REVIEW

pubs.acs.org/EF

Ash-Related Issues in Fluidized-Bed Combustion of Biomasses:

Recent Research Highlights
Mikko Hupa*
Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, FI-20500 Åbo, Finland

ABSTRACT: Finland and Sweden are leaders in the use of biomass fuels in large-scale boilers. In these countries, the dominating
large-scale combustion technology for biomass fuels is fluidized-bed combustion (FBC). Biomass fuels differ in many ways from the
standard fossil fuels used in FBC, such as coal. They often have high moisture contents, lower heating values, and a variety of
impurities, such as chlorine, sulfur, phosphorus, nitrogen, and a variety of ash-forming metals. FBC of biomass fuels is often
connected with operational challenges, which are related to the fuel chemistry and fuel properties. Bed sintering, superheater fouling,
and high-temperature corrosion are crucial factors to take into account when fuels are selected for FBC. It is of vital interest to find
ways of predicting the degree of these kinds of ash-related problems for various fuels or fuel mixtures. This paper reviews some of the
recent progress in our understanding of the fate and behavior of ash-forming matter in FBC. The following topic areas are discussed:
fuel characterization, release of the ash-forming matter during combustion, interaction of the ash and bed material, fly ash formation,
fly ash properties, ash deposits, and fouling and corrosion.

’ INTRODUCTION
Fluidized-bed combustion (FBC) is considered a flexible
technology that makes it possible to burn fuels of widely varying
quality. Besides different coal qualities, including high-sulfur or
high-ash coals, also low-grade fuels, such as various types of
biomasses and waste-derived fuels, have become highly interest-
ing as feed stocks to FBC. Many installations also burn mixtures
of different fuels. Circulating fluidized-bed combustion (CFBC)
is preferred in the largest unit sizes and for coal firing. For
biomass firing, the more simple bubbling fluidized-bed combus-
tion (BFBC) technology has become increasingly popular.
However, the use of biofuels and waste-derived fuels in FBC
may cause several operational problems because of the fuel
impurities. Bed sintering is a problem with high alkali fuels.
Sticky fly ash and problems of fouling and corrosion of the
superheater tubes is another common phenomenon when using
fuels containing chlorine, etc. Fuel ashes from different fuels
burnt together may also interact with each other in a surprising
way, thus sometimes leading to excessive fouling or bed sintering
problems.
This paper reviews some of the recent progress in our under-
standing of the fate and behavior of the ash-forming matter in
FBC of biomasses. The following topic areas are discussed: fuel
characterization, release of the ash-forming matter during com-
bustion, interaction of the ash and bed material, fly ash formation,
fly ash properties, ash deposits, and fouling and corrosion. The
main interest is in the biomass and waste-derived fuels, but some
comparisons to coals are also made.
This is not intended to be a comprehensive review of all
research in the field. Rather, the intention is to give an overview
of the most significant areas where clear progress in under-
standing in the chemical details of the fate of the fuel impurities
has taken place in the last 10 years or so. Also areas where there is
an obvious lack of information and where more research work is
needed will be identified and discussed.
Most of the examples in this review are taken from the research
at Åbo Akademi University in Turku, Finland, but the general
discussion is based on the lively recent research at the many
laboratories active in the field, especially Chalmers University of
Technology, Technical University of Denmark, CANMET in


Canada, University of Graz, University of Umea, University of
Stuttgart, ECN in The Netherlands, and VTT in Finland. The
FBC boiler manufacturing companies have contributed with
relevant information also in the literature.
’ ASH-FORMING MATTER IN THE FUELS
A number of excellent compilations of biomass fuel property
data, including analyses of the ash-forming matter, are available in
the literature 13 and in the form of net-based data banks. 4,5
Further, a number of recent papers deal with detailed character-
istics of ashes from individual particular biomass-based fuels,
such as agricultural wastes, rice husk, straw, rapeseed meal or
cake, corn stalk, palm kernel, olive stones, sewage sludge, forest
residue, or recovered “demolition” wood.620
Table 1 shows the typical elemental composition of ash-
forming matter in selected biomass-based fuels, including the
sewage sludge. At the bottom of the table examples of peat and
coal analyses are included for comparison. The table gives the
elemental composition of the ash-forming matter after ashing the
fuel samples according to a standard ashing procedure. It is
common practice to give the percentage of each of the elements
analyzed as if they were present as their most common oxides. It
is important to note that the elements very seldom are present in
Special Issue: 2011 Sino-Australian Symposium on Advanced Coal and
Biomass Utilisation Technologies
Received: August 1, 2011
Revised: October 12, 2011
Published: October 13, 2011

