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The ash composition

Ash is the general term used to describe the inorganic matter in a fuel. In biomass fuels, the ash content may originate from the biomass itself, e.g. materials that the plant absorbed from the water or the soil during its growth, or from the supply chain, e.g. soil collected along with biomass. In any case, after the collection of a sample the ash content is typically measured by combusting the biomass at a laboratory furnace under controlled conditions, taking into account the relevant standard EN 14 !. It is important to notice that the ashing temperature for biomass fuels is !!" #$, lower than the typical ashing temperature for coals, which is %" #$, &he reason is that biomass ash contains several volatile elements which may not be present in the laboratory produced ash if it is combusted in high enough temperatures. &hus, high temperatures for ash mean a non' representative ash sample, both in terms of (uantity and (uality. It is also fairly obvious that ash collected from real'life application will differ in some e)tent in composition from the fuel ash prepared in the laboratory. *enerally, the ash content of herbaceous biomass is higher than that of woody biomass. +hile ash weight content ,in dry basis- values of less than 1. are e)pected for wood, different herbaceous biomass types have reported values ranging from less than /. up to % 0 1" . or even up to /!. for rice husks. In waste fractions, the ash content may often be as high as 1"'!" . and is only scarcely less than 1" .. 2owever, in waste streams, the ash may well be constituted by glass, ceramics and other substances that have had a household or industrial use but have been erroneously sorted into the combustible fraction. Apart from the supply chain impact, the ash content is heavily dependent on plant type and growing conditions. +ater uptake for e)ample is directly related to uptake of 3i and other inorganic elements in the plant. &hus, $1 plants which have on average higher water uptake compared to $4 plants also tend to have higher ash contents. ,you may want to refer to section "1' ""'"/a-. 2owever, some $1 plants such as cardoon have been widely reported to have an ash content of %. wt db or more. &he use of fertili4ers also affects the ash content in herbaceous biomass, particularly with regard to elements such as potassium, chlorine and phosphorus. 3oil conditions and 0composition also plays an important role in virgin biomass. 3ome researchers have indicated that switchgrass growing on sandy soils resulted in lower overall ash and potassium content compared

to switchgrass grown on clay soils. &herefore, the level of soluble inorganic elements in a soil is important. 5inally, the ash content and composition of a plant tends to vary depending on the part of the plant. 6eaves for e)amples typically contain higher amounts of ash than stems. 5ollowing the preparation of a laboratory ash sample, European 3tandards e)ist for the determination of two main groupings of elements7 minor elements and ma8or elements. Minor elements should be measured according to EN 1!/9 . &hey include the following elements7 As, $d, $o, $r, $u, 2g, :n, :o, Ni, ;b, 3b, < and =n. &he term >minor> stems from the very small concentrations in which they are typically found in the fuel. &heir measurements relates mostly to environmental concerns, e.g. whether the ash contains any to)ic elements, such as mercury, chromium or cadmium, that may return to the environment upon its disposal. ?ther elements, such as =n, may have a role in the formation of aerosols or a minor impact on fouling issues. :inor elements are typically e)pressed as ,mg @ kg- of fuel on a dry basis. Major elements should be measured according to EN 1!/9". &hey include the elements which are most abundant in the fuel ash7 Al, $a, 5e, :g, ;, A, 3i, Na and &i. No significant environmental issue is associated with these elements, however they have a ma8or impact on the ash melting behaviour, slagging@fouling and corrosion. 2igh concentrations of some elements may indicate fuel contamination with soil or sand. &he most important of the above elements are important plant nutrients7 3i, $a, A ,the most important macronutrient after nitrogen-, Na and ;. &here are several ways to e)press ma8or elements7 ,mg@kg- of fuel on a dry basis or as weight percentages in the fuel ash. A tradition left from the use of empirical indices originally developed for coal is to e)press the concentration of ma8or elements as their corresponding o)ides. &he conversion of the weight concentration of a ma8or element to its o)ide is easy if one uses the ration of the o)ide molecular weight to the element atomic weight, as described in EN 1!/9". +eight concentrations of ma8or elements vary greatly between biomass species. &ypically, herbaceous biomass has higher concentrations of silica and lower concentrations of calcium compared to woody biomass. In addition, the alkali concentrations ,A and Na- of herbaceous biomass is (uite high. &he combination of high silica and alkali content is especially problematic, as will be described in section "4'"/'"/a and "4'"/'"/b. 6iterature sources provide a wide range of values, however the impact of growth conditions and supply chains result in (uite different reported for the same biomass type.

Another type of measurement that can be performed in the fuel ash is the determination of the ash melting temperature. &his will also be discussed in more detail in section "4'"/'"/.

