CFB Refractory Improvements for Biomass Co-Firing

Andreas W. Rau Foster Wheeler North America Corp. Clinton, NJ 08809

Presented at 2009 Coal-Gen Conference Charlotte, North Carolina USA August 18-21, 2009
TP_CFB_09_13

CFB Refractory Improvements for Biomass Co-Firing

Andreas W. Rau, Manager-Refractory Services, Foster Wheeler

Abstract: The increasing demand for Circulating Fluid Bed (CFB) Boilers to co-fire biomass and waste fuel products creates increased stress on refractory systems resulting in more frequent replacement cycles and increased maintenance costs. The problems with refractory systems in this application are accentuated due to improper application and/or inappropriate material selection. The primary failure is due to corrosion/erosion associated with varied bio-mass materials. This failure mechanism is the result of alkali related chemical attack which creates compounds that be easily eroded. A secondary concern is the inappropriate use and application of the refractory material. This is less of a concern in CFBs that are not used to co-fire biomass. Chemical attack, or refractory corrosion, is the reaction between the material matrix and the interface of alkalis introduced into the unit (usually from the fuel source, mainly sodium, potassium, and calcium in the forms of carbonates, sulfates, and chlorides). These reactions occur within the microscopic pores of the refractory lining causing weakened bonds, volumetric expansion and ultimately, failure by erosion. Refractory technology has changed dramatically over the past several years. Although various material products are promoted to be more resistant to alkali attack, many of these products rely on high surface temperatures for the formation of silica glass to seal the porosity and reduce the likelihood of alkalis penetrating the surface. Unlike other industrial applications using refractory linings, CFB operating temperatures are lower than the 1850oF required for the formation of the silica glass seal. Because of this, refractory material choices become more limited, relying more on the types of raw constituents, bonding mechanism, ultimate porosity, alumina type, and installation method to achieve higher resistance to chemical attack and extended refractory life. This paper will describe the historical data outlining the results of Foster Wheelers previous analytical studies, operational failure analysis as well as recommendations for new engineered materials for co-firing biomass.

1.

INTRODUCTION

There have been worldwide trends over the past several years steering away from standard coal fuels such as bituminous, anthracite, and lignite toward the combustion of alternate solid fuels such as petroleum coke, wood waste, peat, agricultural waste, tire and refuse derived fuels. Depending upon regional availability, these alternative fuels can result in lower plant operating costs, reduced emissions, and meet government guidelines for replacing fossil fuels with carbon neutral, renewable energy sources.

With the CFB Boilers ability to burn alternative fuels with little or no modifications many existing traditional coal fired facilities have selected or are in the process of selecting alternative fuel sources for co-firing. Refractory linings and coal firing have coexisted for over a century, the refractory lining systems in the existing CFB plants are often not considered when alternative fuels are selected for combustion. Many of the existing CFB facilities that began operation in the late 1980s and early 1990s were lined with older refractory products. Recently they have begun co-firing their current coal with biomass fuels. Although the existing refractory linings have been successful with minimal repair or replacement over the operating life of the plant, annual maintenance costs of these current lining systems have increased dramatically due to premature failures and increased unplanned outages. The initial mode of failure appears to be primarily due to erosion and excessive cracking that has not been previously experienced. As a result, larger replacement areas of the combustor and cyclone linings are required, often resulting in longer planned outage cyclones, or more frequent emergency outages to maintain the thermal and tube protection required for the CFB environment.

2.

FAILURE MODES EXPERIENCED

In the past, CFB refractory systems were constructed with either traditional high-cement alumina-silicate based cast/gunite castables or phos-bonded alumina-silicate ram plastic refractory products. These materials needed to resist abrasion from the fluid bed environment, have moderate structural strengths, and resist the elemental constituents (i.e. sulfur) found in coal based fuels. Early failures due to erosion prompted refractory manufacturers to develop higher abrasion resistant properties to withstand the mechanical erosion experienced in the CFB environment. It was reported by Farris and Allen(1) that alkalis tend to attack refractories by penetrating into them, reacting with the matrix (weakening and depleting the bond) and forming compounds that expand. They have determined that the reaction products formed are alkali aluminum silicates that can form at temperatures as low as 1575oF. Studies have shown that even trace amounts of alkali such as sodium and potassium have been found in coal ash samples. The main factors involved with the resistance to alkali attack are the materials porosity, surface area, purity, and ability of some refractories to surface seal via surface reactions and glazing. It was also studied by Kawamura et. al(2) that calcium aluminate cements (CACs) were susceptible to attack by alkalis, and materials with high levels of CACs were less resistant than castables containing lower levels. In the mid-1990s, the development and use of the low cement alumina silicate based refractory products had increased the life of the CFB refractory systems and failure rates were reduced. Over the recent years, continued advancement of the low cement castable based products has yielded higher strengths, abrasion resistant properties. The improvements in these properties and resistance to alkali attack compared to conventional materials in coal-only fired facilities resulted in extended life of the linings, and provided lower cost installation methods. These materials have become the