r 2011 American Chemical Society 4 dx.doi.org/10.1021/ef201169k | Energy Fuels 2012, 26, 4–14
Energy & Fuels REVIEW

Table 1. Elemental Analysis of the Laboratory Ash of a Variety of Biomass-Based Fuelsa

fuel SiO2 Al2O3 Fe2O3 TiO2 MnO CaO MgO P2O5 Na2O K2O sum (%)

sawdust 2.05 0.25 0.09 0.00 4.21 68.76 7.13 3.01 0.27 16.78 102.54
bark 10.74 3.20 4.96 0.14 1.77 60.16 5.82 5.24 0.67 8.69 101.38
forest residue 36.75 5.81 1.91 0.22 1.46 37.14 2.93 3.17 0.20 7.72 97.32
eucalyptus bark 0.01 0.14 0.07 0.00 4.21 77.43 3.12 1.95 0.36 16.07 103.38
straw 58.49 0.39 0.33 0.03 0.00 21.10 2.13 3.53 0.25 13.59 99.84
rice straw 69.88 0.28 0.24 0.01 0.57 6.16 1.55 1.53 0.40 15.26 95.88
rice husk 95.41 0.10 0.05 0.00 0.12 0.74 0.28 0.53 0.01 1.84 99.09
bagasse 72.96 4.97 2.53 0.29 0.19 11.00 2.06 0.96 0.34 3.86 99.15
grape seeds 3.44 0.57 0.56 0.03 0.05 52.97 3.12 11.81 0.18 17.52 90.24
almond shells 6.22 0.98 0.66 0.06 0.05 36.32 3.01 1.60 0.38 30.66 79.95
olive residues 19.75 1.74 2.69 0.08 0.06 36.50 12.12 2.73 0.11 17.61 93.40
sewage sludge 17.86 9.89 36.65 0.75 0.08 13.28 1.12 19.61 0.53 0.82 100.59
peat 20.20 23.09 26.21 0.44 0.22 19.42 2.07 4.10 0.15 0.64 96.56
coal 46.48 24.60 8.43 0.98 0.16 6.83 2.62 0.48 1.36 2.34 94.28
a
The numbers give weight percent of the elements expressed as their most common oxides (Åbo Akademi data).

