper beating elements are connected to galvanized boilers. A hot water boiler made of copper will therefore also suffer corrosion damage if material entrained from steel water piping becomes active. Even galvanization can only be applied at temperatures up to 60°C. Above this temperature iron becomes anodic and will corrode. Experience with boilers protected with the organic material known as Si 14 EG can be summed up as follows:

• 1 The duroplastic material known as Si 14 EG is proof against all types of drinking water approved by the public health authorities.
• 1 Some 15,000 boilers with such protection have now been in operation for five years without requiring maintenance, and without loss of protection effect.
• 1 As the hot water boilers thus protected also remain free from incrustations, the heat transfer, and thus the hot water output, remain constant.
• 1 The price of a hot water boiler made of carbon steel and protected with Si 14 EG is lower than that of a copper boiler of equal capacity.

The report concludes by listing the technical requirements for duroplastic coating: The areas to be protected must be accessible for working and inspection; edges must be chamfered; welds must be coherent and free from shrinking cavities and should be smoothed; pipe connections should welded flush with the boiler surface. The text is accompanied by photographs of duroplastically protected boilers.     

Diagnose von Korrosionsfällen an einer Saturationskolonne für Synthesegas

Diagnosis of case histories from a synthesis gas saturation column The saturation column, made of steel type 1Cr18Ni9Ti (wall thickness: 8 mm), in which the gas is cooled down to 240°C by a water jet and, simultaneously saturated with water vapour, failed after only 3000 hours' operation; the failure was attributable to a damaged footing tube. An analysis of the damaged parts suggested, that the main cause of the failure was not the design of the equidistant shells, i. e. the welding connection between the tubes and the two shells, which had originally been assumed to be faulty, but in a first line the material selection which was wrong in view of possible corrosion. The tensile stresses resulting from the rigid connection of the footing pipes are but one of the factors contributing to the development of stress corrosion cracking. This opinion concerning the reason of the first failure was confirmed when another failure occurred after another 1000 hours' operation of the column: a thorough inspection revealed some spots where stress corrosion cracking bad developed.     

锅炉高压蒸发器管泄漏原因分析

高压蒸发器管发生泄露。采用化学成分、金相、拉伸与能谱等方法对其材质进行鉴定,结果表明材质不是蒸发器管腐蚀泄露的原因。腐蚀形貌与射线检查结果表明:泄漏点主要发生在焊缝附近的热影响区,通过现场工况调查并结合未泄露管化学清洗前后形貌、酸洗模拟试验与内壁沉积物分析,表明内壁腐蚀特征与停用时积水情况有明显对应关系,酸洗过程不会对金属基体造成明显腐蚀损伤,腐蚀主要发生在化学清洗前;采用停用腐蚀模拟试验对现场工况进行还原,其结果与现场实际管子的腐蚀特征基本一致。因此,基建期间部分管子内局部有积水和污物导致发生停用氧腐蚀是本次蒸发器管泄露的主要原因。     

垃圾焚烧发电锅炉高温腐蚀治理的研究进展

垃圾焚烧发电锅炉水冷壁和过热器管壁的高温腐蚀防护是影响垃圾焚烧炉稳定运行的重要因素。 为提高垃圾焚烧炉运行的安全性,研究者从基材选择、施加表面涂层和温度控制等多方面给出了解决方案,以增加受热面金属管道的使用寿命。 在简介了锅炉高温腐蚀原理的基础上,分别评述了余热锅炉水冷壁和过热器高温腐蚀治理方案的研究进展。 在水冷壁高温腐蚀提治理方法中,敷设浇注料往往会造成烟温后移,恶化尾部烟道腐蚀,而在表面涂层防护技术中,感应重熔技术因其涂层缺陷少、结合强度高、稀释率低,表现出了良好的防腐蚀效果。 余热锅炉过热器受到显著的液相熔盐腐蚀,对于该部位的高温腐蚀治理除了提升材料等级外,应当严格控制入口烟温,适当调节燃烧气氛。     

Effects of fuel impurities on the fireside corrosion of boiler tubes in advanced power generating systems—a thermodynamic calculation of deposit chemistry

Thermodynamic equilibrium calculation relating fuel chemistry with flue-gas composition and volatile condensate deposits on tube metals upon combustion of various “dirty” fuel was conducted for a better understanding of the deposit chemistry of superheater tubes in steam-generating boilers. Corrosive impurities such as sodium, potassium, chlorine, and sulfur, inevitably involved in fuel, were considered in the calculation. Possible influence of flue-gas temperature on deposit chemistry was investigated as well.Based on the flue-gas composition and the deposit chemistry, corrosion environments of steam-generating boilers firing various “dirty” fuel were discussed.     

