Industrial Combustion

Journal of the International Flame Research Foundation Article Number 201002 , June 2010 ISSN 2075-3071

Reuse of Partially Sulphated CFBC Ash as an SO2 Sorbent

Yinghai Wu1*, Marianna Nobili2, Antonio Telesca2, Fabio Montagnaro3, Lufei Jia1 and Edward J. Anthony1

CanmetENERGY, 1 Haanel Drive, Ottawa, Ontario, K1A1M1, Canada

Department of Environmental Engineering and Physics, University of Basilicata, Viale dellAteneo Lucano 10, 85100 Potenza, Italy
3

Department of Chemistry, University of Naples "Federico II", Monte SantAngelo, 80126 Naples, Italy
*

Corresponding author. Tel: +1 613 943 7773; Fax: +1 992 9335; Email: ywu@nrcan.gc.ca (Y. Wu)

ABSTRACT Ashes produced from fluidized bed combustors (FBC) burning high-sulphur fuels often contain 20 30 % unreacted CaO because of the limestone added to remove SO2 in situ. This paper presents the results from experiments into reactivating partially sulphated FBC ash (both bed ash and fly ash) with liquid water, steam and sodium carbonate. The water- or steam-hydrated ashes were subsequently re-sulphated in a thermogravimetric analyzer (TGA) with simulated flue gas. The TGA results show that, while liquid water and steam successfully hydrate and reactivate the unreacted CaO in the bed ash, the treated ashes sulphated to widely different extents. Attempts to reactivate fly ash with hydration failed, although fly ash by itself is extremely reactive. A pilot-scale minicirculating FBC (CFBC) was also used to evaluate the results of reactivation on the bed ash by hydrating with liquid water and admixtures of inorganic salt (Na2CO3) in the form of either powder or solution. When the treated ash was re-injected into the combustor with the fuel, the effect on SO2 removal efficiency was negligible if Na2CO3 was added as powder. Doping with aqueous solution resulted in enhanced SO2 removal; however, the extent was lower than the level achieved if only water hydration was employed. Increasing the amount of water (from 10 % to 30 %) to reactivate the ash did not improve the sulphur capture capacity in the mini-CFBC. Overall, this study

suggests that the most practical way for re-use of the partially sulphated bed ash as a sulphur sorbent is reactivation by water. A proposal for utilization of the fly ash in an economically reasonable way is also discussed. Keywords: FBC, CFBC ash, reactivation, hydration, sulphation

1. INTRODUCTION Fluidized bed combustion (FBC) technology has the advantage of being capable of burning high-sulphur fuels with SO2 removal in situ by limestone addition. At atmospheric pressure, SO2 is typically captured via the following two-step overall process (Anthony and Granatstein, 2001): CaCO3 = CaO + CO2 CaO + SO2 + 1/2O2 = CaSO4 (1) (2)

The limestone particles calcine from a low-porosity solid to a porous CaO matrix (Eq. 1), and then sulphate (Eq. 2). While the calcination reaction proceeds to completion readily, the sulphation reaction does not. When the sulphate layer forms, the pores are filled and blocked by the CaSO4 product, preventing SO2 reaction with the unreacted CaO core. Ca utilization with circulating FBC (CFBC) technology is typically from 20 % to 40 % and the ash usually has a significant amount of CaO remaining, from 20 % to 30 %, in addition to CaSO4.

During hydration, reactions in the CaO/CaSO4 system are dominated by direct hydration of the CaO component (Eq. 3), whereas the formation of gypsum (Eq. 4) is slow and can normally be ignored in hydration experiments lasting for hours. CaO + H2O = Ca(OH)2 CaSO4 + 2H2O = CaSO42H2O (3) (4)

4 Water or steam permeates the outer CaSO4 layer of the particles and reacts with the remaining CaO in the core. The core swells and cracks the sulphated shell, because Ca(OH)2 has a larger molar volume than CaO (33 vs. 17 cm3/mol). The previously inaccessible CaO is, therefore, exposed for further sulphation.

It has been proposed that certain salts (e.g., NaCl, CaCl2, Na2CO3) can promote the SO2 capture capacity of limestones (e.g., Laursen et al., 2001b and 2003). This paper attempts to provide a comprehensive evaluation of the reactivation of ashes obtained from an industrial CFBC boiler by hydration with liquid water and steam, and by addition of Na2CO3 (either in solution or as powder). For a complete discussion of sorbent reactivation the interested reader is referred elsewhere (Anthony et al., 2007).

