High temperature corrosion of boiler waterwalls induced by chlorides and bromides. Part 1: Occurrence of the corrosive ash forming elements in a fluidised bed boiler co-firing solid recovered fuel

In waste fired boilers high temperature corrosion has often been attributed to zinc and lead chlorides. In addition, bromine induced high temperature corrosion has been earlier observed in a bubbling fluidised bed (BFB) boiler co-firing solid recovered fuel (SRF) with bark and wastewater sludge. In Part 1 of this work a measurement campaign was undertaken to determine the occurrence of Cl, Br, Zn and Pb in the fuel, in the combustion gases as well as in the deposits on the boiler waterwalls. It was observed that Cl, Br, Zn and Pb originate to a large extent from the SRF, they are vaporised in the furnace, and may form waterwall deposits. This, complemented by fluctuations between oxidising and reducing atmosphere resulted in rapid corrosion of the waterwall tubes. Concentrations of Cl, Br, Zn and Pb in the fuel, in the furnace vapours and in the deposits are reported in this work. As there is lack of published data on the bromine induced high temperature corrosion, laboratory scale corrosion tests were carried out to determine the relative corrosiveness of chlorine and bromine and these results will be reported in Part 2 of this work. Furthermore, the forms of Cl, Br, Zn and Pb in the combustion gases as well as in the waterwall deposits were estimated by means of thermodynamic equilibrium modelling and these results will also be discussed in Part 2.     

Degradation of alumina refractory bricks by sintering Mn low-alloy steels

The economic importance of the corrosion and wear of refractory materials is indisputable because these processes determine the viability of any high-temperature liner used in metallurgical processes. The degradation mechanism of lining materials (refractory bricks) in contact with corrosive gases can be studied by examining the penetration rate or the chemical corrosion that results from the circulation of the atmosphere over the refractory material (by diffusional and convective transport). During the sintering of steel containing Mn, the high vapour pressure of Mn enables its sublimation during thermal cycling; therefore, Mn is incorporated into the sintering atmosphere. Although the diffusion of Mn in steel samples is beneficial, the presence of Mn in a sintering atmosphere can modify the composition of refractory components. As a result of atmosphere-refractory interactions, a new phase is formed. In this study, the changes in refractory materials as a function of exposure time to atmospheres containing Mn_(g) at the most common sintering temperature, 1120 °C, were investigated. The microstructural changes in the refractory materials and the consequences of the presence of Mn_(g) were analysed using optical microscopy, electron microscopy with X-ray (EDS) microanalysis, X-ray diffraction, and X-ray fluorescence (XRF).     

TP316L在模拟生物质锅炉过热器气相和积灰条件下的腐蚀特性

Corrosion behavior of TP316L was investigated with simulated atmosphere and ash deposition for the superheater in biomass boiler. Corrosion dynamic curves were plotted by mass gain. The results showed that the corrosion was dependent on temperature and was greatly accelerated by ash deposition. The mass gain was distinctly reduced in the presence of SO2 with and without ash deposition on the specimens. Corrosion rates with ash deposit at different temperatures were calculated. Two feasible methods were provided to avoid serious high-temperature corrosion in the biomass boiler.     

Effect of Moisture on the High-Temperature Stability of Unidirectionally Solidified Al2O3/YAG Eutectic Composites

The corrosion resistance of a unidirectionally solidified alumina/yttrium aluminum garnet (Al₂O₃/YAG) eutectic mixture was investigated at high temperature. Samples were exposed to high temperature (1200°–1800°C) in different atmospheres, which included argon, argon/water vapor, air, and air/water vapor. The most important microstructural changes occurred at the interface between the YAG and the Al₂O₃. Those changes consisted of localized thermal grooving, especially when the corrosive atmosphere contained water vapor. The samples exhibited significant weight loss at high temperature (1800°C) after 20 h of exposure. The calculated volume gain that was induced by the increased surface relief was low and limited, except when the corrosive atmosphere contained air, which indicated that the presence of air (particularly oxygen) induced a more-active corrosion process. On the other hand, no change in the flexural strength was observed, even after 100 h at 1800°C in a humid atmosphere, because of the cross-linked structure of the composite, which limited propagation of the groove.     