锅炉水冷壁管开裂原因分析

针对某火电厂锅炉水冷壁管开裂情况,通过宏观形貌、材质分析、硬度检测、显微组织检测、扫描电镜、能谱分析和XRD等手段,对水冷壁开裂管进行取样分析。结果表明水冷壁管开裂的原因是氢腐蚀;主裂纹内部和氧化层缝隙存在大量铜,氧化层导热性能差,恶化局部传热,局部热负荷超过一定极限时,大大加速铜在主裂纹处富集,富集的铜元素又加速了裂纹的扩展。     

核电站消防水稳压罐腐蚀分析及处理

稳压罐是核电站用于盛装消防用水,在火灾事故时可以迅速响应,协助完成灭火动作。核电站消防水稳压罐定期检查时,发现稳压罐内部涂层失效,多处腐蚀严重,腐蚀产物附着在罐壁,检查罐底出口阀门及管道同样存在严重腐蚀情况。分析结果表明,发生腐蚀的主要原因为涂层破坏,基体腐蚀均存在闭塞电池腐蚀过程,但各具特点,在实际维护分析中应各有侧重。建议采取更换阀门、修补稳压罐腐蚀坑、重新整体涂刷防腐涂层的方案,防止发生稳压罐腐蚀穿孔,保证消防系统的正常运行。     

在役天然气管道分层缺陷的检测判定

针对输气管道在线检测过程中发现的管壁异常减薄,采用金属磁记忆、声发射、声定位超声波C扫描、数字X射线等系列技术对异常处进行了检测与验证,综合各种检测结果判定该处缺陷为钢管自身冶金缺陷（可能为夹杂类分层缺陷）,不是天然气造成的腐蚀缺陷,在加强监测的情况下该钢管仍可使用。     

乙烯裂解装置炉管焊缝腐蚀失效分析

针对发生失效的乙烯裂解装置炉管焊缝,采用材料化学成分分析、宏观形貌观察、金相检查、扫描电镜和能谱分析等手段进行了失效分析,同时测量了原料油的终馏点,模拟了含焊接缺陷的炉管内的流场。结果表明:焊缝腐蚀区存在大量硫及低熔点共晶物;失效炉管段的介质温度处于加氢尾油的终馏点附近;活性硫在镍基焊缝偏聚,镍与硫形成的低熔点共晶物在高温下熔化,并被介质冲走,导致炉管快速腐蚀。     

Superheater fireside corrosion mechanisms in MSWI plants: Lab‐scale study and on‐site results

Combustion of municipal waste generates highly corrosive gases (HCl, SO₂, NaCl, KCl, and heavy metals chlorides) and ashes containing alkaline chlorides and sulfates. Currently, corrosion phenomena are particularly observed on superheater's tubes. Corrosion rates depend mainly on installation design, operating conditions i.e., gas and steam temperature and velocity of the flue gas containing ashes. This paper presents the results obtained using an innovative laboratory‐scale corrosion unit, which simulates MSWI boilers conditions characterized by a temperature gradient at the metal tube in the presence of corrosive gases and ashes. The presented corrosion tests were realized on carbon steel at fixed metal temperature (400 °C). The influence of the flue gas temperature, synthetic ashes composition, and flue gas flow pattern were investigated. After corrosion test, cross sections of tube samples were characterized to evaluate thickness loss and estimate corrosion rate while the elements present in corrosion layers were analyzed. Corrosion tests were carried out twice in order to validate the accuracy and reproducibility of results. First results highlight the key role of molten phase related to the ash composition and flue gas temperature as well as the deposit morphology, related to the flue gas flow pattern, on the mechanisms and corrosion rates.     

