Fuel 83 (2004) 13711379 www.fuelrst.

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Ash behaviour in a pulverized wood red boilera case study

Bengt-Johan Skrifvarsa,*, Tor Laurena, Mikko Hupaa, Rob Korbeeb, Per Ljungc
a

Combustion and Materials Chemistry, Process Chemistry Centre, Abo Akademi University, Piispankatu 8, 20500 Turku, Finland b ECN, Petten, The Netherlands c Vattenfall Utveckling AB, Alukarleby, Sweden Received 5 March 2003; revised 13 January 2004; accepted 13 January 2004; available online 5 February 2004

Abstract The behaviour of the mineral matter in a fuel may crucially affect the availability of a boiler when the fuel is red. The ash may cause severe problems in the ue gas channel in forms of reside deposits on heat exchangers. These deposits lower the efciency of the boiler and cause in the most severe cases an unscheduled shutdown. In this paper we report results from a study where the ash behaviour was monitored in a pulverized wood red boiler. Short-term deposit sampling was combined with in situ y ash and ue gas sampling as well as advanced fuel analyses. By combining these three tools we could track down a chain of events the ash went through from the point where it was introduced into the boiler with the fuel until the stage where it formed a deposit on a heat exchanger tube. Sub-micron sized ash particles found in the ue gas with a Berner-type low-pressure impactor were enriched in alkali, sulphur and chlorine. Similar particles were also found on the backside of the air-cooled deposit sampling probes, forming thin initial alkali, sulphur and chlorine-rich deposit layer. These elements were further found by advanced fuel analysis to be associated with the moisture or the organic phase of the fuel. Larger ash particles of the size of 1 10 mm found in the ue gas with the low-pressure impactor were found to deposit on the front side of the sampling probe. These particles consisted mainly of calcium, most likely oxide or carbonate. With the advanced fuel analyses we could nd these particles already as mineral particles in the wood fuel. We also saw some indication that peat could act as a cleaning fuel. In general the results show that a detailed well-performed fuel analysis is a key knowledge when ash behaviour predictions are to be made. q 2004 Elsevier Ltd. All rights reserved.

1. Introduction The interest in ring biomass and waste alone or in combination with other fuels for heat and/or power production has increased continuously during the past 5 years. One driving force is the CO2 neutrality of these fuels. Another is that they represent a new fuel potential for the energy production. However, one great concern when ring these opportunity fuels or mixes of them is the behaviour of the mineral matter in the fuel. During combustion, the ash may crucially affect the availability of a boiler by causing severe reside deposits on heat exchangers. These deposits lower the efciency of the boiler and cause in the most severe cases unscheduled shutdown. Corrosion may
* Corresponding author. Tel.: 358-2-215-31; fax: 358-2-215-4962. E-mail address: bengt-johan.skrifvars@abo. (B.-J. Skrifvars). 0016-2361/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2004.01.008

additionally occur if the deposits contain aggressive constituents. Traditional methods to do ash-related research such as slagging, fouling and corrosion studies have included eld studies at full size boilers [1,2]. In such studies the aircooled probe technique has been a powerful tool [3 5]. By short-term deposit sampling with the air-cooled probe technique, researchers have gained information about the quantity and quality of deposition. Based on these data, more detailed and more phenomenological studies have then opened ways for more accurate descriptions of the mechanisms involved in slagging, fouling and corrosion. In slagging, fouling and corrosion studies also y-ash particle measurements have played an important role. The introduction of the on-line in situ particle amount and size measurement device, the low-pressure cascade impactor [6 8], opened even better possibilities to understand the particle behaviour in the ue gas channel of a combustor.

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With this device you could get quantitative size-segregated measurements of the y ash, as well as size-segregated compositional data of the ash particles [8]. The impactor complements well the short-term deposit probe measurements. A third area that has developed much during the last 15 years is the fuel analytics. Better analyses of the mineral matter in the fuel have opened ways to describe and predict more accurately the fuel mineral matter behaviour in a combustor [9,10]. In this paper we report results from a case study where the ash behaviour was monitored in a pulverized wood red boiler. Short-term deposit sampling was combined with in situ y ash and ue gas sampling as well as advanced fuel analyses to describe the monitored ash behaviour.

