The combustion of coal and biomass fuels in power plants generates deposits on the surfaces of superheater / reheater tubes that can lead to fireside corrosion. This type of materials degradation can limit the lives of such tubes in the long term, and better methods are needed to produce predictive models for such damage. This paper reports on four different approaches that are being investigated to tackle the challenge of modelling fireside corrosion damage on superheaters / reheaters: (a) CFD models to predict deposition onto tube surfaces; (b) generation of a database of available fireside corrosion data; (c) development of mechanistic and statistically based models of fireside corrosion from laboratory exposures and dimensional metrology; (d) statistical analysis of plant derived fireside corrosion datasets using multi-variable statistical techniques, such as Partial Least Squares Regression (PLSR). An improved understanding of the factors that influence fireside corrosion is resulting from the use of a combination of these different approaches to develop a suite of models for fireside corrosion damage.

The Advanced Ultrasupercritical (A-USC) power plants are aimed to operate at steam inlet temperatures greater than 700°C; consequently, a complete materials overhaul is needed for the next-generation power plants. HAYNES 282, a gamma-prime strengthened alloy, is among the leading candidates because of its unique combination of properties, superior creep and LCF strength, fabricability and thermal stability. It is currently being evaluated in wrought and cast forms for A-USC turbine rotors, casings, boiler tubings, header, and valves. The candidate materials for A-USC applications not only require oxidation resistance for steam cycles but fireside corrosion resistance to coal ash is also of an extreme importance. In order to study the effect of both environments on the performance of 282 alloy, the alloy was exposed for extended periods in various oxidizing environments, such as air, air plus water vapor (10%), and 17bar steam up to 900°C. The fireside corrosion resistance of 282 alloy was evaluated at 700°C in synthetic coal ash and at 843°C in alkali salt deposits in a controlled gaseous environment.

Nickel-based alloys and stainless steel Super304H, along with various coatings, are undergoing testing in a steam loop at Alabama Power’s Plant Barry. These materials are being evaluated for use in advanced ultra-supercritical (A-USC) fossil-fired power plants at temperatures ranging from 538°C to 815°C. The loop has been operational for over 18 months, with the alloys exceeding 6,300 hours above 538°C. An additional 7,000 hours at high temperatures are planned before the loop’s removal in 2014. Initial inspections show minimal material corrosion, suggesting their suitability for A-USC applications. This paper details the loop’s design, materials, manufacturing, operation, and inspection findings. Additionally, it describes a methodology for predicting steam-side oxidation and fireside corrosion rates and highlights the significance of this testing for A-USC development and commercialization.

Oxyfuel combustion is considered as one of the most promising technologies to facilitate CO 2 capture from flue gases. In oxyfuel combustion, the fuel is burned in a mixture of oxygen and recirculated flue gas. Flue gas recirculation increases the levels of fireside CO 2 , SO 2 , Cl and moisture, and thus promotes fouling and corrosion. In this paper the corrosion performance of two superheater austenitic stainless steels (UNS S34710 and S31035) and one Ni base alloy (UNS N06617) has been determined in laboratory tests under simulated oxyfuel conditions with and without a synthetic carbonate based deposits (CaCO 3 - 15 wt% CaSO 4 , CaCO 3 - 14wt% CaSO 4 - 1 KCl) at 650 and 720°C up to 1000 hours. No carburization of the metal substrate was observed after exposure to simulated oxyfuel gas atmospheres without deposit, although some carbon enrichment was detected near the oxide metal interface. At 720°C a very thin oxide formed on all alloy surfaces while the weight changes were negative. This negative weight change observed is due to chromium evaporation in the moist testing condition. At the presence of deposits, corrosion accelerated and considerable metal loss of austenitic alloys was observed at 720°C. In addition, clear carburization of austenitic steel UNS S34710 occurred.

Using oxygen, rather than air, in coal-fired boilers has been studied for several years as a strategy to reduce NOx and concentrate CO 2 for capture. In combination with flue gas recirculation, higher levels of CO 2 are expected but increased H 2 O and SO 2 levels also may occur. In order to understand the role of substrate composition on corrosion, a combination of commercial and model alloys were investigated with synthetic coal ash and gas compositions simulating air- and oxyfiring environments. Exposure temperatures ranged from 600°-800°C to cover current operating temperatures up to advanced ultrasupercritical conditions. Using 500h exposures, no consistent negative effect was found for switching to the oxy-firing environment with the same synthetic ash. For model Fe-Cr alloys, 30%Cr was needed to form a thin protective reaction product across this temperature range. Among the commercial stainless steels, 310-type stainless steel showed low reaction rates with the maximum attack at 650°C. At higher temperatures, the depth of attack on Fe-base type 310 stainless steel was less than for Ni-base alloy 740. Initially, this difference was attributed to the Al and Ti additions in alloy 740. However, cast and hot rolled model Ni-18Cr and -22Cr alloys with various Al and Ti additions showed decreased metal loss with increasing Al and Ti additions in the oxy-firing environment at 700° and 800°C. As expected, metal loss was very sensitive to Cr content. A second set of model alloys also examined the effect of Co and Mo.

