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Combustion of Different Types of Biomass in CFB Boilers

Matti Hiltunen RD Partners Kotka, Finland

Vesna Barii, Edgardo Coda Zabetta Foster Wheeler R&D Department Varkaus, Finland

Presented at 16th European Biomass Conference Valencia Spain June 26, 2008

COMBUSTION OF DIFFERENT TYPES OF BIOMASS IN CFB BOILERS Hiltunen, M., Senior adviser, RD Partners, Virsumaentie 91, FI-48600 KOTKA, Finland, matti.hiltunen@rdpartners.fi Barii, V., Senior Researcher, Foster Wheeler, Relanderinkatu 2, FI-78201 VARKAUS, Finland, vesna.barisic@fwfin.fwc.com Coda Zabetta, E., Research Manager, Foster Wheeler, Relanderinkatu 2, FI-78201 VARKAUS, Finland, edgardo.coda@fwfin.fwc.com ABSTRACT: The interest to use biomasses as fuels has increased strongly during the last years as a mean to reduce the CO2 emissions of energy production. Compared to conventional fuels like coal and peat, biomass fuels are more difficult. Fuel quality varies, moisture can be high, fuel handling and feeding are more demanding. With such problems, the most common technologies for industrial combustion of solid biomass fuels are: bubbling fluidized bed boilers (BFB), circulating fluidized bed boilers (CFB) and grate fired boilers. Of these, the technologies based on fluidized bed (BFB and CFB) are becoming increasingly popular. As a drawback, biomass-fired B/CFBs may suffer from bed agglomeration. Ash composition together with sulfur and chlorine contents in biomass fuels are the main factors having an impact on the risk of bed agglomeration in fluidized bed boilers, and on the rate of boiler fouling, deposit formation, slagging, and superheater corrosion. On the basis of ash composition, the biomass fuels can be divided into three groups having significant differences in combustion. This paper reviews in light of experience what are the main differences in fuel and ash properties and how the fuels from each group can be fired in CFB boilers. Keywords: biomass composition, ash, circulating fluidized bed (CFB) 1 INTRODUCTION 2 BIOMASS FUELS

The demand for biomass is growing and prices are increasing drastically. Thus, all types of biomass will be considered as fuels in the near future. Analyzing national and European policies as well as the targets for renewable energy, UNECE/FAO in cooperation with the University of Hamburg recently showed [1] that huge extra amounts of wood will be required in Europe in the future if the targets set by European Commission were to be met. Compared to conventional fuels like coal and peat, biomass fuels are more difficult. Fuel quality varies seasonally and regionally, moisture can be high, fuel handling and feeding are more demanding, and in biomass-fired boilers fouling, formation of deposits, slagging, and superheater corrosion are common problems. With respect to problems addressed above, the most common technologies for industrial combustion of solid biomass fuels are: bubbling fluidized bed boilers (BFB), circulating fluidized bed boilers (CFB) and grate fired boilers. Of these, the technologies based on fluidized bed (BFB and CFB) are becoming increasingly popular. However, biomass-fired B/CFBs may suffer from ashrelated problems. Ash composition together with sulfur and chlorine contents in biomass fuels are the main factors having an impact on the risk of bed agglomeration in fluidized bed boilers, and on the rate of boiler fouling, deposit formation, slagging, and superheater corrosion. On the basis of ash composition, the biomass fuels can be divided into groups having significant differences in combustion properties. This paper reviews, in light of experience, what are the main differences among biomass fuel groups in fuel and ash properties, and how the fuels from each group can be fired in CFB boilers.

The standard CEN/TS 14961 [2] classifies biomass resources in the following main categories: 1. Woody biomass, 2. Herbaceous biomass, 3. Fruit biomass, All categories also include sub-categories, intentional blends and unintentional mixtures. The standard reports technical specifications of properties for commercial fuels like wood pellets, briquettes, chips, sawdust, log wood, olive cake and straw bales. The specified properties include characteristics such as dimensions of the fuel, moisture, ash contents, bulk density, net calorific value, nitrogen and chlorine contents. The standard also lists typical values and typical variations of chemical properties for the solid biomass fuels. The properties include ash content, gross and net calorific values, main combustible elements (C, H, O, N, S), halogens (Cl and F), main ash forming elements and minor ash forming elements in dry fuel. The chemical properties are given for quite many solid biomasses like coniferous and deciduous woods and barks, logging residues, short rotation coppices, straws and grains of selected cereals, grasses, selected husks, stalks, trash and fruit biomasses. Even though an important information and data for various solid biomass fuels are given in standardized format, from the combustion point of view this classification is not able to quantify the fuel properties of various biomasses in sufficient detail. 3 ASHES OF BIOMASS FUELS