2. Experimental 2.1. The test runs The boiler in which the tests were performed is an 80 MWth down-red pulverized fuel boiler, for heat water production situated in Drefviken-Jorbro, Sweden. The measurement campaign consisted of eight different test runs, under which the fuel and boiler load were varied. The main fuel used was pellets or briquettes of wood, which were grinded into powder. The pellets were delivered by three different suppliers (referred to in the further text as Suppliers 1 3). In four test runs peat was added to the fuel. Furthermore, elemental sulphur was injected into the boiler in three test runs. One of the main ideas for using peat and elementary sulphur as additives to the main fuel was to see if there would be any effect of these additions on the ash and ash deposition behaviour in the boiler. The test runs are shown in Table 1 and the standard analyses of the used fuels in Table 2.
Table 1 The different test runs performed during the measurement campaign at Drefviken-Jorbro Test no. 1 Wood fuel Suppl. 1 Suppl. 2 Suppl. 1 Suppl. 2 Suppl. 3 Suppl. 2 Suppl. 1 Suppl. 1 Suppl. 1 Peat 3% S 0.1% S 0.1% Peat 5% Peat 5%, S 0.1% Peat 5% Additions Load (MW) 68 Remarks Fuel shift at approximately 13.00

For each test run a number of deposit probes were used. The deposit probes were equipped with detachable rings. A schematic picture of the boiler and the sampling locations is presented in Fig. 1. Deposit probes were used at four different positions in the boiler. In two of the positions (MP1 and MP2) the ue gas temperature was approximately 920 8C (average value from six deposition measurement periods) and in two positions (MP3 and MP4) approximately 740 8C (average value from 14 deposition measurement periods). Principles of the deposit probe are given in the literature [3 5]. During the measurement campaign, fuel samples and samples of precipitator ash were also taken for analysis, as well as in situ y ash sampling with a Berner-type lowpressure cascade impactor. These samplings were performed in the ue gas channel at a location where the ue gas temperature was approximately 400 8C. Principles of the Berner-type low-pressure cascade impactor as well as its use are given in the literature [6 8].

3. Results 3.1. Fuel ash, ESP ash and deposit samples Fig. 2 presents the deposition rates such as they were measured with the short-term deposit probes. The 100% wood chip ring case collected most deposits but also had the greatest scattering of the results. A decrease in deposit amounts seemed to take place when peat was added to the fuel. Also addition of elemental sulphur to the furnace seemed to decrease the amounts collected. Fig. 3 shows the results of the fuel ash and precipitator ash analyses. As can be seen the fuel ash does not differ very much in chemical composition from the ash sample taken from the precipitator catch (ESP) regardless of the fuel mix that was fed. The deposit samples did, however, differ signicantly, compared to the fuel ash. Fig. 4 presents the results of the chemical analyses of the deposits collected from the hotter locations MP1 and 2. The vertical line on top of each bar indicates the scattering of the value. In the front (wind) side deposits calcium was the dominant element. Some potassium, silicon, iron, and sulphur could also be found but no chlorine. In the back (lee) side deposits potassium was dominating and clearly higher shares of sulphur could be detected than in the front side deposits. Also chlorine was now found in signicant amounts, up to 10 wt% of the sample. An addition of peat to the furnace showed up as a small increase in silicon and sulphur content of both front- and backside deposits. The addition of sulphur showed up as a signicant increase in sulphur content, correspondingly. It also caused a clear drop in the chlorine content of the backside deposits. Fig. 5 presents the corresponding results from the colder locations MP3 and 4. Also here the front side deposits