2. EXPERIMENTAL SET-UP

2.1 Materials The partially sulphated materials, namely bed ash (BA) and fly ash (FA), were produced from a 165 MWe CFBC boiler firing petroleum coke and coal blends. The FA had a mean size of about 40 m. The bed ash was sieved to different size ranges before testing. Table 1 gives the chemical analysis of the BA and FA. BA1 and BA2 were received from separate batches. The initial Ca utilization in the received samples was between 30% and 43% (Table 1), which is typical of normal sorbent conversions in the CFBC system. FA and BA1a were used in the thermogravimetric analyzer (TGA) tests; BA2 was used in the pilot-scale tests. BA1b was subjected to scanning electron microscope

5 (SEM) analysis; the SEM equipment used was a Hitachi S-750 provided with a Link AN10/85S EDX system.

Table 1. XRF analysis of CFBC ash (wt.%) FA BA1a (150-300 m) SiO2 15.9 6.8 Al2O3 4.7 2.2 CaO 46.4 52.6 SO3 19.2 32.6 Loss on fusion 9.1 3.1 CaO utilization Carbon analysis Total carbon Carbonate carbon 30 43

BA1b (300-600 m) 7.3 2.3 59.1 26.8 2.1 32

BA2 (425-600 m) 5.3 1.3 60.9 28.7 1.9 33

4.3 0.73

0.1 0.09

0.36 0.15

n/a n/a

2.2 Reactivation and TGA Test The partially sulphated ash was reactivated by hydration with liquid water and steam. Liquid water hydration was carried out in a flask, which was kept in a constant temperature bath to maintain the specific hydration temperature. The tested hydration temperatures were 5 C, ambient (~22 C) and 60 C. The mass ratio of sample to water was 1:20. Water was always in excess to limit overheating and to ensure that the hydration reaction proceeded to completion. During the hydration process, lasting between 0.5 and 4 h at each temperature, the sample/water mixture was gently stirred to prevent local overheating and any potential sample agglomeration. After hydration the solids were then filtered off with deionized water and transferred immediately to a vacuum oven maintained at 45 C, to dry for 3-4 hours (Wu et al., 2002, 2003).

6 Steam hydration was conducted in a pressure bomb (Parr Reactor) in batch mode. The volume of the reactor was 2 dm3. The sample (~2 g each batch) was loaded into a basket which was suspended in the middle of the bomb and immersed in the steam. The temperature was controlled at 150 C, 200 C and 250 C for hydration times between 0.5 and 2 h at each temperature. The equivalent steam pressures corresponding to these temperatures were 4.8, 15.6, and 39.9 bar, respectively. After steam hydration the solids were dried using the same method as described above (Wu et al., 2004).

Re-sulphation tests on the hydrated samples were performed in a Cahn 1000 TGA at 850 C for 90 min in a simulated flue gas environment with the SO2 concentration at 5000 ppm. Re-sulphation was also carried out on unhydrated ash at the same conditions used in the baseline test.

2.3 Mini-CFBC Test The 75 kWth mini-CFBC consisted of a riser, cyclone, return leg and feeder (Fig.1). The riser had an internal diameter of 100 mm and an internal height of 5 m. Four stock ceramic-insulated band heaters surrounded the bottom section of the combustor to help achieve the appropriate combustion temperatures quickly. The flue gas was continuously analyzed for NOx, SO2, CO, CO2 and O2.

Figure 1. Schematic of mini-CFBC pilot plant

Table 2. Analysis of East Kentucky coal used in mini-CFBC Moisture, wt% (as analyzed) 2.26 Proximate, wt% (dry) Ash 12.36 Volatiles 35.82 Fixed Carbon 51.82 Ultimate, wt% (dry) Carbon 72.41 Hydrogen 5.04 Nitrogen 1.61 Sulphur 1.53 Ash 12.36 Oxygen (by difference) 7.05 30.09 Heating Value (MJ/kg)

Table 2 presents the coal analysis results. Sand of size 0.15 - 0.35 mm was the initial bed material, while East Kentucky coal (crushed to < 5 mm) was used. As summarized in Table 3, various reactivation methods were applied to the original CFBC ash (BA2) to prepare it for use as the sorbent for SO2 capture. The bulk of the ash was quite hot and dry before the addition of water (to 10 %) or aqueous Na2CO3 solution. After further addition of water (to 30 %), the ash was moved to the vacuum oven (45C) to dry for about an hour. Na2CO3 (<40 m) was supplied by Fisher Scientific. All the samples

8 were mixed/stirred by hand in an open sample pan. Untreated ash was used as a sorbent for the baseline test as in the TGA experiment.

