A COMPARISON STUDY OF ACFB AND PCFB ASH CHARACTERISTICS

K.M. Sellakumar and R. Conn

Foster Wheeler Development Corporation, 12 Peach Tree Hill Road, Livingston, NJ 07039, USA

A. Bland
Western Research Institute, 365 N. 9th St, Laramie, WY, 82070, USA

6th International Conference on Circulating Fluidized Beds

Wurzburg, Germany

August 22-27, 1999

A COMPARISON STUDY OF ACFB AND PCFB ASH CHARACTERISTICS

K.M. Sellakumar and R. Conn
Foster Wheeler Development Corporation, 12 Peach Tree Hill Road, Livingston, NJ 07039, USA

A. Bland
Western Research Institute, 365 N. 9th St, Laramie, WY, 82070, USA Abstract - The advent of fluidized bed combustion technology has provided avenues for environmental issues-free use of all types of fossil fuels. With the potential commercial application of Pressurized Circulating Fluidized Bed Combustion (PCFB) technology in the very near future, there is a need to understand the similarities and differences in the characteristics of solid by-products from the conventional Atmospheric Circulating Fluidized Bed Combustion (ACFB) and the PCFB. Similar to ACFB residues, the main components in PCFB residues are from: the inorganic constituents in the coal and incorporated sediments (Al, Fe, and Si), sorbent derived elements (Ca, from limestone, or Ca and Mg if dolomite is used), and sulfur released from the coal during combustion that is captured by the sorbent.

However, the concentration of each component in the residues may show great variations, depending on the feeds and operating conditions in the unit. In general, the residues discharged from PCFB units with the same types of feeds and sulfur retention should have a relatively lower content of calcium but a higher content of coal-derived constituents than those from ACFB units, because a lower sorbent feed is required for pressurized systems. Also, the sorbent-derived components in the residues from both systems are different due to the various sulfation mechanisms under atmospheric and pressurized conditions. Ash samples from the commercial ACFB plants and the Foster Wheeler 10 MWth PCFB pilot plant in Karhula have been used in this study. In this paper, the ash characteristics and where one type of ash- ACFB ash or PCFB ash has better application over the other are described. INTRODUCTION CFB combustion has proven to be one of the most promising technologies for burning a wide range of coals and other fuels and handling wide variations in fuel quality, while still achieving strict air emission requirements. Low-grade fuels that have large ash content and very high sulfur do not normally find acceptance in pulverized coal (p.c.) units. These fuels are burned efficiently in CFB systems. However, if the sulfur content is large, then necessary sorbent has to be added to capture SO2 in solid form. CFB boilers generate two major waste streams, fly ash and bottom ash, which are a mixture of fuel ash, unburned carbon residues, and lime particles coated with sulfate layers. The ash properties are substantially different from the p.c. ashes typically marketed as ASTM Class C and F fly ashes. The operating conditions for CFBC units, in addition to the fuel and sorbent characteristics, directly contribute to the chemical characteristics of the ashes. CFB ashes generally contain a higher content of calcium as an oxide and as a sulfate, but a lower content of silica and alumina than ashes generated from p.c. boilers. One notable exception is ashes resulting from the firing of low sulfur anthracites and bituminous coals; these by-products are composed primarily of fuel ash constituents, since sorbent does not dominate ash chemistry. Consequently, the utilization options for CFB ashes are somewhat more diverse than p.c. ash, due to the effect of sorbent on the overall ash chemistry.

