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Biomass and Bioenergy 30 (2006) 973–982


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Chemical properties of solid biofuels—significance and impact


Ingwald Obernberger, Thomas Brunner, Georg Bärnthaler
Institute for Resource Efficient and Sustainable Systems, Graz University of Technology, Inffeldgasse 2lb, Graz A-8010, Austria
Received 17 November 2005; accepted 9 June 2006
Available online 20 September 2006

Abstract

The chemical composition of solid biofuels (as defined in [Directive 2000/76/EC of the European Parliament and of the Council on the
Incineration of Waste. In: European Commission, editor. Official Journal of the European Communities, vol. L 332; 2000. p. 91–111]
and [CEN/TC 335—WG2 N94. Final draft. European Committee for standardization, editor. Solid biofuels—fuel specifications and
classes. Brussels, Belgium; 2003.] has manifold effects on their thermal utilisation. C, H and O are the main components of solid biofuels
and are of special relevance for the gross calorific value, H in addition also for the net calorific value. The fuel N content is responsible for
NOx formation. NOx emissions belong to the main environmental impact factors of solid biofuel combustion. Cl and S are responsible
for deposit formation and corrosion and are therefore relevant for a high plant availability. Furthermore, Cl causes HCl as well as
PCDD/F and S SOx emissions and both elements are involved in the formation of aerosols (submicron particle emissions). The ash
content influences the choice of the appropriate combustion technology and influences deposit formation, fly ash emissions and the
logistics concerning ash storage and ash utilisation/disposal. Major ash forming elements (Al, Ca, Fe, K, Mg, Na, P, Si, Ti) are of
relevance for the ash melting behaviour, deposit formation and corrosion. In addition, volatile elements such as Na and K are main
constituents of aerosols. Volatile minor elements (As, Cd, Hg, Pb, Zn) play a major role in gaseous and especially aerosol emissions as
well as in deposit formation, corrosion and ash utilisation/disposal. Either partly or non-volatile minor elements (Ba, Co, Cr, Cu, Mo,
Mn, V) are of special relevance for ash utilisation. The present paper discusses the influence of chemical fuel properties on biomass
combustion plants as well as possibilities and recommendations for controlling them.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Biomass combustion; Solid Biofuels; Chemical fuel properties

1. Introduction as well as major (Al, Ca, Fe, K, Mg, Na, P, Si, Ti) and
minor elements (As, Ba, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni,
The whole process of thermal utilisation of solid biofuels Pb, Sb, Tl, V, Zn) in solid biofuels. The present paper gives
(fuel supply, combustion system, solid and gaseous an overview of the influence and impact of these elements
emissions) is influenced by the kind of solid biofuel used, on combustion and points out technological and process
its physical characteristics (e.g. particle size, bulk density, control measures in order to deal with these fuel properties
moisture content, gross calorific value (GCV)) and its best. The fuels considered are all kinds of natural solid
chemical composition [3]. Two work packages of the EU biofuels (as defined as biomass in [1] and as solid biofuels in
project BioNorm (ENK6-CT-2001-00556) thus deal with [2]) and cover wood fuels, herbaceous fuels as well as other
the physical and chemical characteristics of solid biofuels. agricultural residues such as fruit stones and shells.
This paper focuses especially on chemical fuel properties.
The work package concerned aims to develop analytical 2. Principles of solid biofuel combustion and technologies
methods for the determination of (total) carbon (C) and applied
hydrogen (H), sulphur (S), chlorine (Cl) and nitrogen (N)
In the ideal case, combustion represents the complete
Corresponding author. Tel.: +43 316 873 4897; oxidation of the solid organic part of the fuel into the gases
fax: +43 316 48 13 00 4. CO2 and H2O. This conversion occurs in three steps: drying
E-mail address: georg.baernthaler@tugraz.at (G. Bärnthaler). of the fuel (vaporising of water), pyrolysis/gasification

0961-9534/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2006.06.011
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974 I. Obernberger et al. / Biomass and Bioenergy 30 (2006) 973–982