Effect of different reaction atmospheres on the sintering temperature of Jincheng coal ash under pressurized conditions

The sintering temperature of coal ash is studied to further understand ash behavior. The objective of this study is to obtain a detailed understanding of the effect of the reaction atmospheres on the sintering temperature under elevated pressure. A series of experiments and analyses have been completed using a pressurized pressure-drop measuring device and X-ray diffractometer (XRD) analyzer. The results show that the sintering temperatures decline markedly under all reaction atmospheres with the rise in pressure. The pressure influences the sintering temperatures by affecting the reaction rate and the mineral transformations undergone by the coal ash, as observed from the XRD patterns. The sintering temperatures measured under the reducing reaction atmospheres are lower than those for oxidizing atmospheres. The sintering temperature under N₂ is lower than those under other oxidizing atmospheres. The sintering temperature under the gasification atmosphere is close to those under H₂ and CO atmospheres, whereas the sintering temperature under a H₂ atmosphere is lower than that under a CO atmosphere.     

Effect of carbon black on corrosion resistance of Al2O3–SiC–C castables to SiO2–MgO slag

Metallurgical solid waste recycling is the shape of things to come in green development of Chinese iron and steel industry. Utilization of ironworks slag for producing mineral wool at high temperature is an important approach. However, refractory lining is seriously corroded by the SiO₂–MgO based slag at 1600 °C during the production process. Different production steps need different atmospheres, the changeable service atmospheres (air and reducing atmosphere) put forward high requirements for slag resistance. The Al₂O₃–SiC–C castables containing carbon black are usually used in iron runner, which faces high-temperature service condition of 1450 °C–1500 °C. Nevertheless, the function of carbon black in the Al₂O₃–SiC–C castables at 1600 °C is till essentially unknown. In the current study, the carbon black was introduced to tabular alumina based Al₂O₃–SiC–C castables to improve corrosion resistance to SiO₂–MgO based slag at 1600 °C. The result showed that 0.4 wt% carbon black was suitable for the castables, which the slag resistance of castables was significantly improved. The carbon black had contributed to block slag by wettability resistance. By comparison with the castables without carbon black, the corrosion index and penetration index had been reduced by 20.2% and 28.0%, respectively, under air atmosphere. And there were little corrosion or penetration under reducing atmosphere for castables with 0.4 wt% carbon black. For the mechanical properties, the Al₂O₃–SiC–C castables with 0.4 wt% carbon black could serve production process although the carbon black impaired the physical properties.     

Influence of the Environment on the Atmospheric Corrosion of Bronze

This paper presents a comparative study of the atmospheric corrosion of bronze samples exposed for 12 months, at two sites: an urban atmosphere with intense traffic, in the city of Lisbon, and a rural marine atmosphere, Cabo da Roca, with a high degree of humidity, strong winds and high levels of chlorides all the year round. Exposures were started in the summer. Levels of SO₂, NO₂ and chlorides, in both atmospheres, were measured during the period of exposure. Climatic data for both sites was also collected and analysed. Weight losses and weight gains of samples with 4, 6, 8 and 12 months of exposure were measured and the average corrosion rates calculated. Chemical composition and morphology of the patinas formed during the exposure period, at both sites, were compared as well as the morphology of the corroded surfaces. Significant differences, related to the level of pollutants and meteorological variables, were found.     

Oxidation and Corrosion of SiC(particulate)/Al/Al2O3 Composites in Sodium Silicate at Elevated Temperatures

Ceramic-matrix composites (CMCs) fabricated by the directed metal oxidation process (Dimox^TM) may have applications in heat exchangers in high-temperature corrosive environments such as those in the glass industry. The oxidation and corrosion properties of such CMCs with and without preformed metal-free surface layers have been investigated in the temperature range of 1000–1300°C. The untreated CMCs experienced rapid oxidation in air leading to mass increases of 100 to 140 mg/cm² in less than 1 h. This occurred by oxidation of residual metal in the composite to form Al/Al₂O₃ deposits on the surface. After the initial formation of the oxidation product, there is little further reaction during up to 300-h exposures to oxidizing atmospheres. Experimental composite coupons with metal-free surfaces were resistant to oxidation except for localized events associated with flaws. Small amounts of sodium silicate (2 to 40 mg/cm²) painted on the surfaces produced no corrosive effects on any of the specimens. Dynamic corrosion experiments, in which a continuous mist of sodium silicate was sprayed onto the surfaces, produced corrosion at 1300°C.     