Other methods to describe the ash


Apart from the measurements described in the standards, a common laboratory characteri4ation of fuel ash is the determination of mineral composition through B'Cay Diffraction ,BCD- 3pectroscopy. &his method may reveal the presence and relative concentration of different mineral phases. 5or e)ample, it can be determined whether potassium is chemically bound with chlorine in the form of sylvine or with sulphur in the form of arcanite. &here are no standardi4ed guidelines on how to evaluate the results of an BCD analysis for biomass, but if such info is available it can be used by e)perienced technicians and engineers for the design of a better system as certain minerals are associated with erosion or slagging issues. &he European 3tandards for solid biofuels also include EN 1!1"! E3olid biofuels ' Determination of the water soluble chloride, sodium and potassium content>. $hlorine, potassium and sodium are commonly found in the form of water soluble salts which, during combustion, are readily released in the gas phase. An analysis according to this standard may therefore provide an indication of the aggressive content of these elements, in relation to potential slagging and fouling problems. In addition, such chemical are more ease to remove by leaching the fuel. Although in some biofuels the water soluble content of these elements is practically the same as the total content, this is not always the case. 5or the total content, standards EN 1!/9" and EN 1!/%9 apply.

Slagging and fouling


In combustion systems, the heat released from the fuel o)idation is typically transferred to a working medium, such as steam or hot water, which is used for power, heat or cooling demands. &he hot flue gas is not in direct contact with the working mediumF the energy transfer is achieved through heat e)changing e(uipment, such as tubes. ?ptimally, both sides of the tube should be clean in order to achieve the ma)imum rate of heat transfer under the conditions. In practice though, deposits do get formed, especially on the flue gas side. &his problem is most common in solid fuel combustion systems, due to their high ash content compared to li(uid or gaseous fuels.

Deposits add a thermal resistance between the flue gas and the working medium and as a result reduce the heat transfer between them. &hus, the flue gas e)its the combustion system at higher than the design temperatures and energy losses to the environment are increased. Deposits also tend to accumulate over time and, if the flue gas path is narrow enough, they may even block it completely. In some cases, after the accumulation of significant deposits, chunks may fall off and damage the interior of the boiler. All in all, deposits tend to decrease the efficiency of a combustion system and increase the operating and maintenance cost. &he deposit problem is typically classified in two broad terms7 slagging and fouling7 Slagging refers to deposits formed on sections of the boiler e)posed mainly to radiant heat, such as the furnace walls. 3lagging deposits are formed from molten or half molten ash particles that stick to the hot furnace walls. &hey are not formed immediately upon firing up the boiler but accumulate slowly after an initial layer has been formed over the walls. Fouling is used to characteri4e the deposits formed on the convective pass, such as the heat e)changer tubes. In this case, deposits are formed by inorganic vapours that condense on the relatively cooler surfaces of the heat e)changer tubes. Although the mechanisms of formation for slagging and fouling are not the same, both are closely linked with the tendency of the fuel ash components to melt or vapori4e at low temperatures. &he ash melting behaviour is greatly affected by the ash composition. &ypically, elements such as calcium and magnesium increase the ash melting temperature, while silica, potassium and sodium decrease it. It is therefore evident that herbaceous biomass ash is e)pected to have low ash melting temperatures while woody biomass generally will e)hibit high ash melting temperatures. In practice, it is not only the alkali content of herbaceous biomass that affects its fouling behaviour but also the chlorine content. Alkali chlorides facilitate the transport of alkalis in the gas phase, are very volatile and are released in the gas phase in the combustion 4oneF in the convective 4one, they condense on the cooler surfaces as can be seen in the figure.

Figure: Fouling by KCl in a fixed bed straw boiler (Source: DONG Energy)

&he condensed ash particles are molten and form sticky deposits that tend to enhance deposition of even coarse fly ash particles that would normally bounce off the surfaces. &he presence of alkali chlorides also decreases the overall ash melting temperature to values between "" 0 %"" #$ or lower.

Estimating ash deposit behaviour I


&here are two main ways to estimate the tendency of a biomass ash to form deposits. &he first method is the direct determination of the ash melting ,or fusion- temperature. A biomass ash sample is pressed into a test piece with specified dimensions in inserted in a controlled furnace and its decomposition as temperature increased is monitored constantly. &here is not yet a European 3tandard, only a &echnical 3pecification, $EN@&3 1!1 "'1 > 3olid biofuels ' :ethod for the determination of ash melting behaviour ' ;art 17 $haracteristic temperatures method>. Another commonly used standard is the A3&: D 1%! . Although the e)act temperatures to be recorded and definitions thereof differ from the standard, the following may be used for the purposes of this handbook7 &he 3hrinkage 3tarting &emperature ,33&- is the temperature at which the test piece first starts to shrink, possibly due to the release of volatile inorganic materials or due to sintering. &his temperature value is not a part of the common A3&: standard so it is not usually recorded in older data. &he Initial Deformation &emperature ,I&- is the temperature where tips of test piece show the first signs of rounding due to melting. &he 3oftening &emperature ,3&- is the temperature where the height of

the test piece is e(ual to its width. &his temperature is not included in the European &echnical 3pecification, although it is commonly reported. &he 2emisphere &emperature ,2&- is the temperature where the test piece has melted sufficiently to form a hemisphere. &he 5low &emperature ,5&- is the temperature where the test piece has effectively melted and is spread over the supporting tile. A well'known and widely used inde) based on the temperatures above is the slagging inde), which is calculated from the following e(uation7