Recent advances in materials technology for boilers materials in the advanced USC (A-USC) power plants have been reviewed based on the experiences from the strengthening and degradation of long term creep properties and the relevant microstructural evolution in the advanced high Cr ferritic steels. P122 and P92 type steels are considered to exhibit the long term creep strength degradation over 600°C, which is mainly due to the instability of the martensitic microstructure strengthened too much by MX carbonitrides. This can be modified by reducing the precipitation of VN nitride and by optimizing the Cr content of the steels. An Fe-Ni based alloy, HR6W strengthened by the Fe2W type Laves phase is found to be a marginal strength level material with good ductility at high temperatures over 700°C and to be used for a large diameter heavy wall thick piping such as main steam pipe and hot reheat pipe in A-USC plants, while Ni-Co based alloys such as Alloys 617 and 263 strengthened by a large amount of the y’ phase are found to be the high strength candidate materials for superheater and reheater tubes, although they are prone to relaxation cracking after welding and to grain boundary embrittlement during long term creep exposure. A new Ni based alloy, HR35 strengthened by a-Cr phase and other intermetallic phases has been proposed for piping application, which is specially designed for a good resistance to relaxation cracking as well as high strength and a good resistance to steam oxidation and fire-side corrosion at high temperatures over 700°C.

In the “Boiler Materials for Ultrasupercritical Coal Power Plants” program, sponsored by the U.S. Department of Energy and the Ohio Coal Development Office, various materials are being assessed for their suitability in the high-temperature, high-pressure environment of advanced ultrasupercritical (A-USC) boilers. Beyond mechanical properties and fireside corrosion resistance, these materials must also exhibit adequate steamside oxidation and exfoliation resistance. A comprehensive database of steamside oxidation test results at temperatures relevant to A-USC conditions has been compiled over recent years. These tests have been conducted on ferritic and austenitic materials with chromium content ranging from 2 to 26%. The specimens were evaluated for oxidation kinetics and oxide morphology. The findings indicate that steamside oxidation behavior is significantly affected by temperature, the chromium content of the material, and the ability of chromium to diffuse through the material's crystallographic lattice structure. Additionally, surface treatments have been applied to enhance the steamside oxidation resistance of certain materials. While these treatments have shown potential, their effectiveness can be limited by the operational temperatures.

This paper outlines a comprehensive UK-based research project (2007-2010) focused on developing fireside corrosion models for heat exchangers in ultra-supercritical plants. The study evaluates both conventional materials like T22 and advanced materials such as Super 304H, examining their behavior under various test environments with metal skin temperatures ranging from 425°C to 680°C. The research aims to generate high-quality data on corrosion behavior for materials used in both furnace and convection sections, ultimately producing reliable corrosion prediction models for boiler tube materials operating under demanding conditions. The project addresses some limitations of existing models for these new service conditions and provides a brief review of the fuels and test environments used in the program. Although modeling is still limited, preliminary results have been presented, focusing on predicting fireside corrosion rates for furnace walls, superheaters, and reheaters under various service environments. These environments include those created by oxyfuel operation, coal-biomass co-firing, and more traditional coal firing.

A comprehensive fireside corrosion study was undertaken to better understand the corrosion mechanisms operating on the superheaters and lower furnace walls of advanced coal- fired utility boilers. The study intended to evaluate the fireside conditions generated from burning eight U.S. coals individually in a pilot-scale combustion facility. These coals consisted of a wide range of compositions that are of interest to the utility industry. The combustion facility was capable of producing the realistic conditions of staged combustion existing in coal-fired utility boilers. During each of the combustion tests, gas and deposit samples were collected and analyzed via in-furnace probing at selected locations corresponding to the waterwalls and superheaters. Testing of five of the eight coal groups has been completed to date. Results of these online measurements helped reveal the dynamic nature of the combustion environments produced in coal-fired boilers. Coexistence of reducing and oxidizing species in the gas phase was evident in both combustion zones, indicating that thermodynamic equilibrium of the overall combustion gases was generally unattainable. However, the amount of sulfur released from coal to form sulfur-bearing gaseous species in both the reducing and oxidizing zones was in a linear relationship with the amount of the total sulfur in coal, independent of the original sulfur forms. Such a linear relationship was also observed for the measured HCl gas relative to the coal chlorine content. However, the release of sulfur from coal to the gas phase appeared to be slightly faster and more complete than that of chlorine in the combustion zone, while both sulfur and chlorine were completely released and reacted to form respective gaseous species in the oxidizing zone. The information of sulfur and chlorine release processes in coal combustion generated from this study is considered new to the industry and provides valuable insight to the understanding of fireside corrosion mechanisms.

