An introduction to fireside corrosion experience in the central electricity generating board

This paper briefly reviews CEGB fireside corrosion experience. It first summarises the numbers and operating conditions of the plants, and indicates the range of materials used in the boilers. Experience of furnace wall and superheater/reheater corrosion in coal fired plant is summarised, emphasising the need to “control” fireside corrosion rather than being able to eliminate it, and the importance of more corrosion resistant materials, particularly as coextruded tube. Tube life prediction techniques in use by the CEGB are outlined, and three current areas of research are described.     

Oxidation Behavior of Sputtered DD98M Nanocrystalline Coating at 1000 °C

Increasing the efficiency of coal fired steam power plants is an important contribution towards clean coal power. In fact, new ferritic steels are expected to withstand 325 bar and 650 °C. Moreover, in order to facilitate CO₂ capture oxygen can be used instead of air for combustion (oxycombustion) so that no NO_X emissions are produced. Boiler components, such as superheater tubes, are exposed to both steam and fireside corrosion and at higher temperatures, ferritic steels corrode at very fast rates under both atmospheres. A solution can be found in the use of protective coatings, a number of which, applied by techniques capable of depositing said coatings both on the inner and outer surfaces of tubes, are being studied within nationally and European funded projects. In particular, two new Ni and Cr modified aluminide coatings deposited on P92 by non-line-of-sight hybrid processes have been produced and the preliminary results of on-going laboratory testing, both under oxycombustion model atmospheres as well as under pure steam at 650 °C are promising, in particular those exhibited by the Cr enriched aluminide coating. Moreover, results obtained in a pilot oxycombustion boiler operated by CIUDEN in Leon, Spain are also shown.     

Measurement of Corrosive Gaseous Species in Staged Coal Combustion

A comprehensive fireside corrosion study has been performed to gain further understanding of the corrosion mechanisms operating in coal-fired utility boilers. Nine commercial coals from eight coal mines, representing a wide range of coal chemistry, were selected for this study. Combustion of these coals was carried out in a 160 KW_th pilot-scale combustion facility that closely simulated the actual conditions of staged combustion in utility boilers. During the pilot-scale testing, gas and deposit samples were collected and analyzed online via in-furnace probing through sampling ports at elevations corresponding to the lower furnace and superheater locations. The in-furnace gas measurements identified the coexistence of reducing and oxidizing species in the gas phase, revealing the non-equilibrium nature of the combustion products. The amounts of sulfur and chlorine released to the gas phase as sulfur and chlorine-bearing species in both the reducing and oxidizing zones were linearly proportional to the amount of total sulfur and chlorine in coal, independent of their original forms. Furthermore, thermodynamics and kinetics of the sulfur and chlorine gas-phase and gas–solid reactions were considered. Based on comparison of the calculated and observed results, a new ash deposition mechanism is proposed.     

Fireside Corrosion of Superheater Materials in Coal/Biomass Co-fired Advanced Power Plants

A series of laboratory-based fireside corrosion exposures were conducted to assess the effect of such conditions on superheater/reheater materials at higher than conventional metal temperatures. Controlled atmosphere furnaces combined with the “deposit recoat” test method were used to generate the exposure conditions; the gaseous environment simulated that anticipated from air-firing 20 wt% cereal co-product mixed with a UK coal. The exposures were carried out at 600, 650 and 700 °C with four candidate materials: T92, HR3C and 347HFG steels; nickel-based alloy 625. After the exposures, the samples were examined by SEM/EDX to characterize the damage. Pre- and post-exposure dimensional metrology were used to quantify the metal damage in terms of metal loss distributions. For the austenitic steels, the combined deposit/gas/temperature exposure conditions enabled quantification of the characteristic ‘bell-shaped’ curves (of damage as a function of temperature) for fireside corrosion.     