(thermal degradation (devolatilisation) in the absence or


presence of externally supplied oxygen (air), respectively)
and the final oxidation of the charcoal and the flue gases
(see Fig. 1). After drying, the main controlling parameter
of the combustion process is the ratio between the amount
of air added and the amount of air (oxygen) necessary for a
complete combustion of the combustible parts of the fuel,
the lambda (l, excess air) factor.
At l below 1, incomplete oxidation of the fuel
(gasification) takes place and only a part of the fuel energy
is converted into thermal energy. Adding too much air
ðl  1Þ will cool down the process, leading to incomplete
combustion and thermal losses. Thus, the theoretical Fig. 2. Process of biomass combustion—allocation of different stages of
optimum of the combustion process is at l ¼ 1. In reality combustion in grate furnaces. Explanations: data source [27,35].
however, this point is difficult to obtain due to mixing
constraints between the fuel, flue gas and the air added. (with a nominal boiler capacity (NBC) up to around
Thus, depending on the combustion technology utilised, a l00 kWth) as well as industrial application with NBCs in the
total l between 1.1 and 1.8 in large-scale and 1.5 and 2.0 in MWth range for district heating, process heating, electricity
small-scale applications is common in order to achieve production as well as combined heat and power (CHP)
complete combustion. production. The technologies used for small-scale applica-
A lower total l can be achieved by separating the tions include wood-stoves, fire place inserts, heat-storing
combustion stages into different locations in the furnace, stoves as well as boilers for wood logs, wood pellets and
thereby increasing the retention time for reactions and also wood chips [3].
the possibility of optimised control. This type of separa- The furnaces for industrial applications are typically
tion, so-called staged combustion, is shown in Fig. 2 for equipped with mechanical or pneumatic fuel-feeding
fixed bed systems, where drying (I), pyrolysis/gasification systems and process control systems supporting fully
(II) and char oxidation (IIIa) take place in different zones automatic system operation. In general, the larger the
on and above the grate (primary combustion chamber). combustion unit the more flexible it becomes in terms of
Subsequently, the flue gases are completely oxidised by the quality of the solid biofuels used. Thus, solid biofuels
addition of secondary air in the secondary combustion used in medium and large-scale biomass combustion units
chamber (IIIb). comprise not only wood, but also bark, energy crops,
In order to achieve a combustion that is as efficient as agricultural waste products and in some cases mixtures of
possible and produces only low amounts of undesired these.
products, each combustion step must be optimised taking State of the art technologies applied for industrial
into consideration the combustion technology applied and combustion include fixed-bed (grate) furnaces, bubbling
the kind of solid biofuel used. and circulating fluidised bed furnaces as well as dust
The application of solid biofuel combustion comprises burners. The technologies applied for dust precipitation
small-scale (domestic) application for domestic heating (which is the most relevant flue gas-cleaning step for solid
biofuel combustion) include settling chambers, cyclones/
multi-cyclones, electrostatic precipitators, baghouse filters,
scrubbers and panel bed filters, as well as flue gas
condensation units (combination of heat recovery from
the flue gas and dust precipitation).
Possible and appropriate flue gas cleaning technologies
for other emissions will be discussed in more detail in the
following chapters.

3. Chemical composition of solid biofuels—influence on


thermal utilisation

The elements are present in solid biofuels at varying


concentrations depending on the origin and type of
biomass. Tables 1 and 2 contain guiding values for ash
and element concentrations obtained from European
research work [2]. In the following subchapters the
Fig. 1. Process of biomass combustion—principle. Explanations: data influence of these elements on biomass combustion will
source [27]. be outlined and discussed in more detail.
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Table 1
Typical mean values for the chemical composition of wood fuels

Parameter Unit Wood without bark Bark Logging residues Short rotation
coppice Willow
Coniferous Deciduous Coniferous Deciduous Coniferous Deciduous
wood wood wood wood wood wood

Ash wt% d.b. 0.3 0.3 4.0 5.0 2.0 1.5 2.0
C wt% daf 51 49 54 55 52 52 49
H wt% daf 6.3 6.2 6.1 6.1 6.1 6.1 6.2
O wt% daf 42 44 40 40 41 41 44
N wt% daf 0.1 0.1 0.5 0.3 0.5 0.5 0.5
S wt% daf 0.02 0.02 0.1 0.1 0.04 0.04 0.05
Cl wt% daf 0.01 0.01 0.02 0.02 0.01 0.01 0.03
F wt% daf o0.0005 o0.0005 0.001 — — — 0.01
Al mg/kg d.b. 100 20 800 50 — — —
Ca mg/kg d.b. 900 1200 5000 15,000 5000 4000 5000
Fe mg/kg d.b. 25 25 500 100 — — 100
K mg/kg d.b. 400 800 2000 2000 2000 1500 3000
Mg mg/kg d.b. 150 200 1000 500 800 250 500
Mn mg/kg d.b. 147 83 500 190 251 120 97
Na mg/kg d.b. 20 50 300 100 200 100 —
P mg/kg d.b. 60 100 400 400 500 300 800
Si mg/kg d.b. 150 150 2000 10,000 3000 150 —
Ti mg/kg d.b. o20 o20 — — — — 10
As mg/kg d.b. o0.1 o0.1 1 — 0.3 — o0.1
Cd mg/kg d.b. 0.1 0.1 0.5 0.5 0.2 0.1 2
Cr mg/kg d.b. 1 1 5 5 — — 1
Cu mg/kg d.b. 2 2 5 5 — — 3
Hg mg/kg d.b. 0.02 0.02 0.05 o0.05 0.03 0.02 o0.03
Ni mg/kg d.b. 0.5 0.5 10 10 — — 0.5
Pb mg/kg d.b. 2 2 4 5 3 5 0.1
V mg/kg d.b. o2 o2 1 — — — —
Zn mg/kg d.b. 10 10 100 50 — — 70