the ash as the oxides indicated, for instance, K2O, CaO, or P2O5,
but normally as some more complex compounds, such as K2SiO3
or Ca3(PO4)2. Giving the elemental composition as oxides has,
however, the advantage that one obtains a good estimation of the
amount of oxygen in the ash. Most of the elements in their real
compounds possess the same amount of oxygen as in these
simple oxides; Ca3(PO4)2 contains the same amount of oxygen
as the oxides CaO and P2O5 combined (3CaO + P2O5).
Consequently, adding up all of the oxide weight percents
should be very close to 100% if all relevant elements have been
included in the analysis. This helps in controlling if the ash
analysis contains all of the important elements.
However, some ashes may also contain non-oxygen-contain-
ing salts, such as chlorides or sulfides. Sometimes, also, the metals
in the ash may not be fully oxidized to their most stable oxide; for
instance, iron may be FeO instead of Fe2O3, or lead may be in the
metallic form, Pb, rather than as the oxide PbO. Further, some
ashes may contain carbonates, typically alkali carbonates or, if the
ashing is performed at a lower temperature, also calcium
carbonate. To obtain the full 100% in the total oxides, this
carbonate has to be included in the ash analysis and presented as
CO2. Most often, carbonate is not included (like in Table 1).
This will show as a lower total sum of oxides. Grape seeds, Figure 1. Chemical fractionation by leaching of the fuel sample in
almond shells, and olive residues in Table 1 all have less than aqueous solutions of increasing leaching efficiency.23
100% total oxides mostly because of the missing carbonate
analysis. Potassium in these ashes is in the form of carbonate the fuel itself without any ashing procedure. The chemical
(K2CO3). fractionation of the fuel sample implies a procedure where the
The elemental ash analysis is the starting point in establishing fuel is leached in water solutions of increasing “aggressiveness”
the suitability of a given fuel to be burned in a fluidized bed from (Figure 1). This technique was originally introduced to ash-
the ash behavior point of view. Biomass ashes are characterized forming matter in coals by Benson and Holm.21 Later, it has been
by high contents of the metals K (sometimes also Na), Ca, and applied to biomasses and even to waste-derived fuels.2224
Mg. Some biomasses also contain large amounts of Si and P. Recently, the technique was extended to study also the anionic
Peat and coal differ from biomasses in many ways. Their species in woody biomasses.25
proximate volatile content is much lower than most biomasses; Figure 2 shows examples of chemical fractionation of four
their ashes have high contents of Al, Si, and Fe but low contents of K. interesting byproducts or wastes presently being planned to be
This type of elemental analysis tells nothing about the chemical used as fuels: a byproduct from bioethanol processing (distillers
and physical form of the ash-forming matter in the fuels. To know grains), two types of residues from vegetable oil production
more about the form of the ash-forming matter is quite important (rapeseed and palm kernel cakes), and sewage sludge.16 Selective
when trying to predict the behavior of the ash in a combustion system. leaching of the fuel in the three different solutions gives useful
More information about the ash-forming matter can be information of the chemical form of the ash-forming matter in
obtained if the elemental analysis is performed by analyzing the fuel. The water-soluble elements are mostly in the form of
5 dx.doi.org/10.1021/ef201169k |Energy Fuels 2012, 26, 4–14
Energy & Fuels REVIEW

Figure 2. Chemical fractionation of the ash-forming matter in four biomass materials planned to be used as fuels in the FBC.16

Figure 3. Scanning electron microscopy (SEM) image of rice husk ash produced by cautious oxidation in a laboratory furnace at 500 °C. X-ray analysis
of the particle shown in the middle of the right hand image gave a silica (SiO2) content of more than 95%.7 Magnification: true height of the images is
600 μm (left) and 300 μm (right).