Pressurized fluidized bed combustion (PFBC) represents one of the most promising emerging Clean Coal Technologies (CCT). Circulating PFBC technology is being demonstrated at the pilot-scale at Foster Wheeler Energia Oy in Karhula, Finland. Western Research Institute (WRI) has completed a three-year project under sponsorship of the Electric Power Research Institute (EPRI), Foster Wheeler Energy International, Inc., and the U.S. Department of Energy (DOE) Federal Energy Technology Center (FETC) that addressed ash use markets and options for PFBC technologies. FW supplied representative ash samples from the Karhula PCFB pilot combustor operation for this study. The overall objectives of this study were to determine the market potential and the technical feasibility of using PFBC ash in high-volume use applications. The Environmental Protection Agency (EPA) made a final rule that effective September 2, 1993, four large-volume fossil fuel combustion (FFC) waste streams from electric utility power plants are exempted from RCRA (Resource Conservation and Recovery Act of 1976) Subtitle C for hazardous waste regulations (Federal Register 1993). The waste streams include fly ash, bottom ash, boiler slags, and flue gas desulfurization (FGD) sludge. Nevertheless, the fluidized bed combustion (FBC) waste streams were not included in this final regulatory determination due to the lack of information. Since early 1990s, extensive studies have been conducted on the ACFB and PCFB ashes (Young, 1996; Conn and Sellakumar, 1997, Conn, Wu, and Sellakumar 1997; Bland, 1998). In this paper, a review of the ACFB and PPCFB processes, key changes in the by-product constituents, and attendant differences in the physical and chemical properties are described. In addition, the current and potential uses of the by-products are outlined. ACFB AND PCFB PROCESSES In fluidized bed combustors, limestone is added in the bed for sulfur capture. Probable sulfur capture mechanisms in the ACFB and PCFB combustors have been summarized earlier (Koskinen et al., 1993). Numerous studies have confirmed that at atmospheric conditions, the first step in the sulfur capture process is the calcination of CaCO3. CaCO3 (s) CaO (s) + CO2 (g) (1) The calcination reaction proceeds significantly faster than the next step that is the sulfur capture step, called the sulfation reaction. CaO (s) + SO2 (g) + 1/2 O2 (g) CaSO4 (s) (2) Under pressurized fluidized bed combustion conditions, the high partial pressure of CO2 that exists by virtue of the high combustor pressure, prevents the decomposition of CaCO3. At high O2 partial pressures, the desulfurization reaction in pressurized conditions is via the "direct" sulfation of CaCO3. CaCO3(s) + SO2(g) + 1/2 O2(g) CaSO4(s) + CO2(g) (3) However, in the presence of some catalysts SO2(g) can be converted to SO3(g), and the following reaction is also possible (Hajaligol et al. 1988): CaCO3(s) + SO3(g) CaSO4 (s) + CO2(g) (3a) Thermal decomposition of CaSO4 in normal pressurized fluidized bed combustion conditions is not probable because of low temperatures and high pressures in the reactor. However, according to Lygnfelt and Leckner (1989) significant amounts of SO2 may be released from the sorbent in the pressurized fluidized bed combustion if conditions become reducing in the reactor. In summary, it can be concluded that under PCFB conditions: the sulfation of sorbents takes place by a direct reaction between CaCO3 and SOx.. the sulfation rate increases with temperature and the total pressure in the combustor does not limit the sulfur capture by the sorbent. The surface structure of the ash particles from the PCFB process is likely to be different from that of the ash from the ACFB process.