Table 3. Sorbent preparation conditions Reactivation method Additive/ash, wt % Liquid water 10 Liquid water 30 Na2CO3 powder 5

Na2CO3 solution (20 wt %)

10

Reactivation time, min 30 30 (plus 60 min for drying in vacuum oven at 45C) Mixed by hand for 10 min, then allowed to sit in a sealed can for 7 days 30

The mini-CFBC tests were carried out at nominal bed temperature of 850 C and the superficial gas velocity was about 4 m/s. The coal feed rate was about 4 kg/h. The calculated amount of sorbent was premixed by hand with the coal at a Ca/S molar ratio of 2.5. The combustor fired coal without sorbent until reaching steady state conditions, which usually needed 4-5 hours. The test with the addition of sorbent lasted for an additional 2 to 3 hours before switching back to coal firing.

3. RESULTS AND DISCUSSION 3.1 TGA Test 3.1.1 Free lime and Ca(OH)2 analysis The free lime and Ca(OH)2 contents in the original ash are shown in Table 4. In addition, Table 4 shows the back-calculated results for the difference between the total CaO and the the CaO required for CaSO4 and CaCO3 formation (Wu et al., 2004). The free lime content in the FA was 26.7%, analyzed by the sucrose method (a standard method to directly determine the free lime content as described in ASTM-C25), which was quite

9 close to the result obtained by back calculation. In the case of the BA, the content obtained by difference was significantly higher (14 % points in difference) than that determined by the sucrose method, indicating that a considerable amount of the CaO in the BA had combined with fuel ash components, forming the so-called other calcium compounds (OCCs), e.g., Ca aluminate, silicate, ferrite, and in the case of ash produced from petroleum coke firing, also vanadates, etc. In the back calculation the OCCs cannot be distinguished from the CaO, resulting in a higher value for the free lime content. FA had a stronger ability to absorb and react with the atmospheric water vapor during storage which led to a higher Ca(OH)2 content.

Both steam hydration and liquid water hydration results show that the free lime could either decrease or increase following hydration. Table 5 shows the results of the free lime after steam hydration. In the case of FA, the free lime content was significantly reduced after 30 min hydration at all steam temperatures when compared with that of the original ash prior to hydration in Table 4. By contrast, for the BA, the free lime appeared to increase to a slightly higher level after hydration. This apparently paradoxical result has been previously observed by Bulewicz et al. (2000) and was confirmed by Wu et al. (2002, 2003 and 2004) with ashes from the same 165 MWe CFBC burning a different coal and by Montagnaro et al. (2009) with ashes produced from the same CFBC boiler and also from a different CFBC. Bulewicz et al. studied the exothermicity and the free lime level after hydration under pressure for a series of bubbling and circulating FBC ashes and demonstrated that for such ashes, the number of moles of Ca present as [CaO + Ca(OH)2] (i.e., free lime) can change. This is regarded as clear evidence that, during