&he higher the slagging inde), the lower the propensity for formation of strong slagging deposits. *enerally, fuels with a slagging inde) less than 11!" #$ have a severe slagging potential, while values greater than 114" #$ indicate weak slagging potential. <alues in between cover a wide range of severe to moderate slagging potentials. 5or biomass fuels, the I& is also considered a valid indication of the tendency of the ash to cause problems during combustion. &he measurement of ash melting temperature provides a direct correlation between laboratory data and the tendency of an ash to melt. 2owever, it offers no information on the ash composition and the transformations that the ash may actually e)perience in the combustion chamber.

Estimating ash deposit behaviour II


&he second way of evaluating the propensity of a biomass ash to form deposits is the use of appropriate indices, based on its ma8or element ash composition ,see The ash composition above-. 3everal ash indices have been developed, initially for coals, and are known to be (uite accurate in their predictions. 2owever, due to the different composition and morphology for the ash, their value for biomass fuels is contested. New indices are being developed for biomass fuels, although their general applicability is not yet completely accepted. 3ome indices that have been developed include the molar ratio 3i@,$aG:g- or its modified version ,3iG;GA-@,$aG:g- for fuels containing high amounts of phosphorus as is the case with several types of herbaceous biomass. 3ince calcium and magnesium tend to increase the ash melting temperature, the higher this inde), the lower the ash melting temperature and the fouling propensity.

&here are a great number of different indices and key numbers such as the :iles inde), the alkalinity indices, salt ratios, glass formation inde) and a number of others 0 none of which gives the full picture or a definite answer to slagging and fouling behaviour. It must also be understood that depositions occur in such places inside the combustion or gasification reactor where conditions 0 o)ygen content, temperature and gas velocities 0 happen to be favourable. 2ence, any evaluation of average or mean conditions may only be seen as an indication and cannot be used to predict in any detail where, when or to what e)tent depositions will occur. &he application of the different indices, as well as the interpretation of their meaning, should therefore be left to e)perienced technicians or researchers. 2owever, the indices, blunt as they are, once again pinpoint the importance of several elements such as A, 3i and ; in the general description of ash melting behaviour. &he reader will notice that chlorine is absent in those indices despite the fact that, as was mentioned earlier, it is e)tremely important in the fate of potassium in the furnace. &he effect of chlorine will be discussed in the following section on corrosion.

Ash utilization
Apart from some minor loss of inorganics as aerosols or dust particles, most of the biomass ash in combustion applications is collected either as fly ash, which is collected at the ash cleaning e(uipment along the flue gas path, or bottom ash. Although the ash (uantities that are produced by herbaceous biomass combustion are usually not comparable with the amounts of ash that several types of coal produce, nonetheless finding utili4ation pathways for such a combustion residue is an important aspect of any combustion system, if only to maintain its environmentally friendly outlook. Despite this, the issue of ash utili4ation is in several cases omitted from the design phase and postponed until the installation is operating. &wo main reasons contribute to this7 first, the landfilling option can in most cases be chosen, even though it may not be the cheapest optionF second, the composition and properties of combustion ash differs depending on the actual fuel (uality combusted as well as the installation type.

5or coal ash, the issue of ash utili4ation in most cases has a relatively easy answer7 itHs used as an additive for the production of cement or concrete. 2owever, many biomass ashes will contain much higher concentrations of alkali than the standards which regulate the use of coal ashes allow. &hus, the utili4ation of biomass ashes in concrete@cement production is only possible if the ash comes from a co'firing installation ,see "4'"/'"1- and even in this case, the biomass thermal share must be (uite low. :any biomass ashes are rich in potassium, which is an important plant nutrient. ;otassium is easily leached from the ashes and becomes available for plants. ?ther plant nutrients, such as calcium, may also be present. &hus the re'cycling of biomass ashes as a fertili4er is a ma8or option. &here are some issues that need to be considered in this application though7 5ly ashes from biomass combustion may be rich in potassium, but most of the nitrogen has been released in the gas phase. In addition, phosphorus may be present but in an insoluble form, which make take several decades before it becomes accessible to plants. 5or forestry this may be no issue due to the longer growth cycle but for agricultural practices, other nitrogen and phosphorus containing fertili4er may still have to be applied. 5ly ashes also tend to be rich in all the heavy metal contaminants, such as cadmium, that a biomass fuel may contain. &he biomass fly ash must meet certain re(uirements regarding heavy metals concentration before its use as a fertili4er may be considered. &his is particularly relevant in cases when biomass is co'combusted with other, heavily contaminated fuels. 5inally, due to the volatile nature of alkalis, bottom ashes may e)hibit rather low potassium concentrations and thus their return as nutrients in the field might make little sense. &he (uestion of how a system planner should approach the issue of herbaceous biomass ash utili4ation is addressed in more detail in section "4'"/'"9.