simple inorganic salts, such as alkali chlorides or sulfates. Ammonium
acetate leaching releases the organically bound cations by ion
exchange. The final stage, leaching in hydrochloric acid, dissolves
most of the scarcely soluble inorganic salts, such as calcium
carbonate or sulfate. The remaining, insoluble ash-forming elements
are often bound in silicates. Also, sulfur, chlorine, or phosphorus
covalently bound to the organic fuel matrix may stay in this
insoluble leaching residue.22,26
Further information of the character of the ash-forming matter
can be obtained by removal (oxidation) of the organic matter at
temperatures where the ash being formed or exposed does not
sinter or melt into lumps but remains as separate particles of various
kinds. Figure 3 shows the ash formed under gentle oxidation of
the organic matter from rice husk particles. The characteristic,
6 dx.doi.org/10.1021/ef201169k |Energy Fuels 2012, 26, 4–14
0.10.3 mm size silica “skeletons” of the rice husk are clearly
visible.7 Because of this shape and size, the rice husk ash has very
special properties in the FBC. These properties cannot be
predicted on the basis of the chemical composition only.
’ RELEASE OF THE ASH-FORMING MATTER IN THE
FURNACE
Any prediction or modeling of the formation and behavior
of the fly ash requires some fundamental understanding of the
initial release of the ash-forming matter during the burnout of
the fuel particles. One essential question is to what extent the
various ash-forming elements are released as gases during the
burning process and to what extent they stay in the solid ash
Energy & Fuels
residue remaining after the burnout of the particle, respectively.
The further reactions and fate of the ash-forming elements are
very different depending upon this initial split of the elements
into the gases versus the solid ash residue.2729 Frandsen et al.30
give an interesting overview of the methods and challenges in any
systematic prediction of the release of ash-forming matter in
combustion. Their overview focuses on conditions relevant to
grate firing and pulverized fuel firing.
Fuel particles burn in three stages: drying, devolatilization, and
char oxidation. It is of vital interest to know in detail how the ash-
forming matter reacts during these stages. Drying takes place when
the particle temperature reaches the temperature of around 100 °C.
Very little ash-forming matter is expected to be released during the
drying stage of the fuel particle after entering the furnace, even if very
little experimental information to confirm this is available.31
During devolatilization, the dry fuel particle is heated to a
higher temperature under a heavy release of organic vapors and
gases because of thermal decomposition, pyrolysis, of the organic
matrix of the fuel. For most of the biomasses, the majority,
7090% of the combustible matter, will be released as vapors
during this devolatilization stage. Some ash-forming elements are
released during this stage. During the following char burning, the
particle temperature in the fluidized bed can reach 8501000 °C.
During the char burnout, the easily volatilized ash-forming metals
will form gaseous compounds, such as chlorides or hydroxides.
The extent of this release into gases is heavily dependent upon
the burning conditions (temperature and oxygen concentration).
Dayton et al.32 made direct mass spectrometer measurements
of the alkali and chlorine products released during combined
pyrolysis and char combustion. The main gas-phase products
detected containing chlorine or potassium were HCl during the
volatile combustion phase and KCl and KOH during the char
combustion phase. J€aglid et al.33 and Olsson et al.34 investigated
alkali release from biomass pyrolysis by measurements of the
total alkali in the gas phase as a function of the temperature. They
found that 0.10.2% of the alkaline metal content in straw was
released below 500 °C. A larger part of the alkali metal release
took place at a higher temperature (>500 °C). The presence of
chlorine was found to enhance the alkali metal emission at the
higher temperature, while the alkali metal release in the lower
temperature region could not be correlated with the chlorine
content.34 Later, Jensen et al.35 pointed out that some minor
amounts of inorganic matter may be lost during pyrolysis because
of the convective transport of small particles caused by the
liberated gases, and this may be the reason for this low-tempera-
ture alkali release reported by Olsson et al.34
Bj€orkman et al.36 studied the release of chlorine during pyrolysis
of different types of biomasses, applying a heating rate of 50 °C/min.
Below 200 °C, no significant release of chlorine was observed.
However, already at 400 °C, between 20 and 50% of the chlorine
was released, and at 900 °C, between 40 and 70% of the chlorine
was released.
A recent laboratory study by Wu et al.37 on the combustion of
bran showed that sulfur was almost fully vaporized during fixed-
bed pyrolysis below 700 °C. A total of 6070% of the K and P in
bran were released during combustion, in the temperature range
of 9001100 °C. They assumed that the release of K and P was
attributed to the vaporization of gaseous KPO3 generated from
the thermal decomposition of inositol phosphates, which were
considered to be a major source of P and K in bran.
Quite little fundamental information is available of the release
of the various ash-forming elements of biomass fuels strictly
7 dx.doi.org/10.1021/ef201169k |Energy Fuels 2012, 26, 4–14
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Figure 4. Thermodynamic equilibrium calculation of the composition