Application of electrochemical noise to evaluate outdoor atmospheric corrosion of copper after relatively short exposure periods

This study focused on the application of electrochemical noise to assess the protection level of corrosion products formed on copper during relatively short exposure time in different outdoor atmospheres. Electrochemical noise, cathodic reduction measurements and gravimetric (mass loss) analysis were applied to copper samples exposed at urban and rural/industrial areas in Cuba for 4 months. Measurements of Electrochemical current noise indicated that the poorest protective corrosion products were formed on samples exposed to atmospheres with high concentration of H₂S which agreed with the corrosion rate determined by mass loss and electrochemical chronopotentiometry (cathodic reduction). The electrochemical noise methodology proposed in this work showed acceptable and reproducible results by using an electrochemical cell in which the electrolyte was formed by a distilled-water wetted cloth in contact with the compounds present on a corroded metallic surface. This methodology indicated that the corrosion protection level of the corrosion products formed on copper is related to the corrosivity of the atmosphere.     

Hot Corrosion of Stabilized Zirconia Thermal Barrier Coatings and the Role of Mg Inhibitor

The 3–4 mol% yttria‐stabilized zirconia (YSZ) is widely used as a material for thermal barrier coating; however, the corrosive constituents present in fuel typically result in mechanical disintegration of YSZ coatings. The 3–4 mol% YSZ coatings with respective porosity of ~3% and ~22% have been undertaken with the objective to compare the hot corrosion behavior in air and sulfur‐rich atmospheres. The coatings are kept in contact with V₂O₅ + MgO powder mixture at 750°C for different dwell times of 24 and 76 h. The samples kept in air have shown intact YSZ layer for both the coatings, whereas a delamination of YSZ layer is observed for high porosity sample kept in sulfur‐rich atmosphere. XRD patterns of all the samples treated in sulfur‐rich atmosphere have indicated a phase transformation in YSZ from tetragonal to monoclinic. However, no such phase transformation has been found for samples treated in air. The V₂O₅‐induced hot corrosion attack on YSZ coating in air has been successfully inhibited by MgO, which forms a thermally stable Mg₃V₂O₈ compound. However, in sulfur‐rich atmosphere, MgO is partially consumed to form sulfates, which allows certain fraction of V₂O₅ to react with Y₂O₃ causing the degradation of top coat.     

T23,T24合金管材在模拟烟气中的高温腐蚀研究(英文)

Candidate materials for water wall of supercritical and ultra-supercritical utility boilers,T23 and T24,were chosen as the experimental samples and exposed to oxidizing atmosphere,reducing atmosphere and oxidizing/reducing alternating atmosphere separately.The corrosion temperature was 450-550?C.The effects of oxygen con-tent and temperature on the corrosion in reducing atmosphere and alternating atmosphere were investigated.The scanning electron microscope(SEM) and energy dispersive spectrometer(EDS) were used to examine the corroded samples.The results show that the corrosion kinetics of T23 and T24 can be described by the double logarithmic equation and parabolic equation respectively.To describe the corrosion of materials accurately it is not sufficient to analyze the macro-mass gain and the macro-thickness of the corroded layer only,but the EDS should be applied to examine the migration depth of corrosive elements O and S.It is revealed that the corrosion becomes more severe when H2S is present in the corrosive gas.S is more active than O,and Cr can reduce the migration of oxygen but not S.The combination corrosion of S and O and pure [S] has a stronger corrodibility than pure H2S.T24 suffers the most severe corrosion at oxygen content of 0.8%.Corrosion is aggravated when the corrosion temperature is above 450 ℃ in the alternating atmosphere.T23 has better corrosion resistance than T24 and W contributes a lot to the corrosion resistance of T23.     