10 the hydration process, free lime can be released from the OCC, as well as being consumed by reactions with the coal ash components, such as silica. Table 4. Free lime and Ca(OH)2 content in original ash (as wt. % CaO) Free lime Ca(OH)2 BA1a (150-300 m) 15.4 (29.3 ) 0.9 FA 26.7 (29.5) 4.5 back calculated from XRF analysis results shown in Table 1 The Ca(OH)2 content increased rapidly after liquid water hydration for both BA and FA, which was in line with previous findings (e.g., Wu et al., 2002, 2003; Montagnaro et al., 2006). Wu et al. (2003) found that the Ca(OH)2 content increased with water temperature. However, in the case of steam hydration, as shown in Table 5, there was significant difference between FA and BA (Wu et al., 2004). For BA, the Ca(OH)2 content increased quickly after hydration, though the influence of temperature was slight (between 150 and 250 C). For FA, the Ca(OH)2 content still increased at the lower temperature of 150 C. As the steam temperature increased, the Ca(OH)2 content decreased steadily. At 250 C, the Ca(OH)2 content was almost diminished to its initial level (4.5%) in the FA. The free lime at this temperature must have been consumed by reaction with other components present in the system. Table 5. Free lime and Ca(OH)2 content in CFBC ash after steam hydration (wt. % CaO) Hydration Steam temperature time 150C 200C 250C Free lime Ca(OH)2 Free lime Ca(OH)2 Free lime Ca(OH)2 FA 30 min 20.8 2.3 17.2 0.9 15.4 0.4 9.6 1.8 13.4 1.8 5.8 2.7 1h 22.6 2.3 17.8 2.7 14.4 7.9 13.3 1.2 5.7 1.2 2h 19.5 14.1 13.7 6.1 13.2 4.7 BA1a 30 min 19.1 4.3 15.1 0.1 18.3 0.9 15.2 0.2 17.6 1.3 15.4 0.8 (150-300 1 h 18.5 15.2 18.0 13.9 17.8 0.7 16.2 0.7 m) 2h 18.8 1.3 15.5 3.5 16.3 0.8 13.4 2.1 18.7 15.2

11 The most significant changes in the free lime and Ca(OH)2 contents typically occurred in the first 30 min of hydration in either liquid water or steam. There were only marginal fluctuations for extended periods of hydration at given temperatures.

3.1.2 SEM analysis Scanning Electron Microscope (SEM) photographs of the unhydrated and hydrated BA1b (300-600 m) are shown in Fig. 2. The unhydrated particles appear to have an outer shell, clearly seen in Fig. 2a. The shell was not fully sulphated, and consisted of a mixture of CaO and CaSO4, while the core was effectively pure CaO. The particles remained whole, showing little sign of being fractured or having started to disintegrate.

The particles that hydrated at 40 C for 30 min (Fig. 2b) had a cracked shell and some clearly discernable peripheral disintegration as a result of the hydration treatment. With hydration at 150 C for 30 min (Fig. 2c), the disruption or disintegration of particles appears to be more advanced. The sulphate shell around the particle is broken and cracks are found in the core, showing that hydration treatment affected both the shell and the core at these drastic conditions.

12

Figure 2. SEM photographs of bed ash (BA1b). (a) Unhydrated bed ash; (b) Hydrated with 40C water for 30 min; (c) Hydrated with 150C steam for 30 min

3.1.3 Re-sulphation of bed ash in TGA Re-sulphation results for hydrated bed ash are illustrated in Fig. 3. The samples hydrated at 5 C and at ambient conditions showed clearly increasing conversion trends with an increasing hydration time. At 60 C in water and 150 C in steam, however, longer hydration times were less effective in enhancing the SO2 absorption. For these samples, the most rapid increase in sulphate conversion occurred for hydration durations of 30

13 min to 1 hour. It can also be seen that the conversion increased with increasing temperature. One way of explaining these results is to note that hydration for this ash consists of a two-step process, a rapid hydration period which typically finishes in 10 minutes, followed by a much slower process that lasts for hours. For the rapid hydration period, the absolute amount of Ca(OH)2 produced increases at higher temperatures. In addition, hydration at higher temperature is associated with the development of a much greater degree of fragmentation in the bed ash particles. Therefore, it is easy to envisage, for short-term hydration at low temperatures, not only a lower absolute amount of Ca(OH)2, but also reduced mechanical damage to the particles sulphate shell due to expansion and dehydration, leading to a correspondingly lower reactivation; whereas longer hydration at lower temperature produces more Ca(OH)2, thus making more calcium available and enhancing ash reactivation. On the other hand, at higher temperatures, since more of the original CaO is already converted to Ca(OH)2 in the first 30 minutes, longer residence times are subject to the law of diminishing returns and produce only marginal gains. This finding is important for the practice of designing a real hydration system for reactivation of partially used CFBC ash.