URP系列自动超声波探伤机在无缝钢管生产中的应用

URP系列自动超声波探伤机在钢管高速自动探伤中可一次性同时检测无缝钢管纵、横向缺陷以及壁厚、分层的测量,具有灵敏度高、稳定性好等优点。介绍了URP系列自动超声波探伤机的检测原理、设备结构特点、工艺性能、操作维护要求,以及在无缝钢管生产中的在线应用情况。实践证明,该探伤设备能够满足冶金企业无缝钢管超声波检测的要求。     

Integral diagnostic in the failure causes of external corrosion of a natural gas transport pipeline

The objective of this study consisted in investigating the possible causes which give rise to the presence of low wall pipe thicknesses on a 16″ natural gas transport pipeline, even though during the last 12‐year period cathodic protection (CP) potentials were kept in the protection range at which external corrosion should not occur. Results from in‐line inspection from a 16″ natural gas transport pipeline showed 46 indications with more than 80% wall thickness lost due to external corrosion in the second segment of the pipeline. Direct inspection at the indication locations, review of the CP system performance, pipeline maintenance programs and studies, allowed to make an integral diagnostic where it was found out that the main cause of external corrosion was an inappropriate coating application since the pipeline construction, this situation has originated the increase of CP shielding effects through time.     

Analysis of failed nuclear plant components

Argonne National Laboratory has conducted analyses of failed components from nuclear power- gener-ating stations since 1974. The considerations involved in working with and analyzing radioactive compo-nents are reviewed here, and the decontamination of these components is discussed. Analyses of four failed components from nuclear plants are then described to illustrate the kinds of failures seen in serv-ice. The failures discussed are (1) intergranular stress- corrosion cracking of core spray injection piping in a boiling water reactor, (2) failure of canopy seal welds in adapter tube assemblies in the control rod drive head of a pressurized water reactor, (3) thermal fatigue of a recirculation pump shaft in a boiling water reactor, and (4) failure of pump seal wear rings by nickel leaching in a boiling water reactor. Work supported by Commonwealth Edison Company under ACK 85026.     

Korrosion von ölgefeuerten Zentralheizungskesseln

Corrosion of oil-fired domestic boilers Depending on the surface temperature of the flue gas side the corrosion of oil fired domestic boilers proceeds either mainly by acid corrosion or by oxygen corrosion:

• – At surface temperatures of 60°C and higher the corrosion mechanism of acid corrosion prevails and the corrosion rates amount to 0.1–0.3 mm/year (values referred to continuous burner operation). The corrosion products consist of soluble iron(II)- and iron(III)sulfates. Higher corrosion rates can be attributed to an appreciable catalytic formation of sulfur trioxide on the corrosion products formed on the convective heating surfaces.
• – At surface temperatures of 40°C the mechanism of oxygen corrosion already dominates and the corrosion rates are about ten times higher (1.5–3 mm/year, referred to continous burner operation). The high portion of ioron oxide hydrates, especially goethit (α-FeOOH), makes the corrosion products difficult to remove.
• – Distinctly reduced service lives are also expected for the so called reduced temperature boilers (“Niedertemperaturkessel”) and low temperature boiers (“Tieftemperaturkessel”): According to the manufacturers these boilers may be operated at boiler water temperatures well below 60°C, as they are equipped with constructive measures to enhance the surface temperature on the flue gas side. However, these measures are only fully effective under stationary conditions.

Some of the results were obtained from weight loss measurements on test specimen made from St 35.8 and gray cast iron, that were exposed to the flue gases of an oil fired experimental boiler. Other important results come from field measurements of the sulfuric acid content of about 30 boilers that are in practical use.     

