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Energy & Fuels 1999, 13, 390-395

Field Study on Ash Behavior during Circulating Fluidized-Bed Combustion of Biomass. 2. Ash Deposition and Alkali Vapor Condensation
T. Valmari, T. M. Lind, and E. I. Kauppinen*,
VTT Energy and VTT Chemical Technology, Aerosol Technology Group, P.O. Box 1401, FIN-02044 VTT, Finland

G. Sfiris and K. Nilsson

Vattenfall Utveckling AB, Energy Conversion, S-162 87 Stockholm, Sweden

W. Maenhaut
University of Gent, Institute for Nuclear Sciences, Proeftuinstraat 86, B-9000 Gent, Belgium Received April 17, 1998

Fly ash deposition on heat-exchanger surfaces during fluidized-bed combustion of biomass causes operational problems such as reduced heat transfer and corrosion of superheater tubes. Ash deposition and alkali vapor condensation were studied during circulating fluidized-bed combustion of forest residue in a 35 MW co-generation plant. A 70 ( 10% amount of fly ash was deposited on the heat-exchanger surfaces in the convective back pass between soot-blowing periods. Practically all the largest ash particles (d > 10 m) but only a small fraction of particles d < 3 m were deposited. The deposition efficiency of particles with a given size was not correlated with their elemental composition. About 50% of alkali chloride vapors (KCl and NaCl) were condensed in the convective back pass on fine-mode particles (d < 0.6 m) and the other 50% on the coarse-mode particles. Alkali chlorides were not effectively deposited since they were depleted in the largest (d > 10 m) ash particles.

Introduction Ash deposition during fluidized-bed combustion of biomass occasionally causes severe operational problems. In the convective back pass, ash deposition reduces heat transfer and may contribute to corrosion of superheater tubes leading to the increased need for tube replacements. During fluidized bed combustion, ash-forming compounds may either attach to the bed material or become released from the furnace as fly ash particles and inorganic vapors. Coarse ash particles (d > 1 m) include predominantly ash-forming constituents that were not volatilized during the combustion process. Fine ash particles in the submicrometer size range (d < 1 m) are formed from the volatilized ash fraction by nucleation and subsequent condensation.1 A fraction of the volatilized ash species condenses on the coarse ash particles. The concentration of condensed species in ash particles is lower for larger particles, since condensation is favored on small particles.2 During combustion of
* Author to whom correspondence should be addressed. VTT Energy. VTT Chemical Technology. (1) Flagan, R. C.; Seinfeld, J. H. Fundamentals of air pollution Engineering; Prentice-Hall: Englewood Cliffs, NJ, 1988. (2) Hinds, W. C. Aerosol Technology. Properties, Behavior, and Measurement of Airborne Particles; Wiley-Interscience: New York, 1982.

biomass, the fine mode has been found to consist mainly of alkali chlorides and sulfates.3,4 KCl and K2SO4 are usually the dominant species over NaCl and Na2SO4, since the potassium content in biomass is typically higher than the sodium content. Alternatively, vapors may condense directly on the heat exchangers or duct walls or form condensed compounds via chemical reactions. The deposition mechanisms are different for coarse ash particles, submicrometer ash particles, and vapors.5,6 The deposition velocity of coarse particles due to inertial and turbulent impaction is large, leading to an extensive deposition rate, assuming that all the impacted particles also stick on the surface. Fortunately, the sticking efficiency of coarse particles is limited. On the other hand, submicrometer particles are driven toward heat-exchanger surfaces mainly by thermophoresis and diffusion. However, these mechanisms are not as effective as impaction is for coarse particles. Thus,
(3) Christensen, K. A.; Livbjerg H. A Field Study of Submicron Particles From the Combustion of Straw. Aerosol Sci. Technol. 1996, 25, 185-199. (4) Valmari, T.; Kauppinen, E. I.; Kurkela, J.; Jokiniemi, J. K.; Sfiris, G.; Revitzer, H. Fly Ash Formation and Deposition During Fluidized Bed Combustion of Willow. J. Aerosol Sci. 1998, 29, 445-459. (5) Rosner, D. E. Transport Processes in Chemically Reacting Flow Systems; Butterworth-Heinemann: 1986. (6) Raask, E. Mineral Impurities in Coal Combustion; Hemisphere Publishing Corp.: 1985.