choice for CFB Boiler lining systems. Many CFB plants decreased planned outage frequencies from 6 months to 12-18 months. After many plants began co-firing biomass fuels, refractory lining deterioration and failures once again became evident. In all of the cases, increased rates of erosion along with extensive cracking, resulted in exposed tubes, thinning of the linings, and hotspots on the cyclone casings. Moisture in the biomass fuels were the initial culprit. It has been shown that higher moisture fuels will increase the gas and solids velocity through the CFB hotloop, and studies have shown that erosion rates of refractory are exponentially proportional to velocity (i.e. 10% increase in particle velocity can yield an approximate 21% increase in refractory erosion). Although this perception is plausible in the expected high wear areas such as the lower combustor, cyclone inlet, and cyclone target wall, inspections of several units revealed similar modes of failure in loopseal or seal pot zones where high velocity is not experienced. Analysis of various units firing biomass fuels demonstrated higher amounts of alkalis, such as sodium, potassium, and phosphorus (see Table-1). When combusted at CFB operating temperatures, these alkalis will vaporize, react with other elements and pass through the CFB boiler hotloop, condensing and forming deposits on cooler metal and refractory surfaces. In studies performed for NREL(3), it was shown that potassium is a naturally occurring element in many herbaceous plants as an essential nutrient with over 90% of the potassium in clean (non-soiled) fuels as either water soluble or ion exchangeable material. It was verified that its vaporization and subsequent chemical reactions were responsible for the fouling, sulfation, metal corrosion, and silicate formation found in biomass boilers. Although sodium is a minor component of most biomass fuel, it can be substituted naturally for potassium.
Fuel Type Typical Coal Urban Wood Waste (as recd) Demolition Wood (as recd) Land Clearing Wood (as recd) Sugar CaneBagasse (as recd) Bana Grass Switchgrass Almond Shells (as recd) Pistachio Shells (as recd) Walnut-Hulls/Blows (as recd) Olive Pits (as recd) Rice Hulls (as recd) Moisture 7.17% 37.54% 9.01% 49.19% 10.39% 4.51% 13.27% 6.93% 7.54% 47.85% 6.08% 10.94% Alkali lb/MMBtu 0.34 0.54 1.09 0.15 5.66 0.30 1.98 0.41 1.05 0.60 1.17 Water Soluble Na2O K2O N/T N/T 0.008% 0.097% N/T N/T 0.008% 0.095% N/T N/T 0.016% 3.520% 0.004% 0.134% N/T N/T N/T N/T N/T N/T N/T N/T 0.019% 0.592% Fe2O3 3.25% 7.43% 12.02% 5.27% 14.14% 0.63% 1.08% 2.30% 35.37% 1.14% 6.58% 0.14% Elemental Composition Na2O K2O 0.35% 1.10% 1.53% 5.36% 1.13% 2.14% 2.70% 2.19% 0.79% 4.15% 0.38% 42.80% 0.64% 8.24% 1.60% 48.70% 4.50% 18.20% 0.99% 32.90% 27.8% 4.40% 0.21% 3.71% P2O5 0,05% 1.50% 0.94% 0.66% 2.72% 2.74% 3.09% 4.46% 11.8% 6.24% 2.46% 0.43%

Table-1 Composition of Various Fuel Blends in Biomass Units(3)

Once alkali elements such as potassium and sodium vaporize, they penetrate the pores of the alumina-silicate refractory hotface lining. The reactions in the CFB Boiler operating temperature range form alkali-alumino-silicates, which have a greater volume than the original refractory. As these reactions occur over time, microcracks develop within the lining and weaken the physical system. Although the chemical bond strength in the lower calcium aluminate cement materials is less affected by the alkalis, the volumetric change at the surface of the lining will cause degradation and spalling/blistering (see photo 1). The surface of the lining in the CFB environment will

tend to become smooth due to the solids impact, and the reactions will repeat. Over time, the refractory system will appear to be failing due to a pure mechanical erosion affect, when it is actually suffering a corrosion/erosion affect.