Development of fireside waterwall corrosion correlations using pilot-scale test furnace

Fireside waterwall wastage in a pulverized coal-fired boiler was investigated and the relevant rate correlations were developed for three corrosion mechanisms: gas-phase attack by reduced sulfur species, chlorine-based attack, and unoxidized fuel deposition. Rate correlations were based on the published data and the experiments at a pilot-scale test furnace. The parameters of the correlations include local flue gas composition, flue gas temperature, metal surface temperature, deposition, deposit characteristics, and heat flux. Validation work performed using the same furnace and the different operating conditions provided good agreement between predictions and measurements. The correlations in conjunction with computational fluid dynamics simulation are expected to provide a predictive tool that can optimize the furnace operating conditions to reduce fireside waterwall wastage.     

海上油气田CO_2腐蚀预测模型研究

海上油气田油套管CO_2腐蚀问题日益严重,目前常用的CO_2腐蚀预测模型均是针对碳钢管材提出,海上油田多使用1Cr、3Cr、9Cr、13Cr等管材,所以建立适用于海上腐蚀环境的CO_2腐蚀预测模型,对后期油套管进行优化设计具有重要意义。本文结合现有的模型和渤海区域的具体环境针对不同管材建立了新的海油CO_2腐蚀预测模型,并对实际生产条件进行了模拟实验。将实验结果与各模型预测结果进行对比分析,验证了新模型的可行性,为海上油气井油套管管材优选及安全生产提供了理论依据。     

Viscosity of Amorphous Oxide Scales on SiSiC at Elevated Temperatures

The high-temperature corrosion resistance of non-oxide Si-containing ceramics is governed by the properties of the protecting silica scales, which develop in oxidizing atmospheres. Bilayered scales of about 8 µm total thickness with crystalline and amorphous layers were grown on reaction-bonded SiC (SiSiC) to study viscosity aspects of the scale. As the amorphous layer formed at the free surface, specimens were scale bonded by means of high-temperature compression and thereafter tested in symmetric shear relaxation experiments. With this novel technique the scale viscosity was determined in the range between 920° and 1020°C. The tests revealed a strong temperature dependence with viscosity values between those of pure silica and commercial aluminosilicate glass. The results are discussed in terms of impurities deliberately introduced into the oxidation atmosphere during the formation of the silica scale on SiSiC.     

Corrosion of carbon steel and 18% Cr-8% Ni stainless steels in 23% by weight fluorosilicic acid and 10-30-0 suspension fertilizer with fluorosilicic acid added

Research studies conducted by the Tennessee Valley Authority (TVA) have shown that addition of fluorosilicic acid can improve the physical properties of suspension fertilizers made from monoammonium phosphate (MAP) containing metallic impurities. The experimental data showed that addition of as little as 0.6% fluorine as fluorosilicic acid to a 10-30-0 grade suspension improved its viscosity, pourability, and high-temperature storage and increased the water solubility of the nitrogen and P₂O₅. Because fluorosilicic acid is very corrosive in nature, a series of electrochemical and immersion corrosion tests was conducted to study the effect of fluorosilicic acid on the corrosiveness of 10-30-0 suspension containing fluorosilicic acid. The corrosion tests included exposure of mild steel and several popular austenitic stainless steels under static conditions at both ambient temperature and 130°F. Tests were also made with the corrosion test specimens exposed in fluorosilicic acid (23% by wt). This paper includes results of these corrosion tests.Mention of companies and trade names for processes, equipment, and commercial products does not constitute an endorsement by TVA or the U.S. Government.     