Explanations: data source [2]; dafydry basis, ash free; d.bydry basis; ash content measured according to ISO 1171 (1997) at 550 1C.

3.1. Carbon (C), hydrogen (H) and oxygen (O) close to zero (e.g. COo50 mg/Nm3 and CXHYo5 mg/
Nm3 at 11%O2 [4].
C, H and O are the main components of solid biofuels
(Tables 1 and 2). C and H are oxidised during combustion 3.2. Nitrogen (N)
by exothermic reactions (formation of CO2 and H2O). The
content of C and H contributes positively to the GCV, the According to [2], coniferous and deciduous wood has the
content of O negatively. H also influences the net calorific lowest N content. Higher concentrations are found in bark,
value (NCV) due to the formation of water. The C contents logging residues, short rotation coppice (willow and
of wood fuels (including bark) are higher than those of poplar) and straw from wheat, rye and barley. The
herbaceous biofuels, which explains the slightly higher concentrations are usually still higher in rape straw (wheat,
GCV of wood fuels. CO2 is formed and emitted as a major rye and barley straw can also have N contents in this
product of complete combustion. However, CO2 emissions range), miscanthus and fruit residues (e.g. olive or grape
from biomass combustion are regarded as being CO2- cakes, kernels, shells). Grains and grasses usually show the
neutral with respect to the greenhouse gas effect if a highest values (Tables 1 and 2).
sustainable utilisation is assumed [3]. Incomplete combus- During combustion the fuel N is almost entirely converted
tion can lead to emissions of unburnt carbon-based to gaseous N2 and nitric oxides (NOx [NO, NO2]). The
pollutants such as carbon monoxide, hydrocarbons, poly- amount of nitrous oxide (N2O) is very low in modern solid
cyclic aromatic hydrocarbons, tar and soot. An effective biofuel furnaces. Only an insignificant amount of N is
reduction of these pollutants can be achieved by an incorporated in the ash. Recent investigations have shown
optimised combustion process, providing good mixing that one of the main environmental impacts of solid biofuel
between fuel and air, sufficient retention time (41.5 s) at combustion is caused by NOx emissions [4]. NOx can be
high temperatures (4850 1C) and a low total l. In modern formed via three different reaction pathways.
furnaces with effective process control systems the con- Thermal NOx is formed from the reaction of airborne N
centrations of unburned pollutants can be reduced to levels with oxygen radicals at temperatures above 1300 1C.
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Table 2
Typical mean values for the chemical composition of herbaceous fuels and fuels from fruit residues

Parameter Unit Straw Straw Grains Grains from Virgin reed Grass, in Miscanthus Exhausted
from from from rape canary general (China reed) Olivecakea
wheat, rye, oilseed wheat, rye, grass
barley rape barley Summer
harvest