The Department of Energy and Ohio Coal Development Office jointly sponsored research to evaluate materials for advanced ultrasupercritical (A-USC) coal power plants, testing both monolithic tube materials and weld overlay combinations under real operating conditions. Testing was conducted in the highly corrosive, high-sulfur coal environment of Reliant Energy's Niles Plant Unit 1 boiler in Ohio. After 12 months of exposure, researchers evaluated six monolithic tube materials and twelve weld overlay/tube combinations for their high-temperature strength, creep resistance, and corrosion resistance in both steam-side and fire-side environments. Among the monolithic materials, Inconel 740 demonstrated superior corrosion resistance with the lowest wastage rate, while EN72 emerged as the most effective weld overlay material across various substrates, offering consistent protection against corrosion.

Coal ash corrosion testing was conducted on six solution-treated nickel-based alloy plates (Alloy 617, Alloy 263, Alloy 740, Alloy 141, HR6W [45Ni-23Cr-7W], and HR35 [50Ni-30Cr-4W-Ti]) intended for advanced-USC boilers, along with conventional ferritic and austenitic stainless tubes for comparison. Tests used synthetic coal ash (Na 2 SO 4 , K 2 SO 4 , Fe 2 O 3 ) with varying SO 2 concentrations (0.02-1.00 vol%). Results showed maximum metal loss at 700°C, with higher SO 2 levels causing increased corrosion. Materials with higher chromium content demonstrated better corrosion resistance, suggesting chromium content is a crucial factor in material selection for these applications.

One of the pathways for achieving the goal of utilizing the available large quantities of indigenous coal, at the same time reducing emissions, is by increasing the efficiency of power plants by utilizing much higher steam conditions. The US Ultra-Supercritical Steam (USC) Project funded by US Department of Energy (DOE) and the Ohio Coal Development Office (OCDO) promises to increase the efficiency of pulverized coal-fired power plants by as much as nine percentage points, with an associated reduction of CO 2 emissions by about 22% compared to current subcritical steam power plants, by increasing the operating temperature and pressure to 760°C (1400°F) and 35 MPa (5000 psi), respectively. Preliminary analysis has shown such a plant to be economically viable. The current project primarily focuses on developing the materials technology needed to achieve these conditions in the boiler. The scope of the materials evaluation includes mechanical properties, steam-side oxidation and fireside corrosion studies, weldability and fabricability evaluations, and review of applicable design codes and standards. These evaluations are nearly completed, and have provided the confidence that currently-available materials can meet the challenge. While this paper deals with boiler materials, parallel work on turbine materials is also in progress. These results are not presented here in the interest of brevity.

In response to the need to reduce carbon dioxide gas emissions, Japan has been actively researching 700°C-class thermal power plants with a focus on improving overall plant efficiency. This technological advancement is fundamentally grounded in advanced materials development, encompassing the creation of high-strength alloys, fireside corrosion-resistant materials, and steamside oxidation-resistant alloys. A significant challenge emerged as some of the developed materials fell outside the scope of existing domestic technical standards. Moreover, the potential failure modes for advanced ultra-supercritical (A-USC) components operating at 700°C were anticipated to differ substantially from those observed in traditional ultra-supercritical (USC) components at 600°C. Consequently, researchers systematically examined and analyzed the potential failure modes specific to 700°C A-USC components, using these insights to establish comprehensive performance requirements. The research initiative, which commenced in June 2006, was strategically planned to develop a draft technical interpretation by March 2011. This paper provides a detailed overview of the investigative process, encompassing the comprehensive analysis of failure modes, the derivation of performance requirements, and the progression toward developing a new technical interpretation framework for high-temperature power plant components.

Reducing emissions and increasing economic competitiveness require more efficient steam power plants that utilize fossil fuels. One of the major challenges in designing these plants is the availability of materials that can stand the supercritical and ultra-supercritical steam conditions at a competitive cost. There are several programs around the world developing new ferritic and austenitic steels for superheater and reheater tubes exposed to the advanced steam conditions. The new steels must possess properties better than current steels in terms of creep strength, steamside oxidation resistance, fireside corrosion resistance, and thermal fatigue resistance. This paper introduces a series of experimental 9%Cr steels containing Cu, Co, and Ti. Stability of the phases in the new steels is discussed and compared to the phases in the commercially available materials. The steels were tested under both the dry and moist conditions at 650°C for their cyclical oxidation resistance. Results of oxidation tests are presented. Under the moist conditions, the experimental steels exhibited significantly less mass gain compared to the commercial P91 steel. Microstructural characterization of the scale revealed different oxide compositions.