CHARCTERIZATION OF ACFB ASH Chemical Properties: Key oxides of interest for ash use in typical ACFB bottom ash and fly ash are presented in Table 1. The chemical characterization testing included major element composition, as well as phase analysis. There is a general decrease in CaO and SO3 with decreasing sulfur content of the fuel burned. Fuel ash contributes silica, alumina, and certain amounts of alkalis. The fly ash and the bed ash were also analyzed by X-ray diffraction (XRD) for phase composition. The data confirm the observation that the ashes are composed principally of anhydrite[CaSO4], lime [CaO], quartz [SiO2], and associated oxides of iron, magnesium, and dehydroxylated clays originating from the fuel ash components. Physical Properties: The general physical properties of the ashes were also determined, including poured and packed bulk densities, specific gravity, particle size distribution, and moisture. The fly ashes all were relatively fine with greater than 80% passing a 200-mesh screen (74m). As a result, these ashes can readily be made into cement-type pastes without further milling. The poured bulk density of the fly ashes ranged from about 540 (low S fuel) to 916 (high S fuel) kg/m3; the compacted bulk density of the fly ashes were slightly higher and ranged from 840 (low S) to 1167(high S) kg/m3. The specific gravity ranged from 2.2 (low S) to 2.7 (high S) for the fly ashes. CHARACTERIZATION OF PCFB ASH The study of PFBC ash use options has included two different ashes: ash from the combustion of low-sulfur Powder River Basin subbituminous coal (Black Thunder) with limestone sorbent and the combustion of high-sulfur Illinois Basin coal with a limestone sorbent. (Bland, 1998). General Chemistry: With the exception of relatively high mineral carbon, the chemistry of the PCFB ashes is typical of ashes from ACFB of low-sulfur and high-sulfur coals using limestone and dolomite sorbents. Phase analyses of the ashes by X-ray diffraction show that the PCFB ashes are composed principally of anhydrite (CaSO4 ), calcite (CaCO3 ), coal ash oxides, and dehydroxylated clays. The lack of lime (CaO) in the PFBC ashes is distinctly different from AFBC ashes, which contain large amounts of lime. As stated earlier, in PFBC systems, the partial pressure of CO2 favors both calcination and recarbonization. This results in low lime and high carbonates (calcite) in pressurized FBC ash. Key oxides of interest for ash use are presented in Table 1. The loss on ignition (LOI) is composed of the moisture and the organic carbon. The LOI in the PFBC ashes has been corrected for mineral carbon. Moistures are less than 0.1% and the organic carbon contents are less than 2%. The free lime (CaO) content of the PFBC ashes was determined by ASTM C-25 to be in the range of 0.5 to 1.0%. The majority of the lime appears to still be carbonated in the form of CaCO3. Physical Properties : The general physical properties of the ashes were also determined, including bulk densities, specific gravity, and particle size distribution. The PCFB fly ashes measured pouredbulk densities of 795 to 948 kg/m3 and specific gravities of 2.73 to 2.34 for high sulfur and low sulfur fuels respectively. This is just opposite of the ACFB fly ash characteristics. DISCUSSION Ash Characteristics: Leachate characteristics of the ashes were tested according to the U.S. EPA Toxicity Characteristics Leaching Procedure (TCLP) (EPA CFR Part 241). The ash leachate data substantiate that none of the leachates generated from the ACFB and PFBC ashes exceeded the 1976 RCRA limits. As such, these ashes would not be classified as hazardous. Ashes from other coal-fired power systems are already categorized as nonhazardous and have been given an exclusion from these RCRA requirements (Table 2). Ash Utilization Studies: Diverse utilization options have been studied for ACFB and PCFB coal ashes. The potential applications include: - construction applications: cement substitute, concrete block production, brick production, soil stabilizer, roadbase/subbase materials, structural fill materials, and synthetic aggregates;

- agricultural applications: - waste stabilization:

liming and soil amendment; acidic waste stabilizer and sludge stabilizer.