Ash wt% d.b. 5.0 5.0 2.0 5.0 6.4 7.0 4.0 2.0–7.0
C wt% daf 49 50 46 63 49 49 49 48–50
H wt% daf 6.3 6.3 6.6 7.5 6.1 6.3 6.4 5.5–6.5
O wt% daf 43 43 45 25 43 43 44 —
N wt% daf 0.5 0.8 2 4 1.4 1.4 0.7 0.5–1.5
S wt% daf 0.1 0.3 0.1 0.1 0.2 0.2 0.2 0.07–0.17
Cl wt% daf 0.4 0.5 0.1 — 0.6 0.8 0.2 0.08–0.15
F wt% daf 0.0005 — — — — 0.001 o0.0005 —
Al mg/kg d.b. 50 50 — — — 200 — —
Ca Mg/kg d.b. 4000 15,000 500 — 3500 3500 2000 —
Fe mg/kg d.b. 100 100 — — — 600 100 —
K mg/kg d.b. 10,000 10,000 5000 — 12,000 15,000 7000 —
Mg mg/kg d.b. 700 700 1500 — 1300 1700 600 —
Na mg/kg d.b. 500 500 — — 200 1000 — —
P mg/kg d.b. 1000 1000 4000 — 1700 3000 700 —
Si mg/kg d.b. 10,000 1000 — — 12,000 15,000 — —
As mg/kg d.b. o0.1 o0.1 o0.1 — 0.1 0.1 0.2 —
Cd mg/kg d.b. 0.1 0.1 0.05 — 0.04 0.2 0.1 —
Cr mg/kg d.b. 10 10 0.5 — — 1 1 —
Cu mg/kg d.b. 2 2 4 — — 5 2 —
Hg mg/kg d.b. 0.02 0.02 o0.02 — 0.03 o0.02 0.03 —
Ni mg/kg d.b. 1 1 1 — — 2 2 —
Pb mg/kg d.b. 0.5 2 0.1 — 1 1 2 —
V mg/kg d.b. 3 — — — — 3 o1 —
Zn mg/kg d.b. 10 10 30 — — 25 10 —

Explanations: data source [2]; dafydry basis, ash free; d.bydry basis; ayvalues for C, H, O, N, S, CI, F in wt% d.b.; ash content measured according to
ISO 1171 (1997) at 550 1C.

The amount increases with increasing temperature. Prompt biofuels can be expected at fuel N concentrations above
NOx is formed from airborne N at temperatures above 0.6 wt% (d.b.). This could especially occur for straw,
1300 1C under low oxygen conditions in the presence of cereals, grasses, grains and fruit residues (see also Tables 1
hydrocarbons [5,6]. Due to the comparatively low furnace and 2). The technological possibilities for NOx emission
temperatures in solid biofuel combustion plants (around reduction include primary and secondary measures.
800–l200 1C), thermal and prompt NOx formation is only Primary measures include air staging (see primary and
of minor importance. NOx formation from the oxidation of secondary combustion zones in Fig. 2) in combination with
fuel N (during a series of elementary reaction steps) is the a primary l around 0.7, temperatures between 900 and
most important mechanism in biomass combustion units 1100 1C and a flue gas residence time of 0.5 s in the primary
[7–10]. The NOx emissions thus increase with increasing combustion chamber. With these measures a 30–50%
fuel N content, as shown by [11–13]. Furthermore, the air reduction in NOx emissions compared to conventional
supply, the geometry of the furnace, the combustion combustion, is possible [15] (see also Fig. 3). The effect of a
temperature and the type of combustion technology staged combustion can also be achieved by a staged
applied are major influencing variables for NOx formation addition of fuel. This technique shows a slightly larger
[3]. reduction potential but is limited in its application to solid
Comprehensive investigations on the combustion beha- biofuels with lower particle sizes (e.g. sawdust, wood dust)
viour of solid biofuels have resulted in guiding values and [14]. Moreover, the furnace concept and operation is more
ranges for concentrations of combustion-relevant elements complex due to the need for two independent fuel-feeding
in solid biofuels and ashes for unproblematic combustion. systems. For both types of staged combustion, accurate
These values are summed up in [14], together with the process control is needed to ensure an operation at the l
parameters affected, the types of solid biofuels potentially needed in the different zones. If primary measures are not
concerned and appropriate technological countermeasures effective enough to achieve the required limiting values,
(see Table 3 and Table 5). According to this, emission- secondary measures must be applied but should always be
related problems (exceeding of emission limits) for solid combined with primary measures.
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Table 3
Guiding values and guiding ranges for N, CI and S in solid biofuels for unproblematic combustion

Element Guiding concentr. in Limiting If guiding concentr. ranges are not Technological possibilities if the guiding
the fuel wt% (d.b.) parameter kept problems can occur for values are not fulfilled