14

90 CaO Conversion to CaSO 4, % 80 70 60 50 40 30 20 10 0 1 2 3 4 5 Hydration Time, h 60C Water Ambient 5C Steam 150C

Figure 3. The influence of hydration conditions on re-sulphation in TGA (sample: BA1a; re-sulphation temperature: 850 C; SO2 concentration: 5000 ppm; time: 90 min)

3.1.4 Discussion of fly ash Fly ash showed a very distinctive behavior upon sulphation when compared with the bed ash. The unhydrated FA had a very strong ability to absorb SO2, resulting in an apparent conversion of the remaining CaO greater than 110%. The explanation of these results is provided by the observation in the TGA that, when the fly ash was heated to 850 C in N2, a significant weight loss was observed starting from about 820 C. A detailed Fourier Transform Infrared/Thermogravimetric (FTIR/TG) test was conducted on FA held at 1000 C in helium for 15 min and it was found that 25% of the CaSO4 decomposed over this period because the char carbon (see Table 1) in the original FA acted as a reducing agent. This sulphate decomposition process causes the free lime content of the sample to be grossly underestimated and hence produces utilizations over

15 100%. In the re-sulphation tests of the FA, the temperature was, therefore, maintained at 850 C in N2 for about 1 h until completion of this decomposition occurred, before switching to SO2 for 90 min sulphation. An alternative measure of SO2 absorption based on mg SO2 absorbed/g sample was applied for the FA to compare the re-sulphation performance, as shown in Table 6.

Table 6. SO2 absorption capacity of FA after 90 min sulphation, mg SO2/g sample Unhydrated Hydration Temperature time Water Steam Ambient 60 C 200 C FA 510 30 min 510 467 487 1h 430 2h 415 4h 480 452

Hydration with either liquid water or steam caused no enhancement of the sulphur capture capability and, if anything, produced rather a deleterious impact despite the fact that unhydrated FA had the highest ability for SO2 absorption. The failure of fly ash to respond to reactivation agrees with the observation for bed ash by Laursen et al. (2000 and 2001a), that the existence of a well-defined core/annulus structure in the sulphated particle is optimal for reactivation, whereas fly ash particles are generally too small to have the core/annulus structure. This result also agrees with other earlier work. Couturier et al. (1994), who studied the reactivation of fly ash with both water and atmospheric pressure steam, failed to find any evidence that fly ash could be reactivated by hydration. Similarly, the work of Schmal (1985) showed that filter ash could not be reactivated by hydration, and even earlier work by Argonne National Laboratories (Johnson et al., 1981) also found that, for baghouse ash from the 6 x 6 FBC unit owned

16 and operated by Babcock and Wilcox, fly ash sulphation performance actually deteriorated following hydration treatment.

However, it should be noted that fly ash reactivation has been reported several times (e.g., Julien et al., 1995; Khan et al., 1995; Tsuo et al., 1999). In the first two cases the ashes examined came from small pilot-scale rigs, and so this may explain their results (i.e., particles are coarser than fly ash from a full-scale industrial boiler); in the last case, the tests were performed in a small industrial boiler, and a possible explanation is that, if the fly ash underwent some agglomeration during the hydration process, its residence time and utilization may have increased, even if this ash was not actually reactivated by hydration.

A significant amount of char carbon was observed in the fly ash (Table 1). In order to determine what effect this might have, the fly ash was heated in a crucible to 800 C for 2 h in air to remove char carbon and the resulting ash was subjected to limited hydration and re-sulphation tests; again, this material failed to show any indication that water can reactivate such pretreated ashes.

Fly ash often represents the majority of the solid ash product produced by a CFBC. Further, it tends to have relatively low sulphation levels, given its extremely short residence times in the boiler (typically seconds to minutes). This raises the question of strategies available for using it in a reactivation step. It has long been known that, since fly ash is extremely reactive (Lyngfelt and Leckner, 1991), it can be re-injected directly. However, this does not deal with the issue of short residence times. This work clearly

17 shows that hydration with either liquid water or steam is an ineffective strategy. This leaves pelletization of such material as one solution, and early CanmetENERGY work showed that this was an effective, although slightly expensive reactivation method (Anthony and Granatstein, 2001). The benefits of pelletization of fly ash have also been demonstrated at the industrial scale (Moe et al., 1995). However, there is a new way of carrying out this step, in a cost-effective manner, and this idea has been jointly patented by General Comminution and CanmetENERGY, and demonstrated with a small industrial CFBC boiler at Purdue University (Anthony et al., 2003). Here, the bed ash is wet ground to accelerate the hydration process, which occurs in a few minutes. The fly ash (or any other suitable material such as stoker ash) is then mixed into the resulting slurry to produce a dry pelletized material, which is then lightly ground and reintroduced into the boiler. In this way fly ash can be re-injected into the bed in a manner that is likely to increase its residence time without wasting energy by hydrating it.