The key fuel and sorbent properties, which can influence ash characteristics, are sulfur content, ash content, and ash composition including the form of Ca (CaCO3 or CaO). Other important fuel properties influencing ash characteristics are the size and friability of the fuel minerals. These properties will impact on how these minerals will exit the CFB in the fly or bottom ash stream, which can have a significant effect on the utilization of these streams. Extensive literature is now available on the ACFB ash use options based on the studies since early 1980s. (Anthony et al. 1995, Kilgour et al, 1991, Sun et al. 1980, Tavoulareas et al. 1987; Conn et al. 1997; Bland, 1998; Bland, 1999). Details on PCFB ash use has been reported since 1993 (Bland et al. 1994; Bland, 1998). A summary of the current know-how is given below. Ash Use in Construction Applications: ACFB and PCFB fly ashes cannot be classified as Class F or C, because of low FAS (ferric oxide, alumina, and silica) and high SO3 content (Table 1). Even though CFB fly ash may not qualify as a Portland cement admixture, it may have the potential for use in concrete blocks. Bottom and fly ash can be used as an aggregate and pozzolan in concrete blocks. The bottom ash used as an aggregate has a lower unit weight than many naturally occurring aggregates, thus reducing the weight of the block. CFB fly ash with properties of Class C and F can be used as a partial replacement for Portland cement in some block plants. Generally, the carbon content of the fly ash must be limited to less than 5%, since segregation can occur during handling and result in nonuniform blocks. The free lime and sulfate contents of CFB ashes can limit their utilization in concrete block production. Free lime present in ash will form water-soluble calcium hydroxide, resulting in weakening of the block from contact with moisture. As with Portland cement concrete, ettringite can form in concrete blocks due to high ash sulfate levels resulting in mechanical weakening of the block. It is possible that CFB ash may replace some Class C or F fly ash or Portland cement in more moderate strength blocks. Such materials may not be preferred for heavy construction applications, but more for residential uses (Conn et al. 1997). Testing of PCFB ash has indicated that PFBC ash, when mixed with low amounts of lime, develops high strengths, suitable for soil stabilization applications and synthetic aggregate production. Synthetic aggregate produced from PFBC ash is capable of meeting ASTM/AASHTO specifications for many construction applications (Bland 1998). Soil/Mine Spoil Amendment: The technical feasibility of ACFB/PFBC ash as a soil amendment was examined for acidic problem soils and spoils encountered in agricultural and reclamation applications. The results of the technical feasibility testing indicated the following: Ash streams from CFB boilers firing low sulfur semi-anthracite and anthracite waste would not be good candidates for agricultural liming due to very low free lime ( and CaCO3 equivalent) contents. On the other hand, ash streams from CFB boilers firing bituminous coals may be suitable for liming, depending upon how calcium is partitioned between the fly ash and bottom ash. PFBC fly ashes were effective acid spoil and sodic spoil amendments though they have low CaO content. In a comparison with ag-lime, the fly ashes reacted with the acidic spoil at a slower rate and the final pH of the treated material was slightly lower (i.e., fly ash treated, pH 7 and the ag-lime treated 8). the greenhouse studies demonstrated that PFBC fly ash amended spoils resulted in higher plant productivity than the ag-lime-amended spoils. These results possibly are due to pH and nutritional issues, but root penetration was undoubtedly a factor.

CFB ash streams can also be used to stabilize waste streams from a variety of processing operations. This stabilization includes solidification and fixation of sludge materials for landfilling,

neutralization of acidic wastes, and municipal sludge waste sludge. For each of these applications, the suitability of CFB ash is enhanced by its free lime content CONCLUSION In-house and literature data show that ash streams from CFB boilers firing diverse fuels have the potential for use in one or more applications. FW has studied the ACFB bottom ash and fly ash characteristics from both an environmental impact and by-product utilization standpoint. First, the risk screening criteria and exposure analysis results indicate that these CFB wastes are as clean or better than those generated from conventional combustors such as p.c. boilers. As a result, CFB by-products can be used in various applications without impacting the environment. The exact utilization options for ACFB by-products will depend primarily on the type of fuel being fired, and to a lesser extent the type of sorbent utilized for sulfur capture. The PCFB ash differs from the ACFB in the uncalcined CaCO3 in the by-product. As with ACFB ashes, there is a significant market potential for PFBC ash in the construction and soil amendment industries. In particular, PFBC ash represents a technically viable material for use in these currently established applications for conventional coal combustion ashes. It is possible to modify the hydration reaction chemistry of the PFBC ashes through such processes as lime enhancement to produce the geotechnical properties required for construction applications. As a result, PFBC ash should be viewed as a valuable resource, and commercial opportunities for these materials should be explored for future PFBC installations.