N o0.6 NOx emissions Straw, cereals, grasses, grains, fruit Primary measures (air staging, fuel staging)
residues secondary measures (SNCR and SCR
process)
Cl o0.1 Corrosion Straw, cereals, grasses, fruit Against corrosion:
residues, (grains) Fuel leaching
Automatic heat exchanger cleaning
systems
Coating of boiler tubes
Appropriate material selection

o0.1 HCl emissions Straw, cereals, grasses, fruit Against HCI emissions:
residues, (grains) Dry sorption
Scrubbers
Fuel leaching

o0.3 PCDD/F Straw, cereals, grasses Against PCDD/F-emissions:


emissions
Sorption with activated carbon
Catalytic converters

S o0.1 Corrosion Straw, cereals, grasses, fruit See Cl


residues, (bark, grains)
o0.2 SOx emissions See HCI emissions

Explanations: data source [14]; d.b.ydry basis; solid biofuels in brackets can exceed guiding values in special cases but usually keep them.

at a stoichiometric coefficient (NH3/NOx [mol/mol] or


CO(NH2)2/NOx [mol/mol]) of approx. 2.2. The residence
time of the flue gas in the furnace after ammonia/urea
injection should be between 0.3 and 0.5 s. On average a
60–70% NOx reduction can be achieved with SNCR.
When urea is used as reducing agent, an increase of CO
emissions by approx. 10–20 ppm is to be expected. In case
of the SCR, ammonia or urea is injected into the flue gas
(downstream the boiler) at a stoichiometric coefficient of
approx. 1.0. This technique needs a platinum, titanium or
vanadium oxide based catalyst to initiate the reduction
reactions. SCR works optimally at temperatures between
220 and 270 1C using ammonia and 400 and 450 1C using
urea. An average NOx reduction between 80 and 95% can
be achieved by SCR. In comparison to SNCR the
Fig. 3. NOx emissions and emission reduction potentials for different investment costs of SCR are considerably higher, whereas
solid biofuels and flue gas cleaning technologies. Explanations: data the operating costs concerning the reducing agent are
source [36]; NOx calculated as NO2 and related to dry flue gas and 11 lower. A major problem of SCR is the likelihood of
Vol.% O2. catalyst deactivation by alkali metals contained in the flue
gas of biomass combustion systems [14].

Secondary measures include selective non-catalytic 3.3. Chlorine (Cl)