Recent plant experience and research into fireside corrosion in Japan

The increasing use of heavy oil as a fuel in power stations has given rise to intensified research in the field of fireside corrosion in Japan. The problems which have to be tackled are described in terms of experiences gained in the operation of oil and coal fired boilers. The main types of damage encountered are nonuniform wastage of tubes in connection with carburization. In this context significant interdependences have been found in connection with coal deposition (especially sodium and sulphur contents). On the basis of this experiences and of the results of corrosion tests in the laboratory and in the field it has been found that the measure offering the best prospect for corrosion control might be the use of coextruded tubing which would allow a combination of high corrosion resistance and high creep strength. In addition to that some modified alloys (e.g. Alloy 800 H, CR 30 A or NF709) offer an interesting potential whereby the high chromium content (more than 20%) is the main criterium.     

火电厂锅炉水冷壁管的防腐防磨治理

火电厂锅炉水冷壁管高温腐蚀和磨损与炉膛火焰温度、燃煤的含硫量、烟气与灰粉颗粒的冲蚀密切相关。采用高速电弧喷涂技术，喷涂SCZ16合金，对燃煤含硫量高的锅炉水冷壁管进行表面处理获得了良好的效果，并在多个电厂中推广应用。     

Waste incineration plants in the FRG: Construction,materials, investigation on cases of corrosion

The development and future aspects of waste incineration in Germany are described with emphasis to corrosion problems. The heterogeneity of waste and special components are the cause of higher corrosion risk in comparison with other fuels, e.g. coal. The materials used in waste incineration plants are preferably the same as in fossil fuel fired boilers, namely un- and low-alloyed steels. Constructive measures are used to avoid enhanced corrosion. Examples are given for enhanced fire-side corrosion of evaporator and superheater tubes. Corrosion in the combustion chamber is to about 50% caused by local reducing conditions. At the other 50% chlorine compounds play a decisive role. Corrosion in the superheater area is usually caused by “high temperature chlorid corrosion”.     

Field test corrosion experiments in Denmark with biomass fuels. Part 1: Straw‐firing

In Denmark, straw and other types of biomass are used for generating energy in power plants. Straw has the advantage that it is a “carbon dioxide neutral fuel” and therefore environmentally acceptable. Straw combustion is associated with corrosion problems which are not encountered in coal‐fired plants. The type of corrosion attack can be directly ascribed to the composition of the deposit and the metal surface temperature. A series of field tests have been undertaken in the various straw‐fired power plants in Denmark, namely Masnedø, Rudkøbing and Ensted. Three types of exposure were undertaken to investigate corrosion: a) the exposure of metal rings on water/air cooled probes, b) the exposure of test tubes in a test superheater, and c) the exposure of test tubes in existing superheaters. Thus both austenitic steels and ferritic steels were exposed in the steam temperature range of 450–600°C. The corrosion rates were assessed by precision measurements of material loss and internal corrosion. The corrosion products and course of corrosion for the various steel types were investigated using light optical and scanning electron microscopy. Corrosion mechanisms are discussed in relation to temperature and deposit composition.     

Long‐term exposure of austenitic steels and nickel‐based alloys in lignite‐biomass cofiring

The aim of this study was to assess the long‐term impact that the addition of biomass provokes on superheater materials exposed to fireside corrosion environments. Alloys covering a broad range of commercially available materials were investigated. Their corrosion kinetics under different corrosive deposits and atmospheres was evaluated, and their corrosion products analyzed to deepen understanding of the underlying corrosion mechanisms. Therefore, three nickel‐based alloys and three austenitic steels containing 20–24 wt.% Cr were tested at 650°C for 7,000 hr. The long‐term exposure shows new mechanistic aspects of Type II hot corrosion that were revealed by accelerated material depletion. The formation of Ni–NiS eutectic and the formation of a Cr depleted zone close to the substrate corrosion product interface are indicative of the breakaway occurrence. Differences in the corrosion behavior are related to the balance of Ni, Mo, Co, and Cr and can serve as the material selection argument. The evaluation concluded with the finding that alloys presenting Mo and Ni might be preferentially used in fireside corrosion in the presence of biomass, whereas the use of austenitic steels suffer less corrosion if no biomass is present in the corrosive atmosphere.     