10.1021/ef9800866 CCC: $18.00 1999 American Chemical Society Published on Web 12/24/1998

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the deposition rate of submicrometer particles is expected to be smaller than that of the coarse ash, even if their sticking efficiency is high.7 Deposition of submicrometer alkali-rich particles or condensation of alkali vapors on the heat-exchanger surface may create a sticky layer that promotes the coarse particle retention on the deposit layer. Ash deposit becomes problematic if it is too tenacious to be removed by soot-blowing. The biomass ash tenacity is difficult to predict and is usually determined empirically.8,9 Enrichment of alkali chlorides, and in some cases alkali sulfates, has been observed in superheater deposits.8,10 The deposit was found to be harder, i.e., more difficult to remove, in straw-fired boilers if it was directly condensed on the surface or partially melted. The fraction of hard deposit was higher when the sulfur content in the deposit was high.10 The present paper is one in a series describing our experimental results from ash formation studies during a utility-scale circulating fluidized-bed combustion (CFBC) of two different biomass fuels in 1996-1997. Ash retention in the bed and fly ash characteristics upstream of the convective back pass during combustion of forest residue and willow are presented by Valmari et al.11 In the present paper, the ash deposition on the heat-exchanger surfaces is approached by comparing the fly ash characteristics upstream and downstream of the convective back pass. Information was obtained about condensation of alkali chlorides and ash deposition efficiency as a function of particle size and composition during combustion of forest residue. Results for willow have been presented by Lind et al.12 Experimental Section
Measurements were carried out for two consecutive days in a 35 MW circulating fluidized-bed combustion (CFBC) cogeneration plant (Figure 1). The gas temperature in the bed increased from 750 to 830 C on the first day and was about 780 C on the second day. Ash-forming constituents in the vapor and particle phases were collected with a filter sampling system upstream of the convective back pass, after the process cyclone (Figure 1). The flue gas temperature at the sampling station was 850 C on the first day and 830 C on the second day. A Berner-type low-pressure impactor (BLPI) was used for fly ash particle mass size distribution measurements. A more detailed description of the combustion process, analysis results for forest residue fuel, and the results from the measurements carried out upstream of the convective back pass are given by Valmari et al.11
(7) Jokiniemi, J. K.; Pyyko nen, J.; Lyyra nen J.; Mikkanen, P.; Kauppinen, E. I. Modelling Ash Deposition During the Combustion of Low Grade Fuels. Applications of Advanced Technology to Ash-Related Problems in Boilers; Baxter, L., DeSollar, R., Eds.; Plenum Press: New York, 1996. (8) Miles, T. R.; Miles, T. R., Jr.; Baxter, L. L.; Bryers, R. W.; Jenkins, B. M.; Oden, L. L. Boiler Deposits from Firing Biomass Fuels. Biomass Bioenergy 1996, 10, 125-138. (9) Baxter, L. L. Ash Deposition During Biomass and Coal Combustion: A Mechanistic Approach. Biomass Bioenergy 1993, 4, 85-102. (10) Jensen, P. A.; Stenholm, M.; Hald, P. Deposition Investigation in Straw-Fired Boilers. Energy Fuels 1997, 11, 1048-1055. (11) Valmari, T.; Lind, T. M.; Kauppinen, E. I.; Sfiris, G.; Nilsson, K.; Maenhaut, W. A Field Study on Ash Behaviour During Circulating Fluidized Bed Combustion of Biomass. 1. Ash Formation. Energy Fuels 1999, 13, 379. (12) Lind, T. M.; Kauppinen, E. I.; Sfiris, G.; Nilsson, K.; Maenhaut, W. Fly Ash Deposition Onto the Convective Heat Exchangers During Combustion of Willow in a Circulating Fluidized Bed Boiler. Presented at an Engineering Foundation Conference on The Impact of Mineral Impurities in Solid Fuel Combustion, Kona, Hawaii, November, 2-7, 1997.