From the combustion point of view, biomass fuels can be divided into three groups on the basis of their ash composition:

1. Biomasses with Ca, K rich and Si lean ash 2. Biomasses with Si rich and Ca, K lean ash 3. Biomasses with Ca, K and P rich ash Most woody fuels belong to group 1. Rice husk, bagasse or spring harvested reed canary grass are examples of biomass fuels in group 2, sunflower seed and rapeseed cakes are fuels in group 3. 4 BIOMASSES WITH ASHES RICH IN CALCIUM AND POTASSIUM, LEAN IN SILICA Woody biomass fuels have low content of nitrogen (0,30,7 w-% in dry solids), sulphur (0,030,05 w-% in dry solids) and ash (0,16 w-% in dry solids) compared to many fossil fuels. Moisture contents of these fuels are often high, up to 5080 %, reducing net calorific value of fuel. The ash of woody biomass is typically rich in calcium (Ca) and potassium (K), see Table 1. The content of CaO in wood and bark ash is 3050 w-%, although large variations exist. K2O concentrations are up to 15 w-% in ash, but maximum values can be even higher. Also MgO is one of the main ash components in woody ash, 410 w-% in ash. The contents of sodium (Na) are usually low, Na2O is usually below 3 w-% in wood biomass ash. If Na2O contents are high, the reason is usually contamination, or the plants have been growing on salty soil. SiO2 exists naturally in some wood species like spruce and aspen. High contents of Al2O3 and SiO2 indicate contamination by aluminium silicates from soil [3]. The composition of biomass ash is strongly dependent on the species and part of the biomass plant, e.g. trunk, bark, braches, tops and needles have different ash compositions. The nutrients available, soil quality, fertilizers and weather conditions have also significant impact on the ash composition. Deviations of several tens of percent from the mean value of each element are common in biomass ashes. Table I: Examples of ash compositions of coal, peat, conifer bark and forest residue [4 ]. Coal and peat were ashed at 815 C while bark and forest residue at 575 C Polish coal SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O P2O5 Others w-% 47,7 23,8 9,5 3,8 2,9 2,4 1,1 0,4 8,4 Peat w-% 32,1 17,3 18,8 15,1 2,5 1,4 0,5 3,7 8,6 Bark Conifers w-% 4,8 2,8 1,5 45 5,2 8,0 0,9 4,2 27,6 Forest residue w-% 11,6 2,0 1,8 40 4,8 9,2 0,6 4,4 25,6

Olive cake, for example, belongs to this group of biomasses by its composition and combustion properties, although it is classified as fruit biomass in the CEN/TS 14961 standard. Biomass ashes are very fine, a few m in particle size. Ca- and K-containing ashes deposit easily on surfaces, causing fouling of e.g. superheaters, forming CaO, CaSO4 and K2SO4 rich deposits that harden if not removed frequently by soot blowing. The deposits can harden in the superheater area. In the economizer section flue gas temperatures are low, below 500C, and the deposits remain usually loose and easily removable by soot blowing. MgSO4 is not stable at the boiler conditions and it does not actively participate to the deposit formation. Chlorine in the fuel makes the fouling even worse, and induces the risk of high temperature corrosion in the superheaters. The chlorine content in trunk wood is low, 0,010,02 w-% in dry wood. In bark the chlorine content is slightly higher, 0,020,03 w-%. In forest residues (branches, tops of trees) and short rotation coppice like willow the chlorine contents are 0,020,03 w-%, i.e. at the same level with bark. The clear exception is eucalypt bark that can contain very high contents of chlorine. Concentrations up to 0,98 w-% have been analyzed, although normally the values are 0,20,3 w-%. During fluidized bed combustion potassium and calcium from biomass ash can react with quartz (SiO2) from the bed sand already at the normal operation temperatures of 700900 C, forming a layer of Ca,Ksilicate onto the bed particle. The layer becomes thicker in time, and the particle size increases. The layer is sticky, and the bed particles can agglomerate together increasing the bed particle size further. During unsteady operation of the boiler, or on an occasional excursion to high temperature, the whole bed can sinter. The bed agglomeration can be controlled by keeping the bed alkali contents low enough by regularly discharging the bed ash and feeding fresh sand into the bed. The chemistry of fuel ash - bed sand interactions is however complicated. It is usually useful to minimize the quartz contents in the make-up sand. The ash melting point temperatures of woody fuel ashes vary in a wide range. The wide range correlates with variations in ash composition. In general, the higher the fuel alkali and chlorine contents, the lower are the sintering and initial deformation temperatures. Wood ash starts to form agglomerates and to sinter between 900 C and 1000 C in combustion conditions. Coal and peat ashes are usually trouble free at these temperatures, even if the melting point temperatures are in the same range with biomass fuels. Coal or peat is cofired with biomass in many multi-fuel fired boilers. The woody biomass ashes are in general much more reactive than the ashes of fossil fuels. Lower reactivity of coal and peat ashes is connected to a composition with mainly quartz and various silicate-based minerals, like aluminium silicates, calcium silicates and alkali silicates, and iron oxides. Calcium and alkali in these minerals are not in free, reactive form like they are in biomass ashes. Accordingly they are quite inert at the conditions of fluidized bed combustion. Even though combustion of woody biomass fuels is more challenging compared to coal and peat wood