reduction (SNCR) and selective catalytic reduction
(SCR). In both techniques ammonia (NH3) or urea The Cl content of wood is generally very low, while
(CO(NH2)2) is injected to reduce NOx to N2, without or significantly higher amounts are present in herbaceous
with a catalyst, respectively. In the case of SNCR, the biofuels, grains and fruit residues (Tables 1 and 2).
reducing agent is injected into a reduction chamber of the During combustion, the Cl contained in the biofuel
furnace at operating temperatures between 850 and 950 1C mainly forms gaseous HC1, Cl2 or alkali chlorides such as
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KC1 and NaCl. Due to the subsequent cooling of the flue 3.4. Sulphur (S)
gas in the boiler section of the combustion plant, a large
part of the Cl condenses as salts on the heat exchanger Like Cl, the S contained in the solid biofuel (see Tables 1
surfaces or on fly ash particles in the flue gas. Investiga- and 2) forms mainly gaseous SO2 (to a certain extent also
tions have shown that 40–80% of the total Cl released are SO3) and alkali as well as earth-alkali sulphates. Due to the
integrated in the ash in the case of wood chip or bark subsequent cooling of the flue gas in the boiler section of
combustion, or 80–85%) in the case of straw or cereals the combustion plant, SOx forms sulphates and condenses
(whole crop) combustion if baghouse filters are applied. on the heat exchanger surfaces or forms fine fly ash
The integration of Cl in the ash depends mainly on the particles, or reacts directly with fly ash particles deposited
concentration of alkali and earth-alkali metals as well as Si on heat exchanger surfaces (sulphation).
in the fuel, which react with Cl. Investigations have shown that 40–70% or 60–90% of
The main effect of Cl are the corrosive effect of chloride the fuel S were integrated in the ash in the case of wood
salts and HCl on metal parts in the furnace and boiler chip or bark combustion. In the case of (wheat) straw or
[16–20], HCl and particulate (KCl, NaCl, ZnCl2, PbCl2) cereal combustion (plants equipped with baghouse filters)
emissions as well as the influence of HCl on the formation only 40–55% were integrated in the ash. The efficiency of S
of polychlorinated dibenzo-p-dioxins (PCCD) and poly- fixation in the ash depends on the concentration of alkali
chlorinated dibenzofurans (PCDF) [21–24]. and earth-alkali metals (especially Ca) in the fuel (fuels like
According to [14] (Table 3) Cl induced corrosion and wood chips and bark can contain high Ca contents and
HCl emission problems are to be expected at fuel therefore cause a high S fixation) [27].
concentrations above 0.1 wt% (d.b.) and can therefore be The residual S remains in the flue gas as aerosols and in
of relevance for straw, cereals, grasses and fruit residues gaseous form as SO2 (in minor quantities as SO3).
(see also Tables 1 and 2). Measures against corrosion Emissions of SO2 are usually not significant for wood
include automatic heat exchanger cleaning systems, coating combustion due to the typically low concentrations of S in
of the boiler tubes, appropriate material selection as well as the fuel, and, especially in the case of wood chips and bark
optimised combustion and process-control technologies. utilisation, because of the relatively high embedment in the
Washing of the fuel in order to decrease its Cl content ash. According to [14] (Table 3) emission-related problems
(leaching) is an additional measure that can also be applied are to be expected at S concentrations above 0.2 wt%
to reduce HC1 emissions. HC1 emissions can also be (d.b.). This can be of relevance for rape straw and grasses.
reduced by scrubbing the flue gas with limestone or by dry Technological possibilities to reduce SOx emissions are the
sorption with calcium hydroxide (Ca(OH)2), or, to a same as already outlined for Cl emissions (see Section 3.3).
smaller extend by dry sorption with fly ash on baghouse The importance of S does not primarily result from SO2
filter surfaces. emissions but from its role in corrosion processes. Higher
PCDD/F (dioxins) can be formed in very small amounts SO2 concentrations in the flue gas cause sulphation of
from all solid biofuels containing Cl. In general, the alkali and earth-alkali chlorides with decreasing flue gas
PCDD/F emission levels of modern biomass combustion temperature (Fig. 4). This leads to the release of Cl. If these
applications using virgin wood as fuel are well below the reactions take place in ash particles precipitated on the
health risk limit. According to the guiding values specified surface of heat exchanger tubes, the released Cl can cause
in Table 3, emission related problems are to be expected for corrosion by FeCl2 or ZnCl2 formation at the heat
materials with Cl concentration above 0.3 wt% (d.b.) and exchanger surfaces [27,28]. Technological measures against
can therefore be of relevance for herbaceous biofuels (see corrosion have already been stated in Section 3.3.
also Tables 1 and 2). PCDD/F are formed at high oxygen
concentrations on the surface of unburned fly ash particles