2 3 4 5 6 7 8

65 75 32 75 64 67 40

Instable burning No gas analysis

B.-J. Skrifvars et al. / Fuel 83 (2004) 13711379 Table 2 Standard fuel analyses of the Jorbro fuels Peat Wood chips Suppl. 1 Moisture (wt%) Ash (wt% db) Volat. (wt% db) C (wt% db) H (wt% db) N (wt% db) S (wt% db) Cl (wt% db) O (wt% db), diff HHV (MJ/kg) 35.4 12.8 52.1 5.1 1.4 0.3 0.02 28.2 22.4 7.3 0.4 47.1 6.1 ,0.3 ,0.01 44.6 20.3 16.8 3.3 2.8 29.3 6.1 2.1 9.2 2.6 72.3 Suppl. 1 5.9 0.7 48 6 ,0.3 0.12 ,0.01 42.6 20.5 31.7 6.8 9.3 22.5 4.0 0.9 6.9 2.6 84.6 6.1 ,0.3 ,0.01 ,0.01 42.6 20.4 18.6 38.6 3.4 30.5 6.2 1.7 10.3 2.6 111.9 Suppl. 2 8.0 0.4 6.1 ,0.3 0.02 ,0.01 42.9 20.5 12.2 2.7 3.1 33.2 6.1 1.4 8.9 2.2 69.8 Suppl. 3 7.5 0.4

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3.2. Flue gas analyses During the test runs also FTIR analyses of SO2 and HCl were done. These results are shown in Fig. 6. As can be seen from the gure, an addition of peat to the wood chips did not change the amount of emitted SO2 and HCl much but the addition of 0.1% sulphur did. The obvious increase in SO2 emissions was accompanied by an increase also of HCl emissions. 3.3. In situ y ash sampling During the test runs Nos. 3 and 5 in situ y ash sampling was also performed at a location in the ue gas channel where the temperature was approximately 400 8C. These results are shown in Figs. 7 and 8. As can be seen from the gures, alkali sulphates and chlorides were enriched in the smallest sized particles, , 1 mm, while silicon was found in the largest particles, . 10 mm. Calcium seemed to be enriched in the size range 1 10 mm.

Ash analysis (wt% in ash) SiO2 48.5 12.2 Al2O3 Fe2O3 12.1 CaO 8.6 MgO 1.2 Na2O 0.03 K2O 1.6 P2O5 1 Sum 85.2

4. Discussion It is interesting to note that the 100% wood chips seemed to collect the highest amounts of deposits and that adding either peat or elemental sulphur to the furnace seemed to reduce the deposition rates (Fig. 2). The decrease in deposition rates caused by peat might be explained by an eroding (cleaning) effect of the peat ash. This seems to be supported by the fact that no signicant change could be seen in the chemical composition of the deposit when peat was added to the furnace, compared to the case when 100% wood chips were red alone. If the peat ash had affected the deposit chemically one would have expected to see a change in the deposit chemical composition. Erosion caused by silicate type ash is a known effect from coal ring [1]. The reason for the decreasing effect of sulphur addition on the deposition rate is not as clear. One possible

contained large shares of calcium. Potassium and sulphur could now be found in higher shares compared to the MP1 and 2 front side deposits. Also chlorine showed up now on the front side deposits in the MP3 and 4 samples. The backside deposits contained again higher shares of potassium and sulphur than the front side deposits and chlorine was again present in signicant shares. Addition of peat showed up again as an increase in silicon and sulphur content of front and backside deposits and the addition of sulphur increased again the sulphur content of both deposits. It also caused again a clear drop in the chlorine content of the backside deposits.

Fig. 1. A schematic view of the boiler.

Fig. 2. Deposition rates measured with the short-term deposit probe.

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Fig. 3. Fuel ash and ESP ash compositions of the wood chip ring case No. 1, wood chip peat ring case No. 8, and wood chip peat sulphur case No. 7 at Jorbro.

explanation to this effect could be a sulphation of the wood ash, which after this would not be as prone to stick on to a heat exchanger surface, as it would be in a non-sulphated form. This kind of effect is supported by the chemical analyses of the deposits. There is clearly the highest amount of sulphur in the deposits collected from the ring cases when elemental sulphur was added to the furnace. Comparing the in situ y ash sampling results with the short-term deposit samples (Figs. 9 and 10) one can see

a number of other signicant trends. For example, the results show very clearly that the smallest ash size fractions (, 400 nm) showed up on the backside of the deposit probes (Fig. 9) while the larger particles (1 10 mm) impacted on the front side of the deposit probes (Fig. 10). This behaviour is well known [1,11 13]. From the results it can also be seen that the chlorine did not reach the backside of the hotter probe (Tsurf 520 8C) but did reach the backside of the colder probe