Figure 1. Schematic view of the circulating fluidized bed boiler. Fly ash particle sampling locations upstream (1) and downstream (2) of the convective back pass are indicated. Flue gas temperature was decreased to 150 C in the convective back pass. Ash particles were collected after the convective back pass from the flue gas with an electrostatic precipitator (ESP). Heat-exchanger-tube surfaces in the convective back pass were typically cleaned by soot-blowing every second day. The frequency of the soot-blowing periods was determined by the flue gas temperature at the ESP inlet. However, during our measurements, soot blowing was carried out every morning. Fly ash was collected from the ESP hoppers and weighed several times each day. The collection time of ESP ash was 8 h during day 1 and 12 h during day 2. The ESP-collected ash represents a fraction of fly ash that was not deposited on the heat-exchanger surfaces between two sootblowing sequences. The BLPI was used for fly ash particle size distribution measurements also downstream of the convective back pass. A BLPI with a precyclone was located inside the flue gas duct (Figure 2). There were two important differences between BLPI setups at the two sampling locations. When sampling upstream of the convective back pass (850 C), the flue gas sample was cooled between the precyclone and the BLPI to about 100 C by dilution air causing vapor-phase species to condense on ash particles. On the other hand, downstream of the convective back pass, the flue gas temperature was low enough (150 C) that no cooling was needed. Also, precyclone cut diameters were slightly different (aerodynamic diameter 3 m at 850 C and 8 m at 150 C). Two measurements at 150 C with a sampling time of 2 min were carried out during day 1. The first measurement was carried out 1.5 h and the second one 3.5 h after the previous soot blowing in the convective back pass. The precyclone collection at 850 C was started 30 min after the latter measurement at 150 C. Two BLPI-samples at 850 C with sampling times of 9 and 10 min were collected during the precyclone collection that was carried out for 151 min. Two test samples were collected downstream of the convective back pass while the setup was tested under slightly different process conditions (25% higher boiler load). The precyclone contributed 10% of the total mass in one of the two test samples. Precyclone samples appeared to be too small for

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Figure 2. Particle mass size distribution measurement system downstream of the convective back pass. Particles with an aerodynamic diameter >8 m were collected on a precyclone. Particles <8 m were collected with a Berner-type low-pressure impactor located in-duct.
Table 2. Ratio of Fly Ash Particle Mass Concentrations Downstream and Upstream of the Convective Back Passa downstream/upstream, % <0.6 m mass Ca Si P K Na S Cl 98 111 104-113 104-111 97 107 132 86 >0.6 m 20-22 18-21 8-11 22-28 24-27 21-23 16-18 176-191 total 22-25 18-21 8-11 22-28 36-38 26-29 18-20 111-115

a The ratio was calculated from the BLPI-measurements with the shortest time interval (40 min).

Figure 3. Fly ash particle mass concentrations upstream (850 C) and downstream (150 C) of the convective back pass. The precyclone-collected coarse particles (<10% of the total mass) at 150 C are not shown.
Table 1. Fly Ash Particle Mass Concentrations (mg/Nm3) Downstream of the Convective Back Pass (150 C) during Day 1 Measured with the BLPI-Sampling System
<0.6 m 12:16 14:24 >0.6 ma 12:16 14:24 12:16 totala 14:24

mass 14 23 310-340 210-230 320-360 230-260 Ca 0.6 0.4 45-54 41-48 45-54 42-48 Si 0.08 0.06 8-12 7-9 8-12 7-9 P 0.12 0.08 7-10 7-9 7-10 7-9 K 4.5 7.4 10-11 10-11 14-16 17-19 Na 0.5 0.9 2.6-3.0 2.4-2.7 3.0-3.5 3.3-3.6 S 0.9 1.4 5.4-6.9 8.9-10.0 6.3-7.8 10-11 Cl 3.4 5.7 4.5-5.0 4.5-4.9 7.9-8.5 10.2-10.6