Photo #1 Alkali Corrosion effect causing spalling & blistering on High Abrasion Resistant, Bauxite Al2O3 Low Cement Castable after 6 months of co-firing Palm . The same reactions can be occurring within cracks formed in monolithic lining by thermal expansion, thermal cycling, or external stresses acting upon the lining. Alkali vapors can penetrate the refractory within the existing cracks, and these same reactions causing volumetric expansion and more extensive micro cracking. With repeated thermal expansion and contraction, the weakened lining adjacent to the crack will be crushed and carried away by the solids flow. In both the above scenarios, it is not common to find traces of the reactions occurring during inspections of the linings, since all evidence of the weakened lining is eroded away by the solids flow through the unit.

3.

REFRACTORY MATERIAL SELECTION

Within the refractory industry in the USA alone, there are 1000+ different refractory products available for various applications, processes, thermal requirements, and installation methods. Different types of materials can be classified by chemistry, such as Silica (Crystalline and Fused), Aluminosilicates (Fireclay and High Alumina), Basic

(MgO and Cr2O3), and Silicon Carbides. These can further be categorized by Physical Characteristics, such as Brick (Fired, Chem Bond, Carbon Bond) and Monolithic (High Cement, Low Cement, Chem Bond, Insulating, Plastics, and Mortars). All materials exhibit different properties dependent on their designed use, properties and capabilities. Since the inception of the CFB Boiler in the 1970s, refractory products have advanced substantially with respect to physical properties. Earlier failures resulting from physical abrasion/erosion, structural strength cracking, thermal shock, and thermal expansion became a focus for material development. With the exception of the Silicon Carbide type of materials used to provide heat transfer, nearly all of the applications in CFB Boilers utilized the Aluminosilicate classifications of material. These are primarily comprised of alumina, silica, binders (cement, micro silica, clay, and other chemicals) and aggregates, blended to achieve specific properties. 3000oF Low Cement Castable technology became available in the late 1980s in casting grades only, with gunite grades available by the mid 1990s. This dramatically increased the mechanical physical properties for strength and abrasion at the lower 1550-1750OF temperature ranges typically found in CFB Boilers. In the CFB Boiler harsh environments, these newer materials extended overall service life, reduced unplanned failures and maintenance costs. The chemical related attack from coal fuels due to sulfur and minimal alkali content were diminished in coal fired units. As these existing CFB plants began co-firing biomass, similar cracking and erosion failure modes appeared with the existing linings. Outage maintenance costs and replacement scopes suddenly increased. Samples were taken from the refractory surface for analysis, but were typically inconclusive as to determination of a chemical attack cause due to unit erosion, however, samples taken from within exposed cracks showed evidence of alkali penetration. It was found that certain low cement and ram plastic products remained unaffected or showed slower evidence of degradation. In most cases, the original high cement refractory materials had increased rates of degradation. In some units, unplanned outages were related to increased failure of the lining before the next planned outage cycle.

4.

HISTORICAL EXPERIENCE

In analyzing the failure modes of various biomass co-fired CFB refractories, the installed products physical properties (strength, abrasion resistance, service temperature, etc) and chemical classification (Al2O3, CaO, Fe2O3 and SiO2 content, and Al2O3 type) were studied by Foster Wheeler to search for apparent material differences. Initial conclusions of the various products showed that the physical properties had little correlation with alkali attack, but may slow the rate of degradation due purely to mechanical erosion. The calcium aluminate cement content (CaO) did show a direct correlation as originally suspected, consistent with previous studies and previous failure analyses, but it appeared to have little difference in the 1.5-2.5% range of standard low cement refractories. In addition, several manufacturers were contacted regarding their recommended product selections for this type of environment. Opinions varied greatly