combustion technologies are nowadays well established owing to continuous boiler and material development. Thanks to a good operational practice developed by experiences, nowadays a number of woody biomass fired boilers are successfully operated by skilled operators with high availability, over 8000 h/a, for example in the pulp and paper industries. This know-how comes from a lot of learning. When woody biomass fuels are fired in high efficiency boilers with high steam temperatures and pressures, the negative properties of biomass fuels and their ashes are amplified. The boiler fouling, deposit formation and corrosion are elevated compared to coal or peat fired boilers. When firing woody biomass besides the composition of ash it is crucial to know reactivities of the ash components. Biomass fuels are often co-fired with other fuels. It is also important to understand the interactions of ashes and reactions of flue gas components with the ash components [5]. Virgin wood biomass fuels are commonly used in boilers of conventional design, i.e. principally similar than the boilers designed for fossil fuels. Radiative unprotected superheaters are used above the combustion zone. The final superheater stage is nowadays usually INTREX superheater in Foster Wheeler CFB boilers. The furnace and boiler are dimensioned to take into account the lower heat value of biomass fuel and higher flue gas flow rates. Steam temperatures up to 540 C and pressures over 100 bar are common. During the past 30 years Foster Wheeler has booked over 300 CFB boilers ranging from 7 to nearly 1000 MWth. Of these, nearly 50 are designed for biomass (co-)firing with a total cumulative capacity of 6247 MWth. Note that in this paper, peat is not included among biomass fuels. The boilers include industrial CFB boilers, utility boilers and hot water boilers. Figure 1 shows a modern biomass fired 240 MWth CFB boiler Sderenergi AB, Igelsta (92 kg/s, 540C, 90 bar) in Sdertlje, Sweden. The boiler will start operation in 2009, and it will be the largest biomass fired boiler in Sweden. The design fuels are biomass, recycled fuel pellets and demolition wood.

5 BIOMASSES WITH ASHES RICH IN SILICA, LEAN IN CALCIUM AND POTASSIUM The fuels in group 2 are very diverse by chemical composition and combustion properties. Most fuels in this group belong to herbaceous, or agricultural biofuels. Some of the fuels, like straws of cereals have also relatively high potassium (K) and chlorine (Cl) contents. Rice husk and bagasse have very high SiO2 contents in ash, see Table 2. Table II: Examples of ash compositions of wheat straw, rice straw, rice husk and bagasse [5, 6] ; ashed at 575 C Wheat straw w-% 59,9 0,8 0,5 7,3 1,8 16,9 0,4 2,3 10,1 Rice straw w-% 69,9 0,3 0,2 3,4 1,6 15,3 0,4 1,5 7,4 Rice husk w-% 95,4 0,1 0,1 0,4 0,3 1,8 0,0 0,5 1,4 Bagasse w-% 73,0 5,0 2,5 6,2 2,1 3,9 0,3 1,0 6,0

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O P2O5 Others

Figure 1: Cross-section of a modern biomass fired 240 MWth CFB boiler Sderenergi AB, Igelsta (92 kg/s, 540C, 90 bar) in Sdertlje, Sweden.