ing day 2 was carried out to evaluate the elemental composition of the precyclone fraction. The elemental contents of the precyclone sample and the size-classified BLPI-samples were analyzed with particleinduced X-ray emission (PIXE) and instrumental neutron activation analysis (INAA). PIXE was used for Si, P, and S, INAA for Na, and the average of the two methods for Ca. K and Cl were analyzed from the precyclone sample by INAA, whereas the average of the two methods was used for BLPI samples. Samples for scanning electron microscopy (SEM) were collected downstream of the convective back pass on polycarbonate (Nuclepore) filters. Samples were coated with platinum and analyzed with a field-emission scanning electron microscope (FE-SEM, Leo DSM 982 Gemini) equipped with an energy-dispersive X-ray analyzer (EDS, Noran Voyager 3).

Results and Discussion The fly ash mass concentration was 1050 mg/Nm3 upstream of the convective back pass during day 1, as detected with the BLPI. The particle size distribution was bimodal (Figure 3) with a coarse mode in the size range of 0.5-100 m, which included 98% of the total particulate mass. The fine-mode fraction consisted mainly of alkali chloride vapors that were condensed during quenching.11 Coarse Ash Deposition on the Heat-Exchanger Surfaces. The ash accumulation rate on the ESP-

Minimum and maximum limits are calculated assuming 0% and 10% of the total mass in precyclone, respectively. Elemental composition of the precyclone fraction is based on a separate collection carried out during day 2.

weighing (<10% of the total mass) or for chemical analysis in the other test sample and in the two actual samples. Therefore, minimum and maximum limits for precyclone sample mass were calculated assuming 0% and 10% of the total mass in precyclone, respectively. A separate precyclone collection dur-

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Figure 4. Elemental mass size distributions upstream (850 C) and downstream (150 C) of the convective back pass. The precyclone contributions (d > 2 m) at 850 C are deduced as products of the measured total mass size distribution curve and the analyzed contents of each element in the non size-classified precyclone sample.

hoppers was 19 kg/h during day 1 and 27 kg/h during day 2. These values represent only 24% and 35% of the calculated fly ash flow rate (78 kg/h during both days). The calculated fly ash flow rate was the difference of the feed rate of ash-forming constituents with the fuel and the removal rate of the fuel-originated ash with the bottom ash. During day 1, the mass concentration downstream of the convective back pass according to the BLPI was 320-360 mg/Nm3 1.5 h after the previous soot blowing and 230-260 mg/Nm3 2 h later (Table 1). The ash flux calculations and the BLPI measurements show that about 70 ( 10% of the fly ash was deposited on the heat-exchanger surfaces. This fraction is then released during the next soot blowing. The estimated amount of ash accumulated in the convective back pass during the usual 48 h period between soot blowings was 2600 kg according to ash flux calculations. The fly ash mass concentration decrease in the convective back pass was clearly size-selective. The coarse-mode mass concentration was decreased by about 80%, as a consequence of impaction on the heat-

exchanger surfaces. Figure 3 shows that practically all the particles larger than about 10 m were deposited. The deposition efficiency decreases quickly as the particle size decreases from 10 to 5 m. It can be seen that most of the particles smaller than 5 m were not deposited, although the deposition efficiency in the size range of 1-5 m cannot be evaluated precisely due to different cyclone cut diameters at the two sampling stations. Si was most effectively deposited out of all the elements studied (90%, Table 2 and Figure 4). This is due to a fact that Si was enriched in the coarsest ash particles, which were deposited most effectively. There was 93% of Si found in precyclone-collected particles (d > 3 m) upstream of the convective back pass, whereas only 80% of the total mass was in that size range. Deposition efficiencies for Ca, P, Na, and S were approximately the same as the one for total mass, whereas K and especially Cl were deposited with much lower efficiency. The reason for the lower deposition efficiency of K and Cl is, again, found from the size