Fig. 4. MP1 and 2 deposit sample compositions during the wood chip ring cases 1 and 5, wood chip sulphur cases 3 and 4, wood chip peat ring cases 2, 6 and 8, and wood chip peat sulphur case No. 7 at Jorbro. Tsurf 520 8C. Front side (wind) and backside (lee) deposits separately. The vertical line on top of each bar indicates the scattering of the analysis, based on 34 separately collected deposit samples.

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Fig. 5. MP3 and 4 deposit sample compositions during the wood chip ring cases 1 and 5, wood chip sulphur cases 3 and 4, wood chip peat ring cases 2, 6 and 8, and wood chip peat sulphur case No. 7 at Jorbro. Tsurf 520 8C. Front side (wind) and backside (lee) deposits separately. The vertical line on top of each bar indicates the scattering of the analysis, based on 3 4 separately collected deposit samples.

(Tsurf 320 8C). This can be seen when comparing the results presented in Figs. 3 and 4. It is further interesting to note that the known effect of SO2(g) to inhibit chlorine to form condensed alkali chloride compounds [14 16] can also be seen from the results, both in the deposit analyses (Figs. 3 and 4) as well as in the in situ y ash analyses (Figs. 7 and 8). When sulphur was added to the fuel, chlorine decreased in the smallest sized ash particles, disappeared completely from the deposit samples and increased in the ue gas as HCl (Fig. 6). To get some further information of the fuels we performed a chemical fractionation analysis on one of the wood chip fuels. The results from these analyses are shown in Fig. 11. In the fractionation analysis the fuel is leached successively with increasingly aggressive solutions, starting with water, continuing with ammonium acetate and nishing with hydrochloric acid. Depending on what ashforming elements are solved into the solvents, indications

can be made on how the ash-forming elements have been associated to the fuel. Details of this can be found in the literature [10,17 20]. In Fig. 11 the analysed ash-forming elements are shown on the x-axis and the amounts found in the three solutions as well as in the insoluble rest are shown on the y-axis. The y-axis values are expressed as mg per kg dry fuel. The cross on top of each bar indicates the total amount of an element analysed from the fuel while the top of the bar indicates the same, however, reached by analysing the element in the three solutions and the insoluble rest fraction. If the top of the bar matches the cross a good mass balance closure has been reached in the fractionation analysis.

Fig. 6. Flue gas analyses of SO2(g) and HCl(g) during the ring cases Nos. 1, 8, 7, 5, 3 and extra.

Fig. 7. In situ y ash sampling from the test run No. 5, 100% wood chips. All analyses were performed with SEM/EDS. The size fractions 30 nm, 4.0 mm, 6.8 mm, 10.3 mm were not analysed.

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Fig. 8. In situ y ash sampling from the test run No. 3, 100% wood chips 0.1% elemental sulphur. All analyses were performed with SEM/EDS. The size fractions 30 nm, 4.0 mm, 6.8 mm, 10.3 mm were not analysed.

Fig. 9. A comparison of the composition of the 60, 100, 170, 260 and 400 nm sized particles with the backside (lee) deposits collected at MP3 and 4 in the boiler during ring of wood chips alone.

Fig. 10. A comparison of the composition of the 1.0, 1.6, 2.5 and .10 mm sized particles with the front side (wind) deposits collected at MP3 and 4 in the boiler during ring of wood chips alone.

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Fig. 11. The chemical fractionation analysis of the wood chip fuel from Supplier 3, red in Jorbro alone or in combination with peat and/or elemental sulphur.