Estimating corrosion behaiour


$orrosion occurs when the protective o)ide layer that is formed on tube walls is attacked primarily by chlorine or sulphur containing compounds. &he sulfidation and chloridation of the tube surfaces results in the formation of an outer layer that does not have the protective properties of the o)idised one. Its defective structure means that it can be scaled off easily due to erosion and thus become sub8ect to further corrosion. &hus, corrosion refers to the deterioration of intrinsic properties of the wall or tube material. $ontrary to slagging@fouling, which can be controlled to

some e)tent by cleaning procedures, such as soot'blowing even while the boiler is operating, corrosion is permanent and severely affects the lifetime of the e(uipment. Chlorine corrosion is particularly relevant for the combustion of herbaceous biomass and waste fractions or refuse'derived fuels. It can occur through either one of three main mechanisms7 *as phase corrosion, which is the direct attack of gaseous 2$l or $l/ to heat'e)changer surfacesF &he formation of alkali sulphate and@or alkali chloride melts, which dissolve the protective o)ide layer of the heat'e)changer surface &he active o)idation mechanism which refers to the sulfation of alkali metal or heavy metal chlorides in the tube near the deposition layer. 5rom this mechanism, $l is released, which subse(uently attacks the tube surface. Active o)idation is the most critical mechanism regarding high'temperature corrosion. As can be seen, its e)tent relates mostly to the formation of alkali chlorides deposits on tube surfaces. As was mentioned before, most of the alkalis in herbaceous biomass high in chlorine are typically released in the gas phase as alkali chlorides, it is clear that fouling and corrosion are closely linked in herbaceous biomass and the e)tent of fouling is a good indicator of the corrosive properties of a fuel. A number of measures can be taken to reduce the corrosion potential. &hese include7 1) Reducing the chlorine content of the fuel. 5or herbaceous fuels this can be achieved via leaching during storage, as discussed in section "1'"/' )))). +ith waste fuels, the content of chlorine is mainly determined by how well the fractioning and separation of ;<$ works in the waste collection system. Ioth ways, the overall chlorine that enters the combustion chamber is reduced. 2) Proper design of the combustion chamber. If the gas temperature where alkali chlorides are brought into contact with the tube surfaces is low enough, the deposits are not molten but solid and their corrosion potential is reduced. 3uch a temperature would be about J!" #$. &his is a common design in waste incinerators. &he price paid is a reduction of the electricity efficiency of the plant as discussed in te)t section "4'"/'"%f. Also, special coatings or steel alloys for the construction of the tube surfaces may be used, although this increases the capital costs of the boiler. ) Use of additives or complementary fuels that influence the combustion conditions towards the formation of compounds with lesser corrosion potential. &he general idea would be that the alkali content of the biomass ash would react with certain other elements and become bound in structures without chlorine. &hus chlorine would end up in the gas phase as

2$l, which is less critical for corrosion, while the alkali compounds would either have higher melting temperatures and@or lower corrosion potential. 3uch additives fall in one of three categories7 Al3i additives, such as kaolin and dolomite ;hosphorus containing additives, such as dicalcium phosphate 3ulphur containing additives, such as ammonium sulphate. &he molar ratio ,AlG;G/3-@,AGNa- for the fuel plus additives indicates whether there is sufficient additives to capture the alkali. In practice, ratios greater than 1 are re(uired. Knfortunately, most commercial additives are (uite e)pensive and have a heating value of 4ero or negligible. A fuel price increase of up to /" . can be e)pected in many cases. 2ence, it is preferable to co'fire herbaceous biomass along with fuels that naturally contain one of the three additives or high concentrations of the critical elements. &he evaluation of the corrosion potential for herbaceous biomass can be performed again using certain empirical indices. 5or e)ample, the sulphur to chlorine molar ratio is calculated as /3@$l. &he molar concentrations of each element can be found by dividing its weight composition in the fuel by its molecular weight. 5uels for which this ratio is high tend to form a protective sulphate layer on the tubes. If the ratio e)ceeds 4, only minor corrosion is e)pected ' with values over % the chlorine presence in the deposits is minimal. &his e)plains the tendency to co'fire herbaceous biomass along with fuels containing high concentrations of sulphur, such as certain coal types or peat.