The composition of biomass ash is strongly dependent on the species and part of the biomass plant. The available nutrients, soil quality, fertilizers and weather conditions have significant impact on the contents of potassium, sodium, chlorine and phosphorus especially in agro-biomass ashes. In straw the content of potassium as well as the leachability of potassium (and sodium) correlate with chlorine content and leachability of chlorine. This property can be used to reduce alkali and chlorine contents of agro-biomasses during harvesting and storage. On rainy years the chlorine content in agrobiomass like straws is lower than in dry years. Watersoluble chlorides are partly washed away by rain. Time of harvesting is an important for multi-annual crops; for example, harvesting dry reed canary grass in spring in Northern countries produces crops with low content of chlorine and potassium compared to the autumn harvest. From the combustion point of view, the ash properties are significantly improved in spring harvested reed canary grass. Straws of cereals have about 510 w-% ash. SiO2 is the main ash component, but variations are large. The other main ash components are K2O 530 w-%, CaO 4 14 w-%. Occasionally, also Na2O and P2O5 contents are quite high, up to 10 w-% and 8 w-%, respectively. The chlorine contents in straws are high compared to woody fuels: up to 2 w-% in dry wheat straw has been analyzed. Chlorine content in rice husk is relatively low, commonly below 0,1 w-%, but in rice straws content of chlorine can be as high as 0,7 w-%. The ash melting properties of straws of cereals are challenging. The sintering temperatures are in the range 700900 C, and ash softening points below 1000 C. Complete melting happens often below 1200 C. From experience, straw is known as a reactive but difficult fuel with high fouling, slagging and corrosion properties.

The bed agglomeration mechanism during straw (type 2 ash) CFB combustion is different compared to woody biomass (type 1 ash) fired boilers. During straw combustion the bed agglomeration is caused by separate sticky and partly molten ash particles, and not by a sticky alkali and calcium silicate layer that is gradually formed on the bed particles like during wood combustion. The molten straw ash particles consist on potassium chloride and low melting potassium silicates formed in reactions between potassium and silica present inherently in the fuel ash. Therefore, the quality of bed material does not have any significant impact on the bed agglomeration rate with fuels like straw [8]. Foster Wheelers 77.5 MWth CFB boiler in Gren, Denmark (29 kg/s, 92 bar, 505 C) has been co-firing straw with coal since 1992. Shredded straw is blown pneumatically into return legs below the two hot cyclones. The straw is mixed with the hot circulation material flowing into furnace from the loop seals. At the beginning of the boiler operation, Gren CFB has experienced severe fouling and chlorine induced high temperature corrosion problems in the convective superheaters due to relatively high superheat temperature (505 C) of the steam. At late 1990s the final superheater in the convection cage was replaced with an INTREX superheater. Thereafter, superheater problems were significantly reduced. Straw firing in large-scale industrial CFB boilers is difficult, however it is feasible if co-fired in small shares with fuels like coal. Another fuel that belongs to the same type 2 ash is rice husk with the ash contents from 1525 w-% in dry solids, which is higher compared to many other biomass fuels. Rice husk ash contains over 90% SiO2 in most cases, making it very different from the straws of other cereals and even the rice straw ash. Potassium and calcium contents in rice husk ashes are low compared to rice straw, containing up to 15% K2O and 3,5% CaO. Thanks to its exceptional ash composition, the ash melting temperatures of rice husk are very high, about 1500 C. The armour-like SiO2 -based structure of rice husk remains during the ashing process, as Skrifvars et al. [7] have shown. They found that when rice husk was burned alone, ash particles did not stick onto heat-exchanger surfaces and caused no significant fouling or slagging. When co-fired with other fuels, the rice husk ash particles in the fly ash seems to be able to keep the boiler surfaces without fouling, even if a fouling fuel such as eucalypt bark is co-fired with rice husk. This cleaning effect by rice husk ash is probably more a physical effect than anything else [7]. Rice husk is commonly used as a fuel in countries farming rice. Grate firing and fluidized bed firing are in use. Rice husk is a special biomass fuel that can be cofired quite easily also in CFB power plants. It does not cause fouling or slagging, but has slightly erosive effect due to a large particle size and sharp edged SiO2 particles in ash. The erosivity of rice husk is high enough to sand blast to some extent the boiler when co-fired with for example wood bark that have ash with fouling propensity. Rice husk storing is difficult and it requires huge storage volumes due to a low bulk density. Therefore, rice husk is a seasonal fuel. In large boilers rice husk is

co-fired with other fuels like coal and bark. Foster Wheeler has supplied several such boilers in Asia, e.g. two 370 MWth CFB boilers in Tha Toom, Thailand (134/122 kg/s, 161/35 bar, 542/542 C). 6 BIOMASSES WITH CA, K AND P RICH ASH