Bromine as an ash forming element in a fluidised bed boiler combusting solid recovered fuel

Plastic materials are the main sources of chlorine in solid recovered fuels (SRF). Chlorine is attributed to be the main initiator of slagging, fouling and corrosion in biomass and waste combustion as it lowers the melting point of ash forming matter and reacts chemically with the heat transfer surface steels. SRF may also contain sources of bromine in the form of brominated flame retardants (BFRs) applied in many plastics and textiles. Results presented in this paper from an experimental campaign at an 80 MW_th bubbling fluidised bed (BFB) boiler show that bromine is behaving in a similar manner as chlorine: bromine was found at the corrosion front in boiler membrane wall tubes, and as water soluble salts in aerosol samples collected from the furnace and electrostatic precipitator (ESP) ash. It is evident from these results and the data in the literature that most of the salts of bromine are, by both their fate and physical and chemical properties, similar to those of chlorine. It can be concluded that it if there is a source of bromine in the fuel corrosive high vapour pressure bromides can be formed analogously to chlorides.     

富氧燃烧技术在锅炉节能方面的应用探讨

介绍了富氧燃烧方式的技术特点,对其节能机理进行了较为详细的阐述,并以某电站300MW电站锅炉为例,采用ASMEPTC4-1998得出了空气和富氧（30%O2/70%CO2）2种气氛下锅炉的热效率,详细计算分析了煤粉在空气气氛和富氧气氛下锅炉各受热面的传热特性。计算结果表明：采用O2/CO2的富氧燃烧技术可大大提高锅炉热效率,且锅炉的辐射吸热量增加、对流吸热量降低,在炉内的辐射受热面积变化不大的情况下,锅炉的对流受热面积降低很多,同时烟气中高浓度的CO2将会降低分离回收CO2的成本。     

Radiochemical study of the corrosion process of some types of carbon steel in acid media

This paper is a study on the kinetic of corrosion of some types of carbon steel; OLC-15, OLC-35, OL-37 and OLC-45 in acid corrosive media; HCl, HClO₃, HClO₄ and H₃PO₄, in various experimental conditions. In order to follow the evolution of the corrosion process, we have used a radiochemical method based on the principle of isotopic dilution. The corrosion process, specific for the systems under study, has been quantitatively described by means of a kinetic parameter called “the degree of resistance of metallic sample against the action of the aggressive medium”. Out of the experimental data, we have noticed that, at each moment, the degree of resistance of each type of steel under study in the acid corrosive solutions with the same concentration, increases in the series:

, whence we have drawn the conclusion that the hydrochloric acid is a much stronger corrosive medium than the chloric, perchloric and phosphoric acids.     

燃煤电站锅炉水冷壁壁面高温腐蚀问题分析与对策

以对冲燃烧方式的电站锅炉水冷壁壁面高温腐蚀问题为研究对象，从腐蚀机理与燃烧特性角度对水冷壁燃烧区域进行腐蚀特性建模分析，研究水冷壁近壁区域还原性和腐蚀性气氛作用下的硫化物型熔盐腐蚀部位分布规律，腐蚀发生严重的区域将集中在两侧墙的燃烧器周围区域、下层冷灰斗区域、上层燃烧器与顶层燃尽风喷口之间的两侧墙中间区域。现场实测数据验证可知，燃煤电站锅炉水冷壁近壁区域在氧浓度极低情况下，H₂S、CO等物质浓度严重超出腐蚀判定指标要求，水冷壁壁面腐蚀严重，腐蚀发生部位与数值模型结果吻合。结合工程经验，给出了水冷壁壁面高温腐蚀防治的具体措施。     

煤在O2/CO2中燃烧的Nox释放规律

利用一维沉降炉,对3种煤在O₂/CO₂和空气两种气氛下燃烧NO_x析出特性进行了比较,分析了炉膛温度、过量空气系数对NO_x生成量的影响,并对O₂/CO₂气氛下NO_x的生成和破坏机理进行了分析.研究发现两种气氛下NO_x都有一个峰值出现,挥发分含量高的煤种峰值靠前, 挥发分含量低的煤种峰值靠后,O₂/CO₂条件下,峰值出现较空气条件下提前且有所下降;空气条件下NO_x的生成量随温度提高较快地增加,而O₂/CO₂气氛中NO_x的生成量随温度变化比较缓慢;在两种气氛下NO_x的峰值均随过量空气系数的增加而增加,高挥发分煤在O₂/CO₂气氛下NO_x峰值低于空气条件下峰值,而低挥发分煤则受影响较小.