by manufacturer and were based on practical experience gathered from various historical process applications where known failure of previous linings by alkalis occurred. In general, these process temperatures were lower or higher than that found in a CFB Boiler. In a report issued by Walton(4) based on actual tests in cement plant refractories where potassium salts may be present, it was found that high alumina refractories were experiencing shorter than expected life in operating zones between 1400-1700oF, similar to that in a CFB Boiler. It was believed that the potassium was reacting with the alumina in the material and the formation of feldspar (leucite) resulted in compound expansion that caused the failures. Testing by Hanley and Tomlinson(5) concluded that such reactions can occur, and will result in particle expansion rates of +29% (linear by volume). It was determined that materials with higher silica content would tend to form kaliophilite (KAlSiO4) at operational temperatures, which can form a siliceous barrier layer in these temperatures on the surface of the lining to prevent excessive alkali penetration. This barrier seals the permeability of the hotface. The approach taken to reduce the failure rate was to lower the refractory materials alumina content by providing a higher silica/alumina ratio. Aluminosilicate refractories with Al2O3 content below 50% and SiO2 below 45% were selected for trials, and found successful at cement kiln operational temperatures. This generally equates to a lower grade of aluminosilicate material than commonly found in CFB boilers. The negative aspect of this conclusion relates to the lower physical properties such as abrasion resistance that is inherent with these lower grades of material for use in the higher expected wear zones in a CFB boiler. Many material manufacturers and product data sheets may recommend these types of materials for biomass applications, but caution is required when selecting these materials with respect to physical properties. In CFB boiler zones such as the loopseal or sealpot where abrasion resistance is not a limiting criteria, selection of products in this range may be feasible. When comparing various high abrasion resistant products, Foster Wheeler found that some products showed little to no degradation in the first year of operation with biomass fuels. These initial products were chosen based on physical properties primarily for the high wear zones. Although their initial abrasion resistance results were typically better than the standard low cement products being used, they also had a different source of alumina. Most products in the aluminosilicate classification utilize bauxite as the primary alumina source. These products in the low cement range were successfully used in coal only fired CFB boilers. Typically, for frequent failure zones, such as the air and fuel penetrations, materials have been upgraded to higher purity, mullite based high alumina products that offer more resistance to abrasion. When used in co-fired and 100% biomass CFB Boilers, there was no evidence of degradation related to alkalis. It was found by Kennedy(6) in the application of a mullite based refractory in a slagging gasifier, that the lining experienced premature failure related to cracking and spalling in the presence of high levels of sodium. It was believed that the compound (NaOH) reacted with the refractory to form carnegieite and beta-alumina. These resulting products caused similar failures by volumetric expansion within the surface of the lining when combined with potassium. Although normal operation of the gasifier ranges from

1500-2200oF, they found evidence in the samples taken of a pure form of carnegieite that is only stable above 2280oF. It was later found that the gasifier had been operating intermittently in the temperature range conducive for these reactions to occur. In laboratory testing by Nicia(7) et. al, various refractory materials were subjected to high concentrations of potassium salts and fired for 7 days. Using SEM imaging, all samples reported matrix penetration of the corrosive salts to some degree. Although the mullite (3Al2O32SiO2) based sample did exhibit some degree of penetration, it was less than with other refractory materials. After a cyclone targetwall refractory failure within 6-8 months of operation in a co-fire wood waste CFB Boiler that utilized a high abrasion low cement product manufactured and installed by Foster Wheeler in fired pre-cast shapes, the initial mode of failure was abrasion and the material quality was suspect (see photos 2 & 3). Material samples were taken and tested for physical properties, and proved to be above specification. Further analysis(8) had determined the presence of calcium silicates, alkali silicates, magnesium silicates, and aluminum silicates found in a surface deposit of weakened refractory that had not yet eroded in the environment. The alkali silicates (presumed to be sodium and potassium), penetrated the hotface lining and caused reaction products with volumetric expansion leading to weakening by micro-cracking and eventual erosion. Since operational temperatures in this CFB Boiler were in the 1700-1800oF range, Foster Wheeler selected and installed replacement materials utilizing an extreme abrasion resistant, high purity mullite (3Al2O32SiO2) based low cement that was successful in resisting the alkali attack. At the time, this product was only available in a castable grade.

Photo #2 Corrosion effect on High Abrasion Resistant, Bauxite Al2O3 Low Cement Shapes after 6 months of co-firing Wood Waste.