Sunflower stalk ash and rapeseed expeller ash from food production are examples of the third type of agrobiomass ash, having K2O, CaO and P2O5 as the major ash components, see Table 3. Table III: Examples of ash compositions of sunflower stalk and rapeseed expeller [6, 9]; ashed at 575 C Sunflower stalk w-% 3,1 0,1 0,2 6,6 4,3 27,5 0,0 18,5 39,7 Rapeseed expeller w-% 0,0 0,0 0,3 15,0 9,0 22,8 0,0 41,1 11,8

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O P2O5 Others

The available nutrients, soil quality and fertilizers have significant impact on the contents of potassium, sodium and phosphorus in the ashes of this biomass group as well. Also these agro-biomasses contain some chlorine increasing the risk of chlorine induced high temperature corrosion of superheaters. The ash melting temperatures are in the same range as straw. Sintering may start at about 700 C, and the ash is completely molten below 1200 C. Sunflower residues and rapeseed cake are mainly used as cattle meal, and they have been not utilized much as a fuel. However, if the production of liquid biofuels from these plants will increase, also the use of residues from the fuel production may increase. According to quite limited combustion experience so far, these fuels are very fouling [9], but they can be cofired with coal in moderate shares in normal high efficiency CFB boilers [10]. There are also indications that combustion of high alkali, high phosphorous fuels is possible in CFB boilers with Ca-additive such as limestone. The role of limestone can be summarized as: 1) to provide calcium for the reaction with phosphorous forming high-temperaturemelting calcium phosphates instead of low-temperaturemelting potassium phosphates, and 2) to coat silica particles preventing the reaction of potassium (calcium) phosphates and silica originating from the fluidizing sand, which can form low-temperature-melting potassium (calcium) silicates, especially relevant for fluidized bed combustion conditions [11].

CONCLUSIONS

Solid biomass fuels can be ranked in three classes based on ash composition. The fuels in each group show similarities in fluidized bed combustion, e.g. in the mechanisms of bed agglomeration. Between the three groups fuels have significant differences in combustion properties. The ranking of the fuels based on ash composition is useful when the combustion properties of a biomass fuel are evaluated and predicted. The classification is helpful also when ash reactions in multifuel systems are to be predicted. 8 [1] REFERENCES

Mantau, U. et al; Wood resources availability and demands. Implications of renewable energy policies. UNECE/FAO policy forum on Opportunities and impacts of bioenergy policies and targets on the forest and other sectors: what is the future contribution of wood to meeting UNECE regions energy needs? , Geneva, 10 Oct. 2007. [2] CEN/TS 14961, Solid biofuels Fuel specifications and classes. [3] Werkelin, J., Distribution of ash-forming elements in four trees of different species. Masters thesis. report 02-5. bo Akademi, Faculty of Chemical Engineering, Process Chemistry Group, 2002. [4] Alakangas, E; Suomessa kytettvien polttoaineiden ominaisuuksia (Properties of fuels used in Finland), VTT Research Notes 2045. Espoo 2000. (in Finnish). [5] Hupa, M.; Ash behaviour in fluidized bed combustion recent research highlights. Circulating Fluidized Bed Technology IX, May 1316, 2008. Hamburg, Germany. Proceedings. p.845856. [6] http://www.ecn.nl/phyllis/ Database for composition of biomass and waste. [7] Skrifvars, B-J et al; The fouling behavior of rice husk ash in fluidized-bed combustion. 2. Pilot-scale and full scale measurements. Energy & Fuels 2005, Vol 19 No 4, p. 15121519. [8] Erhardsson, T. et al; Bed agglomeration risk related to combustion of cultivated fuels (wheat straw, reed canary grass, industrial hemp) in commercial bed materials. Vrmeforsk Report 998. Stockholm, November 2006. (in Swedish). [9] Nevalainen H. et al; Deposits and emissions during the co-combustion of biodiesel residue with coal and biomass in a CFB pilot. Circulating Fluidized Bed Technology IX, May 13-16, 2008. Hamburg, Germany. Proceedings.p.863 868. [10] Derda, P. et al; Fate of alkali metals during cocombustion of biodiesel residues with coal in a semi-industrial CFB boiler. Circulating Fluidized Bed Technology IX, May 13-16, 2008. Hamburg, Germany. Proceedings. p 857862. [11] Barii V. et al; The role of limestone in preventing agglomeration and slagging during CFB combustion of high-phosphorous fuels. To be presented at World Bioenergy 2008, 2729 May 2008, Jnkping, Sweden.

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