As can be seen from the results, all alkali and chlorine was solved out by water. Sulphur seemed to stay in the rest. This can be explained by the fact that sulphur usually forms covalent bounds, in this case most likely to the organic structure of the fuel and could therefore not solve out with any of the solvents used here. Calcium solved out completely in water, ammonium acetate and HCl. Almost no silica was solved out at all. We also performed SEM analysis on the fuel. In Fig. 12 we show a SEM micrograph of the same wood chip fuel as was analysed with the fractionation analysis. The surprising result from this analysis was that we could nd mineral grains, consisting of almost pure calcium in the wood

Fig. 12. SEM/EDS analysis of the wood chip fuel from Supplier 3 (above), red in Jorbro alone or in combination with peat and/or elemental sulphur. For comparison a similar analysis of Scandinavian bark (below) [18].

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structure, on top of other silicon-rich mineral grains, coming from dust, soil and dirt. Later analyses have shown that these kinds of calcium-rich mineral grains can also be found in bark fuels to a much higher extent than in pure steam wood [18,21]. There are further strong indications that these calcium-rich mineral grains consist of calcium oxalate and are released from the fuel as mineral particles of roughly 2 10 mm forming CaO particles at higher temperatures (. 800 8C), CaCO3 at lower temperatures (, 800 8C), the calcination carbonation temperature being dependent on the CO2 partial pressure [20]. The presence of these calcium-rich mineral grains in the fuel may also explain the calcium-rich ash size fraction of 1 10 mm that we measured in the boiler. It can also explain the front side deposits rich in calcium that we detected. It has earlier been shown that CaO particles can deposit on cooled tubes, forming deposits by rapidly carbonating (formation of CaCO3 from CaO) on the surface [22].

Acknowledgements This work was partly done within the EU nanced project JOULE JOR3-CT98-0198 Prediction of ash and deposit formation for biomass co-combustion and the Finnish TEKES national research program CODE (Combustion Development by Modelling). The nancial support is acknowledged. The fractionation analysis work was coordinated and performed by Dr Maria Zevenhoven. Her careful and signicant contribution to this work is gratefully acknowledged. Part of the results included in this paper were presented at the United Engineering Foundation Conference, Power Production in the 21st Century, Impact of Fuel Quality and Operations, October 28 November 2, 2001, Snowbird, Utah, USA.

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[1] Raask E. Mineral impurities in coal combustion. Behaviour, problems and remedial measures. New York: Hemisphere Publishing Corp.; 1985. [2] Bryers R. Fireside behaviour of mineral impurities in fuelsfrom Marchwood 1963 to the Sheraton Palm Coast 1992. In: Benson S, editor. Inorganic transformations and ash deposition during combustion, 1992. New York: United Engineering Trustees Inc.; 1992. p. 368. ISBN 0-7918-0657-X. [3] Crane WM, Lindsay AW, Thurlow GG. An air-cooled probe for the collection of deposits in coal-red boilers. J Inst Fuel 1955;28:291. [4] Jackson PJ, Raask E. A probe for studying the deposition of solid material from the uegas at high temperature. J Inst Fuel 1961;34:275. [5] Hupa M, Eriksson B-E, Klingstedt G. A rapid method for investigation of ash deposition in boilers. Pap Timber (Paperi ja Puu) 1978;60(11):719. [6] Newton GJ, Raabe OG, Mokler BV. Cascade impactor design and performance. J Aerosol Sci 1977;8:33947. [7] Berner A. Design principles of the AERAS low-pressure impactor. In: Liu BYH, Pui DYH, Fissan HJ, editors. Aerosols, science, technology and industrial applications of air-borne particles. New York: Elsevier; 1984. p. 139 42. [8] Kauppinen E, Pakkanen T. Coal combustion aerosols: a eld study. Environ Sci Technol 1990;24:18118. [9] Huggins FE, Kossmack DA, Huffman GP, Lee RJ. Scanning Electron Microsc 1980;1:531. [10] Benson S, Holm PL. Comparison of inorganic constituents in three low-rank coals. Ind Engng Chem Prod Res Dev 1985;24:145 9. [11] Hedley AD, Brown TD, Shuttleworth A. Trans ASME, Ser A, J Engng Power 1966;88:173. [12] Samms JAC, Watt JD. Br Coal Utilisation Res Assoc Monthly Bull 1966;30(7):225. [13] Reid WT. External corrosion and deposits, boilers and gas turbines. New York: Elsevier; 1971. [14] Skrifvars B-J, Lauren T, Backman R, Hupa M, Binderup-Hansen P. The role of alkali sulfates and chlorides in post cyclone deposits from circulating uidized bed boilers ring biomass and coal. In: Gupta R, Wall T, Baxter L, editors. Impact of mineral impurities in solid fuel combustion. New York: Kluwer Academic/Plenum Publisher; 1999. [15] Henriksen N, Larsen OH, Blum R, Inselman S. High-temperature corrosion when co-ring coal and straw in pulverized coal boilers and circulating uidised bed boilers. Presented at the VGB