in a temperature window between 180 and 500 1C. In
addition to Cl, carbon, oxygen and catalysts (Cu) are
necessary for PCDD/F formation. These emissions can
thus be significantly reduced by reducing the entrainment
of unburned fuel particles, by ensuring a complete
combustion of the flue gas and a complete burnout of
the fly ash particles at low excess air ratios as well as by
low heavy metal contents in the solid biofuel. Efficient fly
ash precipitation at low temperatures (o200 1C) is a
secondary measure designed to reduce PCDD/F emissions
in the flue gas, since the greater part of PCDD/F is
normally bound on the surface of the fly ash particles due
to their formation process [25,26]. Further secondary
measures include dry sorption with activated carbon or Fig. 4. Mechanisms involved in ash formation during biomass combus-
catalytic converters. tion. Explanations: adapted from [37].
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3.5. Ash content Chlorides and low melting alkali- and alumosilicates may
also significantly decrease the ash melting point [29]. This
The ash content of the fuel (see Tables 1 and 2) is can cause sintering or slag formation in the combustion
essential for the choice of the appropriate combustion and chamber (reduced plant availability and lifetime). In
gas-cleaning technologies. Furthermore, fly ash formation, addition, melts occurring in fly ash particles may cause
ash deposit formation as well as logistics concerning ash hard deposit formation on cooled furnace walls or heat
storage and ash utilisation/disposal (see also Section 3.6) exchanger tubes [27]. Hard deposit formation due to sticky
depend on the ash content of the fuel [27]. Fuels with low fly ash particles can be accelerated by alkali and heavy
ash content are therefore preferable. Wood usually metal salt mixtures (mixtures of alkali chlorides and
contains relatively low amounts of ash, while significantly sulphates with Zn and Pb chlorides) [28].
higher values are typically found in bark, straw, grasses, Straw, cereal, grass and grain ashes, which contain low
grains and fruit residues (Tables 1 and 2). concentrations of Ca and high concentrations of Si and K
Grate or fluidised bed combustion are suitable technol- (see Table 4), start to sinter and melt at significantly lower
ogies for ash-rich fuels. Underfeed stokers are not suitable temperatures than wood fuels. This fact must be considered
for ash-rich fuels due to the formation of ash layers on the when selecting the appropriate combustion and tempera-
surface of the fuel bed which can cause irregular break- ture control technology [3].
throughs of the gas and combustion air resulting in Together with Cl and S, K and Na play a major role in
increased emissions [27]. corrosion mechanisms (see Sections 3.3 and 3.4). More-
The composition, density, size and amount of the fly ash over, low melting mixtures of alkali and heavy metal
emissions formed are influenced by the amount of ash- chlorides can also cause corrosion by sulphation reactions.
forming elements in the fuel as well as by the combustion During combustion, a fraction of the ash-forming
technology and process control applied. A more detailed compounds in the fuel is volatilised (especially K, Na, S,
insight into ash formation and particulate formation Cl, Zn, Pb, Cd, to some degree also refractory species like
processes is given in Section 3.6. Ca, Mg and Si) and released to the gas phase (see Fig. 4).
The volatilised fraction depends on the chemical composi-
3.6. Major and minor elements tion of the fuel, the surrounding gas atmosphere, the local
temperature and the combustion technology in use. For
Major (Al, Ca, Fe, K, Mg, Na, P, Si, Ti) and minor (As, instance, high combustion temperatures and a reducing
Ba, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Tl, V, Zn) atmosphere enhance the volatilisation of the environmen-
elements form, together with Cl and S, the ash compo- tally relevant heavy metals Zn, Pb and Cd. By subsequent
nents. These elements are of relevance for ash melting, nucleation or condensation, these volatiles, together with
deposit formation, fly ash and aerosol emissions as well as solid phase sub-micron particles released from the fuel bed,
corrosion (together with S and Cl) and the utilisation/ form fine fly ash particles (aerosols) with sizes between
disposal of the ashes. 1 nm and 1 mm. They mainly consist of K, Na, S and Cl.
Typical concentrations of major and minor elements in Due to the high volatility of Cd, Zn and Pb amounts of
different solid biofuels are given in Tables 1 and 2. Table 4 these heavy metals can also be present in the aerosol
shows concentration ranges for selected major and minor fraction depending on the heavy metal concentration in
elements in solid biofuel ashes. the fuel.
As already mentioned major and minor elements The non-volatile compounds remaining in the charcoal
influence the ash melting behaviour. Ca and Mg usually form, by coalescence or melting, ash particles with a wide
increase the ash melting point, while K decreases it [3,27]. range of compositions, shapes and sizes, related to the