3.2 Mini-CFBC test Five sorbents were tested in the mini-CFBC and the results are given in Table 7. It is not surprising that the untreated ash had a negligible sulphur removal capacity, because the partially sulphated particles had a CaSO4 layer on the surface, which prevented SO2 reaction with the unreacted CaO core. The sulphur capture capacity was greatly enhanced by water hydration. With as little as 10 % water added to the original ash, the SO2 removal efficiency achieved was 40 %. Interestingly, hydration with 30 % water did not produce a more positive result. It has been noted that with addition of 30 % water, the bulk of the ash was wet and sticky, requiring vacuum oven treatment to dry it, before re-introduction into the combustor. In contrast, with 10 % water, the ash was dry enough

18 that there was no difficulty in stirring it manually, which suggests that there would be no problem in using such a reactivation method industrially with these water addition levels. The agglomeration effect of the hydrated ash with 30 % water addition may cause difficulty for diffused SO2 in reacting with the available CaO. Table 7. Mini-CFBC test results Sample Ca/S molar ratio Non-treated ash 2.5 Reactivated by liquid 2.5 water (10 %) Reactivated by liquid 2.5 water (30 %) Addition of Na2CO3 2.5 powder (5 %) Addition of 20 % Na2CO3 2.5 solution (10 %)

Average bed temperature, C 834 827 14 823 844 830

Sulphur removal efficiency, % 3 40 1 23.8 0 30

When Na2CO3 was added in solution, the sulphur capture capacity was enhanced, but the extent was lower than that of reactivation with water. This indicates the water in the salt solution played a more important role in reactivation than did the Na2CO3. Another test result showed that there was no effect on SO2 removal efficiency if Na2CO3 was introduced as powder. All these results explain that reactivation simply with water is a practical way for re-use of the partially sulphated ash. To further increase the sulphur capture capacity, mixing of reactivated ash with fresh limestone could be applied. Laursen et al. (2001b and 2003) reported that very small amounts of Na2CO3 can produce sorbents with a high sorption capacity. However, all the promising results were conducted in a laboratory-scale fixed bed reactor with synthetic ashes. Performance in an actual FBC unit, such as CanmetENERGYs mini-CFBC, with real FBC ash may not be as favorable. Anthony et al. (2007) have recently reviewed literature on sorbent

19 reactivation, and showed that, from the work of many different authors, the addition of certain salts can indeed affect the performance of sorbents. One of the possible reasons that there was no effect when Na2CO3 was added as powder is related to sintering and pore blockage in the particles caused by the formation of melts, which may happen when adding solid Na2CO3 particles with limestone or FBC ash in coal firing conditions. This possible explanation will need further study for confirmation.

4. CONCLUSIONS CFBC ashes usually contain significant amounts of unreacted CaO when limestone is added into the combustor for in situ SO2 removal. The bed ash can be reactivated with either liquid water or steam. For ashes hydrated at ambient or lower temperatures, longer hydration times correspond to better sulphation performances, while at higher temperatures, longer hydration times produce only marginal improvements. The additional CaO conversion increases with increasing hydration temperatures at the given hydration time. The most significant changes of free lime and Ca(OH)2 content typically occurr within the first 30 minutes of hydration.

The original fly ash contained a significant amount of char carbon and the CaSO4 decomposed to a large extent in the heating process (820 ~ 850 C) prior to re-sulphation. Moreover, there was no significant evidence of reactivation due to any hydration treatment attempted for the fly ash. Because fly ash is extremely active without hydration, if this ash stream is to be utilized it might be used directly rather than being hydrated. Pelletization is one of the possible options for the reuse of fly ash.

20 With the sorbents tested in CanmetENERGYs 75 kWth mini-CFBC, the sulphur capture capacity was significantly enhanced by hydration with 10 % water. Increasing the percentage of water used for reactivation failed to show any more positive results, possibly due to the agglomeration effect during hydration. Although promising results were reported based on laboratory-scale tests with synthetic samples, reactivation of CFBC ash with either Na2CO3 powder or solution was not favorable in the mini-CFBC. The most practical way to reuse partially sulphated ash is reactivation with water, either as liquid or steam.