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distribution curves. K and Cl were depleted in the coarsest ash particles that were deposited with high efficiency. In fact, the elemental concentrations in ash were similar upstream and downstream of the convective back pass, within experimental accuracy. This indicates that the deposition efficiency of particles with the same size did not depend on their elemental composition. Alkali chlorides were an exception from this rule. Their behavior is discussed below. Condensation of Alkali Chlorides. Alkali chlorides (KCl and NaCl) were the only compounds predominantly present in the vapor phase upstream of the convective back pass. They were condensed during quenching of the flue gas sample. On the other hand, in the case of samples collected downstream of the convective back pass, alkali chlorides were condensed prior to sampling during flue gas cooling in the convective back pass. The different conditions during condensation resulted in different sizes of fine-mode particles. The mean size of the fine mode was 0.1 m in samples collected upstream of the convective back pass and 0.2 m downstream of the convective back pass (Figure 3 and size distributions for K, Na, and Cl in Figure 4). Rapid cooling by quenching favored formation of new ultrafine particles via nucleation. This resulted in smaller sizes and higher numbers of the fine particles in samples collected upstream of the convective back pass, as clearly indicated by the mass size distribution data. The similar experimental setup resulted in finemode particles of identical mean size at the two sampling stations during combustion of willow.12 In that case, the fine mode was dominated by alkali sulfates, which were already condensed before the first sampling station. The total chlorine concentration was not decreased in the convective back pass. About 70% of Cl was found in fine-mode particles in samples collected upstream of the convective back pass but only 50% in samples collected downstream of the convective back pass (Figure 4, Table 1). The high number of fine particles formed during quenching caused a higher fraction of alkali chlorides to condense on the fine particles. The fine-mode mass concentrations were 23 and 25 mg/Nm3 during the two measurements carried out upstream of the convective back pass. The concentrations detected downstream of the convective back pass were 14 and 23 mg/Nm3. The decrease in concentration was 23% as calculated from the averaged values but only 2% if calculated from the measurements carried out with the shortest time interval (40 min). The difference in concentration was caused mainly by the higher fraction of alkali chlorides condensed on coarsemode particles in samples collected downstream of the convective back pass, not by deposition or condensation on the heat-exchanger surfaces. In fact, the total Cl concentration downstream was 11-15% higher than upstream, indicating that the deposition efficiency of alkali chlorides was below the detection limit. Almost 90% of chlorine was found in particle size range d < 3 m, which was not effectively deposited. The concentration of a condensed species in particles is proportional to 1/d2 assuming that (i) particles are much larger than the gas mean free path, (ii) mass of the condensed species is small enough so that the

Figure 5. Cl concentration in fly ash in samples collected upstream (850 C) and downstream (150 C) of the convective back pass.

increase in particle diameter due to condensation can be neglected, and (iii) particles are spherical.2 The concentration of chlorine in ash decreased as the particle size increased, but the decrease was slower than 1/d2 (Figure 5). Assumptions i and ii were valid for the condensation of alkali chlorides in the supermicrometer size range. However, the supermicrometer particles were not spherical but agglomerates with a highly irregular surface structure, which possibly facilitated increased condensation on them.11 The theoretical prediction of the condensation rate on nonspherical particles is complicated and beyond the scope of this work. Detailed information of the surface area and structure in each size fraction would be needed. The Cl concentration in the precyclone, located in-duct at 850 C, was very small because alkali chlorides were not yet condensed at that temperature. It should be noted that our results concerning Cl include only compounds that were found in the condensed form in our samples, i.e., alkali chlorides. The reactions of gaseous Cl compounds (HCl) on the deposit layer may have resulted in retention of Cl on the heat exchangers. Fine Particle Morphology and Composition. Most of the fine fly ash particles were spherical or rounded (Figure 6). Some of them had a slightly rectangular shape, suggesting crystalline structure. The major elements in fine particles downstream of the convective back pass were K (average of two BLPI measurements 39%) and Cl (30%). The SO42- contribution was 23%, assuming that all the sulfur detected was present as sulfate. The other elements contributing to more than 1% of the fine ash were Na (5%) and Ca (3%). Here we have compared the elemental concentrations to the total concentration evaluated by adding up the measured elemental concentrations, including oxygen assumed to be bound in SO42-. The contributions sum to 83% of the mass evaluated by weighing the substrates, indicating a slight difference between gravimetric and elemental analysis results. The molar ratio (K + Na)/(Cl + 2S) should be equal to 1 if all four elements were present only as KCl, NaCl,

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Figure 6. SEM micrographs of fine-mode fly ash particles (diameter about 0.1 m) collected downstream of the convective back pass.