表面蒸发式空冷器管束失效分析与防护研究

目的 查明表面蒸发式空冷器管束失效原因,提出避免再次失效的对策。方法 目测管束失效部位宏观形貌,用金相显微镜得到管束基体的金相组织,用电子显微镜观察管束失效部位的微观形貌,用能仪谱获得管束基体及其失效部位的化学成分等。结果 目测可见失效部位管件表面有红褐色腐蚀产物存在,且管壁减薄非常明显,远离失效部位的管件表面完好;金相显微分析表明,管件基体金相组织与标准20#钢金相组织吻合;电子显微镜观察表明,管壁表面腐蚀产物疏松多孔;能谱分析表明,管件基体化学成分主要缺少了Cr、Ni、Cu这3种合金元素,管壁表面腐蚀产物化学成分由Fe、Zn、O、S组成。结论 Cr、Ni、Cu合金元素的缺失导致了管基体耐蚀性能降低,管程内烃类介质的含硫组分和管壳外换热介质的氧成分成为腐蚀源,电偶效应下的全面腐蚀导致管件基体快速减薄而穿孔泄露。使用化学成分符合国标的20#钢生产管束,并保证管束表面镀锌层的完整性,尽量减少烃类介质的含硫组分和换热介质的氧等含量,可以避免管束再次失效。     

电站锅炉过热器管失效规律研究

过热器管是锅炉受热面中工作环境最恶劣的炉管,频繁地出现由材料断裂造成的泄漏与爆管失效事故,对电力企业造成了严重的经济损失。根据过热器管不同的失效原因,将过热器管的断裂失效分为韧性断裂、脆性断裂、蠕变断裂及腐蚀断裂。通过对过热器管失效实际案例进行分析,建立了过热器管失效树,同时概括了引起失效的损伤因素。为避免在生产过程中出现引起过热器管失效的重要损伤因素,在设计、运行、维护等环节提出了相应的防范措施。     

Development of 25%Cr SMAW welding materials – development of high Cr ferritic overlay welding materials for recovery boiler

In place of the 18%Cr overlay welding material, which has been used for furnace water wall tubes of recovery boilers, a 25%Cr overlay welding material with good corrosion resistance has been newly developed. In consideration of dilution with a carbon steel tube, the Cr content of the new welding materials are designed to be more than 20%Cr. And in order to fine the grains of the weld metal, some elements, such as Nb, Al and Ti, are added to these welding materials. Mainly two types of welding materials, which have Austenite + Martensite + Ferrite of materials for the three-phase and fully ferritic materials, are examined. As results of weldability tests and bending properties, the fully ferritic welding materials are superior to the three-phase materials, respectively. On the point of the corrosion test, which are exposed into some smelt ashes obtained from the recovery boilers, the corrosion rate of the full ferritic material was confirmed to be the about half of that of 18%Cr overlay welding material. The 25%Cr overlay welding material was found to exhibit excellent corrosion resistance. This study introduces the development of 25%Cr ferritic welding material and methods for reliable overlay welding and examines the weldability, the bend property and the corrosion resistance of the 25%Cr overlay welded metal on tube.     

超超临界机组水冷壁高温腐蚀问题的探讨

介绍了国内首台超超临界机组水冷壁发生高温腐蚀的基本情况。对水冷壁管进行外观检查、金相分析和能谱微区成分分析,结果表明,管子外表面存在高温硫腐蚀,对发生腐蚀的原因作了探讨,并提出了预防措施。     

锅炉炉管内壁氧化膜壁厚的测量

介绍了内壁氧化膜测量在锅炉受热面的应用，阐述了锅炉受热面内壁厚层氧化膜测量的原理，对厚层氧化膜测量特例进行了分析，并结合氧化膜测量工程实例对其应用进行了阐述，结果表明，锅炉受热面内壁氧化膜壁厚测量对锅炉的检验与维护有指导意义。     

轿车空调冷凝器泄漏失效分析

某型轿车空调冷凝器在沿海地区使用过程中出现泄漏,通过对失效冷凝器进行气密试验、损伤特征观察分析、金相组织检查以及能谱成分分析等试验,对冷凝器泄漏失效的原因进行了分析.结果表明,空调冷凝器泄漏失效是山于铝扁管形成了穿透性的腐蚀坑所致,高盐下湿交替的环境和维护不当是形成腐蚀失效的主要原因,铝扁管中杂质元素的存在加速了轿车空调冷凝器的腐蚀失效.