Table 4
Concentration ranges of combustion relevant elements in various solid biofuel ashes

Ash/Element Wood chips (spruce) Bark (spruce) Straw (wheat, rye) Cereals (wheat, triticale)

(wt% d.b.) (wt% d.b.) (wt% d.b.) (wt% d.b.)

Si 4–11 7–17 16–30 16–26


Ca 26–38 24–36 4.5–8.0 3–7
Mg 2.2–3.6 2.4–5.6 1.1–2.7 1.2–2.6
K 4.9–6.3 3.5–5.0 10–16 11–18
Na 0.3–0.5 0.5–0.7 0.2–1.0 0.2–0.5
(mg/kg d.b.) (mg/kg d.b.) (mg/kg d.b.) (mg/kg d.b.)

Zn 260–500 300–940 60.0–90.0 120–200


Cd 3.0–6.6 1.5–6.3 0.1–0.9 0.1–0.8

Explanations: data source [3]; d.b...dry basis.


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characteristics of the parent material. They consist mainly recommended for use (such as wood pellets and wood
of refractory species such as Ca, Mg and Si as well as of chips).
smaller amounts of bound volatile compounds such as K, According to Table 5, problems in respect to ash melting
Na and Al. The major part of this ash usually remains on are to be expected at Ca concentrations below 15 wt%
the grate and forms the bottom ash, while the rest gets (d.b.) and K concentrations above 7 wt% (d.b.) in the ash
entrained with the flue gas and forms the coarse part of fly and can therefore be of relevance for straw, cereals, grasses
ash with particle sizes between some mm to some l00 mm and grains. Technological countermeasures include appro-
Coarse fly ash particles can cause depositions on furnace priate temperature control on the grate and in the furnace
walls and heat exchanger surfaces and contribute to as well as in the boiler section. Measures against emissions
particulate emissions. include efficient dust precipitation, appropriate fuel selec-
Upon cooling the flue gas in the convective heat tion or fuel pre-treatment (e.g. fuel leaching).
exchanger section, vapours of volatilised compounds can The ash from (chemically non-treated) solid biofuels
condense or react on the surface of existing fly ash should, in favour of a sustainable utilisation, be recycled to
particles. Due to the much larger specific surface of the agricultural or forest soils in order to close the natural
fine fly ash particles in comparison to the coarse fly ash cycles of mineral nutrients. The environmental pollution of
particles, the concentrations of condensing or reacting ash the last decades, however, has led to higher concentrations
forming elements (K, Na, S, Cl, Zn, Pb) increase with of heavy metals in solid biofuels. Of special importance in
decreasing particle size. This also explains the very high this respect are the ecologically relevant elements Cd, Zn
heavy metal concentrations found in aerosol particles from and Pb. Problems with ash utilisation for recycling
biomass combustion plants [30–32], Particulate emissions, purposes are to be expected at Zn and Cd concentrations
together with NOx emissions, are considered as one of the above 0.08 and 0.0005 wt% (d.b.), respectively (according
main environmental impacts from biomass combustion [4]. to present Austrian guiding values for solid biofuel ash
Efficient dust precipitation and treatment of the resulting utilisation). This is mainly of relevance for fuels such as
condensates from flue gas condensation units are bark, wood chips and sawdust (ashes from grains can
recommended to control particulate and heavy metal contain relatively high amounts of Zn). Ashes from straw,
emissions [14]. cereals (whole crop) and grasses usually contain signifi-
Particles larger than 5 mm (coarse fly ash particles) can be cantly lower amounts of heavy metals (see Table 4).
precipitated by cyclone separators, while effective precipi- For fuels where high ash concentrations of environmen-
tation of particles smaller than 1 mm (aerosols) requires tally relevant heavy metals are to be expected appropriate
electrostatic precipitators or baghouse filters [33,34]. primary and secondary measures are necessary in order to
Electrostatic precipitators and baghouse filters are cost ensure an efficient and environmentally friendly ash
intensive and thus economically viable only for medium utilisation. These include the following procedures.
and large-scale combustion units [34]. If no dust precipita- The heavy metals are fractionated during combustion.
tion technology is applied or if the precipitation technology This is achieved by air staging and an appropriate
used is characterised by a limited efficiency, as in the case combustion temperature (4800 1C), which cause evapora-
of small-scale solid biofuel combustion units, only fuels tion of volatiles including the environmentally relevant
with low ash content and low concentrations of volatile ash heavy metals (Zn, Cd, Pb). Only small quantities of heavy
forming elements (like K, Na, S, Cl, Zn and Pb) are metals remain in the bottom ash, the major portion is

Table 5
Guiding values and guiding ranges for elements in solid biofuel ashes for unproblematic combustion

Element Guiding concentr. in Limiting parameter If guiding concentr. ranges are not Technological possibilities if the guiding
the ash wt% (d.b.) kept problems can occur for values are not fulfilled

Ca 15–35 Ash melting point Straw, cereals, grasses grains Temperature control on the grate and in the
furnace
K o7.0 Ash melting point, depositions, Straw, cereals, grasses, grains Against ash melting: see Ca
corrosion Against corrosion: see Cl
— Formation of aerosols Straw, cereals, grasses, grains Efficient dust precipitation, fuel leaching

Zn o0.08 Ash recycling, ash utilization Bark, wood chips, sawdust, grains Fractionated heavy metal separation, ash
treatment
— Formation of aerosols Bark, wood chips, sawdust; grains Efficient dust precipitation, treatment of
condensates
Cd o0.0005 Ash recycling, ash utilization Bark, wood chips, sawdust See Zn
— Formation of aerosols Bark, wood chips, sawdust See Zn

Explanations: data source [14]; guiding values for ashes related to the solid biofuels ashed according to ISO 1171 (1997) at 550 1C; d.b.ydry basis.
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contained in the fine fly ash. The fly ash is precipitated in a by the European Commission under the Fifth Framework
two-stage process. The coarse fly ash particles are Programme and contributing to the implementation of key
separated by a cyclone/multi-cyclone; this ash fraction action 6 ‘‘Economic and Efficient Energy for Competitive
can be mixed with the bottom ash (‘‘usable ash mixture’’) Europe’’ within the ‘‘Energy’’-sub-programme of ‘‘Energy,
and be used on agricultural land or in forests as secondary Environment and Sustainable Development’’.
raw material with fertilising and liming effects. The heavy
metal rich aerosols are precipitated in fine filters (filter fly
ash); this fraction must be separately collected and References
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