The development of oxy-fuel combustion technology for coal-based power generation may produce combustion products different from those typically found in traditional boilers. In particular, the enrichment of CO 2 and perhaps SO3 could alter the chemical equilibrium to favor the formation of certain carbonates and sulfates in the deposit. Higher concentrations of these gases would also increase the potential for condensation of carbonic and sulfuric acids in lower-temperature areas of the boiler. To address these concerns, B&W has instituted a comprehensive research program to better understand the effect of oxy-coal combustion on fireside corrosion. The scope of this program includes gas and deposit analyses of actual combustion products sampled from B&W's Clean Environment Development Facility (CEDF) during the oxy-coal combustion of three commercial coals. The sampling locations consist of regions representing the lower furnace, superheater bank, and pulverizer outlet. Following the gas and deposit analyses, a series of laboratory corrosion tests will be performed to expose candidate alloys and coatings to conditions simulating the oxy-coal combustion environments. The technical approaches and results of the fireside corrosion program obtained to date are discussed.

As the demand for worldwide electricity generation grows, pulverized coal steam generator technology is expected to be a key element in meeting the needs of the utility power generation market. The reduction of greenhouse gas emissions, especially CO 2 emissions, is vital to the continued success of coal-fired power generation in a marketplace that is expected to demand near-zero emissions in the near future. Oxycombustion is a technology option that uses pure oxygen, and recycled flue gas, to fire the coal. As a result, this system eliminates the introduction of nitrogen, which enters the combustion process in the air, and produces a highly-concentrated stream of CO 2 that can readily be captured and sequestered at a lower cost than competing post-combustion capture technologies. Oxycombustion can be applied to a variety of coal-fired technologies, including supercritical and ultra-supercritical pulverized coal boilers. The incorporation of oxycombustion technology in these systems raises some new technical challenges, especially in the area of advanced boiler materials. Local microclimates generated near and at the metal interface will influence and ultimately govern corrosion. In addition, the fireside corrosion rates of the boiler tube materials may be increased under high concentration oxygen firing, due to hotter burning coal particles and higher concentrations of SO 2 , H 2 S, HCl and ash alkali, etc. There is also potential to experience new fouling characteristics in the superheater and heat recovery sections of the steam generator. The continuous recirculation of the flue gases in the boiler, may lead to increasing concentrations of deleterious elements such as sulfur, chlorine, and moisture. This paper identifies the materials considerations of oxycombustion supercritical and ultrasupercritical pulverized coal plants that must be addressed for an oxycombustion power plant design.

The “Coal Ash Corrosion Resistant Materials Testing Program” by The Babcock & Wilcox Company (B&W), the U.S. Department of Energy (DOE), and the Ohio Coal Development Office (OCDO) at Reliant Energy's Niles plant provides full-scale in-situ testing of advanced boiler superheater materials to address fireside corrosion, a key issue for improving efficiency in new coal-fired plants and service life in existing ones. In 1998, B&W developed a system with three identical sections containing multiple segments of twelve different materials from contributors like Oak Ridge National Laboratory (ORNL), cooled by reheat steam and installed in 1999 above the furnace entrance in the Niles Plant 110 MWe Unit #1 firing high-sulfur Ohio coal to test materials at advanced supercritical steam temperatures (1100°F+) in corrosive conditions. The first section was evaluated after 29 months in 2001, the second in 2003, and the final section is expected for removal in 2005. This paper outlines the program, test system, and materials, and it presents the evaluation results for the first two sections.

A consortium which includes Energy Industries of Ohio, the Electric Power Research Institute, Inc., and four major US boiler manufacturers (the Babcock & Wilcox Company, Riley Power, Foster Wheeler, and Alstom Power) is conducting a 5-year materials development program to advance the technology in coal-fired power generation. As part of this development effort, new high temperature, corrosion resistant alloys must be evaluated and qualified for dependable operation in a corrosive coal-fired environment to produce steam for Ultra Supercritical (USC) cycle operation up to 760°C (1400°F) and 35 MPa (5000 psi.) To evaluate the fireside corrosion resistance of candidate materials for USC power generation, two superheater test loops comprised of seven different advanced alloys were designed and fabricated by the Babcock and Wilcox Company (B&W) in Barberton, Ohio. These loops were installed at the Reliant Energy power plant located in Niles, OH, and testing of these loops was initiated in December, 2003. Following a minimum of 18 months of testing, the loops will be removed for metallurgical examination and assessment by B&W. This paper describes some of the considerations in designing, fabricating, and installing the two USC test loops, as well as the methodology for monitoring their performance during operation.