REFERENCES
Anthony, E.J., Iribane, A.P., and Iribane, J.V., Proc. of the 13th Intl. Conf. on Fluidized Bed Combustion, Orlando, FL, (1995), Vol. 1, pp. 523-533. Bland, A.E. US DOE Contract DE-FC21-93MC30126, Final Report (Western Research Institute Report WRI-98-R017), June, (1998). Bland, A.E., Proc., 1998 Advanced Coal-Based Power and Environmental Systems 98 Conference, US Department of Energy, Morgantown, WV, (1998). Bland, A.E., Proc. of the 15thIntl. Conf. on Fluidized Bed Combustion, Savannah, GA, (1999). Conn, R.E., and Sellakumar , K.M., Proc. of the 14th Intl. Conf. on Fluidized Bed Combustion, Vancouver, Canada, (1997), pp. 507-518 Conn, R.E., Wu, S., and Sellakumar, K.M., 1997 Pittsburgh Coal Conf., Taiyuan, China (1997). Conn, R.E., Sellakumar , K.M. and Bland, A.E., Proc. of the 15th Intl. Conf. on Fluidized Bed Combustion, Savannah, GA, (1999). Federal Register, Part V, United States Environmental Protection Agency, 40 CFR Part 261, Vol. 58, No. 151, August 9, 1993. Hajaligol, M.R., Longwell, P.J., Sarofim, A.F, Ind. Eng. Chem. Res. 27, (1988), pp.2203-2210. Kilgour, C. L., and McGowan, K.I., Electric Power Research Center, Iowa State University, Final Report, October (1991). Koskinen, J., Lehtonen, P., and Sellakumar , K.M., Proc. of the 13th Intl. Conf. on Fluidized Bed Combustion, Orlando, FL, (1995), pp. 369-378 Lygnfelt, A., and Leckner, B., Proc., 10th International Conference on Fluidized Bed Combustion, Manaker, A., ed., ASME, New York, (1989), pp. 675-684 Sun, C. C., and Peterson, C. H., Proc. Sixth Intl. Conf. on Fluidized Bed Combustion, Philadelphia, PA, (1980), Vol. 3, pp. 900-912. Tavoulareas, S., Howe, W., Golden, D., and Eklund, G., Proc. of the 9th Intl. Conf. on Fluidized Bed Combustion, (1987), Vol. 2, pp. 916-926. Young, L., Fifth Intl. Conf. on Circulating Fluidized Beds, Beijing, (1996), Pr5

Table 1 Typical Ash Chemistry of Fly Ashes from Different Fuels

Fuel ACFBHigh sulfur Bit. 12.19 4.60 FA (1) 7.4 68.8 13.7 0.47 2.8 35.2 ACFB Low sulfur Bit. 7.32 Class S, % Ash, wt. % SO3 FAS (3) Free CaO Moisture LOI >325 mesh (max) Note: 1. 2. 3. 0.55 FA 8.0 49.2 28.5 na na na 3 max 6(2) max 34 max 3 max 6 max 34 max F 5 max 70 min C 5 max 50 min 3.39 FA 20.83 50.63 <1 0.15 0.82 37.83 0.48 FA 12.27 57.57 <1 0.09 0.81 25.58 Pozzolan in Portland Cement PCFBHigh sulfur Bit. 11.3 PCFB - Low sulfur Bit. 7.9

Ash %

FA= Fly Ash; na= not available Use of Class F Pozzolan containing up to 12% LOI may be approved by user if acceptable performance records or test results exist. FAS= Fe2O3+Al2O3+SiO2

Table 2 Typical Ash Leachate Data for Fly and Bottom Ashes from Different Fuels
Regula tory Limit, mg/L Arsenic Barium Cadmium Chromium Lead Mercury Selenium Silver 5 100 1 5 5 0.2 1 5 ACFB- High sulfur Bit. FA 0.004 0.41 <0.001 <0.001 <0.5 <0.002 <0.2 <0.01 BA 0.013 0.36 <0.001 <0.001 <0.5 <0.002 <0.2 <0.01 ACFB - Low sulfur Bit. FA 0.003 0.18 0.007 0.016 <0.5 0.005 <0.2 <0.01 BA 0.001 0.19 <0.001 <0.001 <0.5 <0.002 <0.2 <0.01 PCFB- High sulfur Bit. FA <0.04 0.26 <0.01 0.12 <0.1 <0.002 <0.2 <0.1 BA <0.04 0.32 <0.01 <0.05 <0.1 <0.002 <0.2 <0.1 PCFB - Low sulfur Subbit. FA 0.041 0.395 <0.01 <0.05 <0.1 <0.002 <0.2 <0.01 BA <0.04 0.241 <0.01 <0.05 <0.1 <0.002 <0.2 <0.01