K2SO4, and Na2SO4. The values in the two BLPI samples were slightly under 1 (0.90 and 0.93). However, the molar ratio of interest is (K + Na + 2Ca)/(Cl + 2S) when it is assumed that Ca in the fine ash was present as CaSO4. The values of this molar ratio were 1.11 and 1.01. The molar ratio was not significantly larger than unity, indicating that other alkali compounds, e.g., carbonates, were not common in the fine ash. Conclusions The fly ash behavior in the convective back pass during circulating fluidized-bed combustion of forest residue was studied experimentally in a 35 MW power plant. The fraction of K and Na that entered the convective back pass as vapor-phase compounds was condensed as chlorides (KCl and NaCl). About 50% of the alkali chlorides were found in the fine-mode particles (d < 0.6 m) and the other 50% in the coarsemode particles. There was 70 ( 10% of fly ash deposited on the heatexchanger surfaces in the convective back pass between two soot-blowing sequences. The ash deposition efficiency was found to depend on the particle size during our measurements carried out 1.5-3.5 h after the previous soot blowing. Practically all of the largest ash particles (d > 10 m) were deposited by impaction on the heat-exchanger surfaces. In contrast, only a small fraction of particles smaller than 3 m was deposited. The deposition efficiency of particles with a given size was not found to be correlated with their elemental composition. The ash species which were volatilized and condensed (alkali chlorides) were not deposited efficiently, because condensation was favored on the fine particles. However, volatilized ash species may also deposit efficiently. Vapors may chemically react with coarse ash particles which are deposited with high efficiency. This was the case with sulfur. There was 80% of the sulfur in fly ash deposited, even though sulfur was volatilized during the process. The volatilization was evidenced by small retention of sulfur in the bed.11 The behavior of sulfur was totally different during combustion of willow at the same plant under process conditions essentially similar to the ones during the forest residue measurements.12

More than 50% of sulfur in the fly ash was present as fine alkali sulfate particles during the willow measurements. Consequently, the deposition efficiency of sulfur in the convective back pass was lower than the average fly ash deposition efficiency. In fact, the behavior of sulfur was the most significant difference observed between the two fuels. At first sight, the small deposition efficiency of potassium and especially of chlorine would seem to be in disagreement with the earlier findings that alkali sulfates and chlorides are enriched in superheater deposits when burning biomass with high alkali content.8 However, the effect of periodic soot blowings have to be considered when studying the long-term behavior of ash deposits. Soot blowing removes most of the deposit but not necessarily the innermost deposit layer, which may be enriched with alkali compounds. In addition, the reactions of gaseous Cl species with the deposit could also lead to enrichment of chlorine on the deposit. Finally, since about 70% of the fly ash was deposited in the convective back pass, it is proposed that the emission taking place during soot blowing is of major interest when studying the fly ash behavior and the performance of gas cleaning devices. Acknowledgment. This study was funded by Finnish Technology Development Center (TEKES), VTT Chemical Technology, and Foster Wheeler Energia via the LIEKKI 2 national combustion research program as well as by the Commission of European Community, Vattenfall Utveckling AB, and VTT Chemical Technology via Joule 3 (Contract No. JOR3-CT95-0001). We acknowledge the discussions with Mr. Jouni Pyyko nen, Dr. Jorma Jokiniemi, and Dr. Jouko Latva-Somppi from the VTT Aerosol Technology Group, Dr. David P. Brown for carefully revising the manuscript, as well as the contribution of the power-plant operating staff. W. Maenhaut is indebted to the Fonds voor Wetenschappelijk Onderzoek-Vlaanderen for research support. He is also grateful to J. Cafmeyer and K. Beyaert for assistance in the chemical analyses.
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