5. Acknowledgments

The authors would like to thank Mr. William Richards of Nova Scotia Power for supplying the bed ash and fly ash samples used in this work. Assistance from Professor Julio Iribarne of the University of Toronto for SEM analysis is gratefully acknowledged.

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21 Reactivation of partially-sulfated limestone particles from a CFB combustor by hydration. Canadian J. of Chemical Engineering, 72 (1994), 91-97. Julien, S., Brereton, C. M. H., Lim, C. J., Grace, J. R., Chiu, J. H. and Skowyra, R. S.: Spent sorbent reactivation using steam. Proceedings of the 13th ASME Fluidized Bed Combustion Conference, pp. 841-848, Orlando, FL, May 7-10, 1995. Johnson, I., Myles, K. M., Fee, D. C., Moulton, D. S., Shearer, J. A., Smith, G. W., Turner, C. B. and Wilson, W. I.: Exploratory and basic fluidized-bed combustion studies. Argonne National Laboratory Report ANL/FE-82-4, Annual Report October 1980-September 1981 (1981). Khan, T., Kuivalainen, R. and Lee, Y. Y.: Improving limestone utilization in circulating fluidized bed combustors through the reactivation and recycle of partially utilized limestone in ash. Proceedings of the 13th ASME Fluidized Bed Combustion Conference, pp. 831-840, Orlando, FL, May 7-10, 1995. Laursen, K., Duo, W., Grace, J. R. and Lim, J.: Sulfation and reactivation characteristics of nine limestones. Fuel, 79 (2000), 153163. Laursen, K., Duo, W., Grace, J. R. and Lim, J.: Characterization of steam reactivation mechanisms in limestones and spent calcium sorbents. Fuel, 80 (2001a), 1293-1306. Laursen, K., Grace, J. R. and Lim, J.: Enhancement of the sulfur capture capacity of limestones by the addition of Na2CO3 and NaCl. Environmental Science & Technology, 35 (2001b), 4384-4389. Laursen, K., Kern, A. A., Grace, J. R. and Lim, J.: Characterization of the enhancement effect of Na2CO3 on the sulfur capture capacity of limestones. Environmental Science & Technology, 37 (2003), 3709-3715. Lyngfelt, A. and Leckner, B.: Sorbent size reduction and conversion versus particle size in fluidized bed boilers. Proceedings of the Institute of Energys Fifth International Fluidized Bed Combustion Conference, pp.179-190, London, UK, December 10-11, 1991. Moe, T., Mann, M. D., Hajicek, D. H., Henderson, A. K., Swanson, M. L. and Weiss, A. J.: Demonstration of pelletized fly ash reinjection for reduction of limestone consumption and ash disposal. Proceedings of the 13th ASME Fluidized Bed Combustion Conference, pp.1267-1274, Orlando, FL, May 7-10, 1995. Montagnaro, F., Salatino, P., Scala, F., Wu, Y., Anthony, E. J. and Jia, L.: Assessment of sorbent reactivation by water hydration for fluidized bed combustion application. Journal of Energy Resources Technology, 128 (2006), 90-98. Montagnaro, F., Nobili, M., Telesca, A., Valenti, G. L., Anthony, E. J. and Salatino, P.: Steam hydration-reactivation of FBC ashes for enhanced in situ desulphurization. Fuel, 88 (2009), 1092-1098. Schmal, D.: Improving the action of sulfur sorbents in the fluidized-bed combustion of coal. Ind. Eng. Chem. Process Des. Dev., 24 (1985), 72-77. Tsuo, Y., McClung, J. and Sellakumar, K.:

22 Improving limestone utilization in a commercial-scale circulating fluidized bed boiler through ash reactivation and recycle. Proceedings of the 15th International Conference on Fluidized Bed Combustion, paper no. FBC99-0131, Savannah, GA, May 16-19, 1999. Wu, Y., Anthony, E. J. and Jia, L.: An experimental study on hydration of partially sulphated FBC ash. Combustion Science and Technology, 174(10) (2002), 171-181. Wu, Y., Anthony, E. J. and Jia, L.: Experimental studies on hydration of partially sulphated CFBC ash. Canadian J. of Chemical Engineering, 81 (2003), 2000-2014. Wu, Y., Anthony, E. J. and Jia, L.: Steam hydration of CFBC ash and the effect of hydration conditions on reactivation. Fuel, 83 (2004), 1357-1370.