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。     

Fireside corrosion in German fossil-fuel fired power plants. Appearence,mechanism and causes

Fireside corrosion in German fossil fuel-fired boilers is described out of the view of a laboratory engaged with failure analysis. With German boiler design and German fossil fuel ferritic steels can be used for the tubing in the evaporator and superheater section. Corrosion rates, which have to be expected normally are below 10 nm/h for evaporator tubes and below 25 nm/h for superheater tubes. The appearance of corroded tubes is described and discussed in respect of the corrosion mechanism. In the evaporator section enhanced corrosion risk is mainly due to an increased chemical load, namely reducing conditions or chlorine compounds in the combustion products. In the superheater section higher than normal metal temperatures and stresses, by which the integrity of the oxide layer is destroyed, are the most important factors for increased corrosion rates.     

External corrosion in coal-fired boilers: Assessment from laboratory data

The reactions of coal impurity constituents in the flame are discussed in this paper with particular reference to the formation of corrosive deposits on the heat transfer surfaces in boilers. Consideration is given to the factors which make it difficult to give accurate predictions of metal wastage rates in these environments at high temperatures on the basis of laboratory experiments. These difficulties arise from variations in the operating conditions and are particularly problematic for the steam generating tubes which are located in the walls of the combustion chamber. Non-equilibrium reducing conditions can exist in this region and there is a large temperature gradient through the ash deposit and the corrosion scale on the tube surface. Molten sulphate deposits can be formed on the superheater tubes at the highest temperatures, and the temperature gradient again has an important influence on corrosion rates. The nature and concentrations of the coal impurities and also the influence of heat flux therefore have to be taken into account in the prediction of corrosion rates from laboratory data which may frequently have been obtained under isothermal conditions.     

燃煤火电厂锅炉“四管”的高温腐蚀

燃煤火电厂锅炉的高温腐蚀主要发生在受热面的“四 管”,即水冷壁管、过热器管、再热器管和省煤器管.腐蚀的主要类型是硫腐蚀、氯腐蚀、 水蒸汽腐蚀和钒腐蚀.本文综述了燃煤火电厂锅炉存在的典型高温腐蚀现象和机理,并简要 的介绍了一般防腐蚀措施.     

Studies of corrosion in power plant boiler tubes by measurement of oxygen isotopes and trace elements using secondary-ion mass spectrometry

Recent advances in secondary ionization mass spectrometry (SIMS) techniques allow the resolution of differences in the natural abundances of the isotopes of ¹⁸O and ¹⁶O, and their ratio in both conducting and insulating materials. These techniques have been used in this study to measure the oxygen isotope signatures and their spatial distribution in corrosion products formed during high-temperature oxidation of steel boiler tubes from fossil-fuel power plants. The data obtained in this study are interpreted in terms of oxygen isotope fractionation between the available oxygen reservoirs and oxides formed on or within the metal. Results are presented for three different corrosion scenarios: steamside/fireside corrosion, aqueous phosphate corrosion and corrosion due to H₂ damage. Constant, but isotopically depleted values observed in magnetites formed during steamside corrosion and H₂ damage are indicative of interaction with locally derived meteoric water (which constitutes the boiler feed water). In contrast, isotope distributions in maricite (NaFePO₄) suggest equilibrium fractionation between this phase and precursor magnetite. Oxygen isotope patterns in fireside magnetites exhibit a complex zoning that requires at least two isotopically distinct species with significantly different transport rates.     

Danish experience with fireside corrosion

Fireside corrosion has not been a severe problem in Danish power plants. Furnace wall corrosion has only been seen in one unit caused by insufficient control of the burners. High temperature corrosion has only been seen in units, where the final stage of superheater/reheater was placed in gas temperatures above 1300°C or where the difference in tube length was too big. Since 1970 the final stages of superheater and reheater are made of X20 CrMo V 12.1, which has showed excellent behavior. For estimation of the remaining service life of superheater/reheater, they are examined after 100,000 h in service.     