5. Conclusions By combining short-term deposit sampling with in situ y ash and ue gas sampling as well as advanced fuel analyses, we could track down a chain of events the ash went through from the point where it was introduced to the boiler with the fuel until the stage where it formed a deposit on a heat exchanger tube. Sub-micron sized ash particles, found in the ue gas with the Berner-type low-pressure impactor, were enriched in alkali sulphur and chlorine. Similar particles were also found on the backside of the air-cooled deposit sampling probes, forming thin initial alkali sulphur and chlorine-rich deposit layers. These elements were found by chemical fractionation analysis to be associated with the moisture or the organic phase of the fuel. Larger ash particles of the size 1 10 mm, found in the ue gas with the low-pressure impactor, were found to deposit on the front side of the sampling probe. These particles consisted mainly of calcium, most likely carbonate. With the SEM/EDS analysis done directly on the fuel we could show that these particles most likely were present already as mineral particles in the wood fuel. We also got some indications that peat could act as a cleaning fuel. It was speculated that if its ash was of right type, i.e. contained a large enough number of silicate particles, that could stay inert in the furnace, they could act as eroding agents when passing through the heat exchanger tube packages. We could also again detect the effect of SO2(g) inhibiting the formation of condensed alkali chlorides.

B.-J. Skrifvars et al. / Fuel 83 (2004) 13711379 Conference of Corrosion and Corrosion Protection in Power Plants, Essen, Germany, November 2930, 1995. Michelsen HP, Larsen OH, Frandsen F, Dam-Johansen K. Deposition and high temperature corrosion in a 10 MW straw red boiler. Presented at the Engineering Foundation Conference of Biomass Usage for Utility and Industrial Power, Snowbird, Utah, USA, April 29May 3, 1996. Baxter LL. Task 2. Pollutant emission and deposit formation during combustion of biomass fuels. Quarterly Report to National Renewable Energy Laboratory, Sandia National Laboratories, Livermore, California, USA, 1994. Zevenhoven M. Ash forming matter in biomass fuels. Report 01-03. PhD thesis. Abo Akademi University; 2001. Skrifvars B-J, Blomquist J-P, Hupa M, Backman R. Predicting the ash behaviour during biomass combustion in FBC conditions by

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combining advanced fuel analyses with thermodynamic multicomponent equilibrium calculations. Presented at the 15th Annual International Pittsburgh Coal Conference, Pittsburgh, PA, USA, September 1998. [20] Zevenhoven M, Skrifvars B-J, Yrjas P, Hupa M, Nuutinen L, Laitinen R. Searching for improved characterization of ash forming matter in biomass. Proceedings of the 16th FBC Conference, Reno, Nevada, USA, May 2001. [21] Lopez C, Korbee R, Skrifvars B-J, Frandsen F, Little J. EUproject. Prediction of ash deposit formation for biomass PF cocombustion. To be presented at the Engineering Foundation Conference on Ash Deposition, Snowbird, Utah, USA, October 28November 2, 2001. [22] Skrifvars B-J, Hupa M, Hyoty P. Superheater fouling in coal-red boilers due to limestone injection. J Inst Energ 1991;64:12.