Photo #3 Corrosion affect on High Abrasion Resistant, Mullite Al2O3 Low Cement Shapes after 6 months of co-firing Wood Waste. In the past several years, more economical versions of this product utilizing a more stable mullite alumina have been developed, and are now available for various installation methods. In another case, a 100% agriculture and wood waste fueled CFB boiler experienced premature failure at the cyclone target wall and loopseal/sealpot refractory (see photo 4). The failure mechanisms included erosion and cracking/degradation related to increased levels of potassium and iron. Although the lining did not completely fail in the initial 12 months of operation, the degree of degradation would not allow another 12 months continuous operation before failure. In order to avert an unplanned outage for repair/replacement, it was elected to replace this wall on an annual basis. The original high alumina brick had been replaced with various alternative materials. While a silicon carbide (SiC) brick was utilized and proved to be more resistant to the alkalis present compared to the original bauxite high alumina brick, it also failed due to the increased thermal expansion of these SiC materials after successive thermal cycles of the boiler. Replacement material selected and installed by Foster Wheeler for the targetwall utilized an extreme abrasion resistant, high purity mullite based low cement product. Due to less severe erosion typically experienced in the loopseal/sealpot, a lower cost, similar mullite matrix material to that used in the target wall was installed in this location. Both were successful in resisting the alkali attack.

Photo #4 Corrosion affect on a Loopseal Body with Abrasion Resistant, Bauxite Al2O3 Low Cement Gunite after 2 years of firing Agricultural and Wood Waste.

5.

CONCLUSION

With the advancements in material technology in the aluminosilicate refractory classifications over the several few years to provide higher physical properties with respect to abrasion, coal fire CFB Boiler linings have improved in reliability and length of service. Plants have been able to extend planned outage cycles from 6 months to as much as 18 months of continuous operation without refractory failure. With the increasing demand for alternative fuel sources in the power generation industry, most CFB Boiler facilities have began co-firing biomass based fuels. With the demands on the refractory linings, primarily due to moisture and alkalis present, the selection of proper refractory materials has become more critical. Material data sheets often state products are resistant to alkalis, but this has been found to apply to varying industrial furnaces and applications, often used successfully in higher temperature applications. Review of technical data and properties are often based on performance at 2500oF. CFB Boiler operating temperatures are often lower than most other processes requiring refractory. Although it is known that low cement aluminosilicate refractories result in better resistance to low levels of alkalis in the 1500-1700oF compared to the traditional high cement refractory material previously used, it has been found that biomass fuels containing higher levels of sodium and potassium have resulted in more rapid degradation of the installed linings.

Foster Wheeler has been revealed that the high alumina products or simply higher physical properties do not necessarily provide better resistance to alkali attack, but rather the type of alumina and silica content that result in increased refractory performance when co-firing biomass fuels in CFB Boilers. Although the surface permeability of any refractory hotface lining is a critical factor with the alkali reactions occurring, one still needs to consider the abrasive atmosphere. For lower erosive zones of the CFB boiler, Foster Wheeler recommends to lower the refractory materials alumina content to provide a higher silica/alumina ratio, this will seal the permeability of the hotface to alkali penetration, thus increasing its resistance and reducing failure rates. While this has been effective in the low erosion areas in CFB Boilers such as loopseals/seal pots and outlet ducts, these products may lack the physical abrasion resistance required in the upper cyclone areas. When increased levels of moisture and alkalis are found in biomass fuels, the higher wear areas by CFB design become more prone to erosive and alkali attack. Foster Wheeler has been found that the type of alumina can provide greater resistance and increase service life. Mullite has shown to be superior to the standard bauxite used in traditional low cement aluminosilicate products.

References (1) J.E. Allen and R.E. Farris, Aluminous Refractories Alkali Reactions, Iron Steel Eng,. 50[2] 67-74 (1973) (2) J. Kawamura, J. Kishimoto, E. Hosoi, and K. Aoki, Consideration On Alkali Corrosion of Alumina Cement-Bonded Castable Refractories, Taikabutsu, 33, (1981) (3) T. Miles, L. Baxter, R. Bryers, B. Jenkins, and L. Oden, Alkali Deposits Found In Biomass Power Plants, Summary Report for National Renewable Energy Laboratory , (1995) (4) M. Walton, Alkali Attack on Cement Plant Refractories An Alternate Prospective, RefMet (date unknown) (5) K, Hanley, O. Tomlinson, The Usage and Development of Monolithic Refractories in the Cement Industry, Refractories Engineer, Journal of the Institure of Refractories Engineers, October 1998. (6) C.R. Kennedy, Alkali Attack on a Mullite Refractory in the Grand Forks Energy Technology Center Slagging Gasifier, American Society for Metals, Volume 3 (1981)

(7) K. Nicia, M. Hupa, L. Hupa, E. Zabetta, Testing Procrdures fro Ceramic Refractory Materials in Bottom Grid of Biomass/Waste-Fired CFBS (2008) (8) R. Stevenson, Refractory Performance Report for Foster Wheeler, (2003)