硫铁矿制酸系统余热锅炉二级过热器管失效原因分析

分析了余热锅炉中二级过热器管(材质为12CrMoV)的失效原因,结果表明管子的腐蚀和超温可能与失效过程有关,但管子表面腐蚀是二级过热器管失效的主要原因。 利用X-射线衍射、金相、电子探针、红外、差热分析和化学分析等方法,研究了取自现场的腐蚀产物形貌、化学组份和结构。腐蚀产物主要是Fe_2O_3、Fe_2(SO_4)_3和铁的硫化物。因此腐蚀机制可能是Fe_2(SO_4)_3在高温下分解产生高分压的SO_3所引起的硫化和氧化。在分析结果的基础上,提出了解决这种问题的可能途径。     

二次过热器炉管的腐蚀损伤分析与表征

采用金相检验、扫描电镜、三维视频系统及能谱分析等方法，对350MW火力发电机组经13万h运行后二次过热器炉管内表面严重腐蚀损伤进行了检测与表征。结果表明，该炉管内表面的损伤主要是由水中的氯离子及溶解氧作用下引起的点腐蚀所致，为此提出了相应的预防措施。     

Influence of novel cycle concepts on the high‐temperature corrosion of power plants

The aim to reduce CO₂ emissions has triggered the evaluation of new cycle concepts for power plants. CO₂‐capture concepts are also evaluated to add on new and existing power plants. For combined cycle power plants (CCPP), different cycles are investigated such as integrated gasification (IGCC) or oxy‐fuel firing. Besides the difference in combustion compared to a conventional CCPP, the environmental boundary conditions are changed and will affect the oxidation and corrosion life of the materials in the hot‐gas path of the gas turbine and the heat‐recovery steam generator. For the circulating fluidised bed power plants, the biomass co‐firing and the oxy‐fuel firing are also foreseen for CO₂‐emission reduction. The fireside corrosion of the water walls will be influenced by these concepts and the changed fuel. The corrosion risk has been evaluated for two new power plant concepts: combined cycle with exhaust gas recirculation and pulverised coal‐fired boiler with oxy‐fuel firing. Based on this evaluation, the consequences for the testing conditions and the material selection have been discussed in detail.     

垃圾焚烧电厂过热器腐蚀影响因素及防护涂层研究进展

垃圾焚烧电厂过热器管道的高温腐蚀一直是制约电厂焚烧温度的关键问题,因此研究开发耐高温、耐腐蚀、长寿命的关键服役材料是保证垃圾焚烧炉正常有序运转及安全生产的关键。对近年来垃圾焚烧电厂腐蚀问题的研究现状进行了梳理,对近期垃圾焚烧电厂过热器腐蚀与防护的研究成果进行了综述。首先,从过热器腐蚀影响因素的角度,归纳了焚烧环境中存在氯、硫、温度、水蒸气等诸多因素影响下的腐蚀特点,对各个影响因素下的腐蚀机理进行了概述,氯作为影响腐蚀的关键因素,重点对氯导致腐蚀的活性氧化机理和电化学机理进行了阐述。其次,讨论了应用在过热器表面的涂层制备技术的发展,包括热喷涂、热扩散、堆焊、激光熔覆等,探讨了制备方法,以及应用技术的优缺点。分析了材料成分(Ni、Mo、Cr、Al、Si、Pt等元素)的添加与涂层耐腐蚀性能之间的关系。再次,从焚烧垃圾预处理的角度,进一步讨论前期可通过对垃圾脱水、添加共燃剂等方法,达到脱硫、脱氯的目的,以此降低烟气中硫、氯的含量,减小其对腐蚀的影响。最后,对垃圾焚烧电厂过热器管道材料和涂层的选择进行了总结和展望。     

余热锅炉省煤器管腐蚀原因分析

 对在役使用的余热锅炉省煤器管进行了现场取样,经化学成分分析、机械性能测试,省煤器管束符合材质要求.通过外观检验、壁厚测量、扫描电镜、能谱和X射线衍射,对省煤器管腐蚀原因进行了分析.结果表明,余热锅炉以瓦斯气作为燃料,总硫含量波动大,硫分在燃烧时绝大部分变成了SO2,其中有一部分可进一步氧化成SO3,SO3与水汽作用而在省煤器低温部位凝结成H2SO4.腐蚀产物分析证实蚀坑内腐蚀产物为硫酸铁,管外表面附着物经检测也有其它硫酸盐形式.证实管外表面蚀坑处于易于形成露点的位置管材外表面局部腐蚀是因露点腐蚀造成.露点腐蚀蚀坑深达0.9mm,并已连片出现,难以满足省煤器管使用条件.管内表面腐蚀产物主要为Fe2O3,说明管内表面受除氧水均匀腐蚀. 