of the ash in the flue gases from combustion of the fast growing willow
tree Salix.44
under conditions relevant to the FBC. Advanced aerosol mea-
surements in the flue gases of full-scale FBC boilers have shed
some light to the total share of vaporized material in FBC
conditions.27,28
It is clear that all ash-forming elements have their characteristic
tendency to react during combustion, depending upon their
chemical form in the fuel. One expects some connection between
the advanced fuel characterization, e.g., chemical fractionation,
and the behavior of the element in combustion. The ash-forming
matter, which is present as non-soluble silicates, will probably
have a low tendency to release volatile species during combus-
tion. On the other hand, soluble alkali compounds in the fuel may
easily be released as vaporized compounds.22,26,38
More light needs to be shed on the more quantitative
connection of advanced fuel characterization and laboratory
analyses, on one hand, and the release and formation of the
initial ash particles during the burnout of the particle at FBC
conditions, on the other (see the next paragraph).
’ FORMATION OF FLY ASH
A typical fly ash particle size distribution from CFBC of
biofuels is a bimodal curve, with the smaller maximum at around
0.20.5 μm and another maximum at a particle size of several
micrometers.27,28,39 This type of curve, in principle similar to the
ones for ashes from pulverized coal combustion, is a result of the
two different routes of ash formation. The sub-micrometer
particle fraction originates in condensation of volatilized metal
compounds, and it is typically highly enriched in sulfates,
carbonates, or chlorides of alkali metals.27,28 Also, zinc and lead
salts may be enriched in the sub-micrometer fraction, when fuels
such as demolition wood are used.40,41
There is a complicated interaction between the formation and
composition of the sub-micrometer fly ash and the content of
sulfur (SO2) and chlorine (HCl) in the furnace.31,39,42,43 In
simple terms, it is a question of competition of the various
reaction routes of the volatilized potassium. Dependent upon the
detailed conditions, the released potassium can be converted into
chloride, carbonate, or sulfate or it can react with the bed material
to silicates (see the next paragraph).
Thermodynamic equilibrium calculations have been shown to
be useful when discussing the chemical composition of the fly
ash. Figure 4 is a first thermodynamic prediction of the composi-
tion of the ash after combustion of the fast growing willow tree
Energy & Fuels
Salix as function of the temperature.44 In this calculation, the
input was simply the total amount of ash-forming elements being
considered together with the combustible matter from the fuel
and a stoichiometric excess of air of 10%. The figure gives the
main stable solid phases of the ash and also indicates the presence
of a liquid phase at temperatures above about 900 °C. This liquid
phase is a mixture of potassium sulfate and potassium carbonate.
In the calculations behind Figure 4, all ash-forming matter in
the fuel has been taken into consideration. This kind of calcula-
tion should, however, be complemented with information of the
“reactivity” of the elements in the fuel. All ash-forming matter in
the fuel is not equally reactive or “available” to the chemical
conversions. Some ash constituents are present in such stable or
inert compounds in the fuel that they do not react further in
combustion, and, consequently, these constituents should be
excluded from such equilibrium analyses. One attempt to do this
would be to exclude the non-soluble metals based on chemical
fractionation. These metals are most often bound together with
silicon as practically “non-reactive” silicates of various kinds.
In CFBC, only part of the ash will follow the flue gases after the
cyclone. For these conditions, it may be of interest to study the
composition of the fine, sub-micrometer fly ash only. Here, the
equilibrium assumption appears acceptable; the gas chemistry
including the condensation of the aerosol particles is quite rapid
and seems to reach chemical equilibrium within the conditions of
a CFBC furnace. However, these thermodynamic calculations
require information of the percentage of the ash-forming matter
that is released as gaseous species. The release information is
needed for the ash-forming metals but also for sulfur and chlorine
because these are the key reactants transforming the fly ash
metals into their various compounds. This is the weak point of
such predictions; these kinds of release percentages need to be
established empirically (see above). Advanced fuel characteriza-
tion (e.g., chemical fractionation) could be used as one starting
point to such empirical information. Similar to that mentioned
above, some promising generic laboratory studies have produced
first empirical release data for some biomasses at grate or
pulverized fuel conditions,30,38 but much more work is required,
especially under FBC conditions.
In CFBC applications, often limestone is added for sulfur
capture. This is another complication to any predictions of the fly
ash chemistry. The fly ash composition is strongly dependent
upon the presence of SO2 available for the fly ash metals. If the
SO2 level is reduced by adding limestone, this will naturally
influence the fly ash chemistry.
’ INTERACTION BETWEEN ASH-FORMING MATTER
AND THE BED MATERIAL
A highly unwanted property of some biomass fuels is their
tendency to cause bed agglomeration. Bed agglomeration has
been studied since the early days of the FBC technology. Bed
sintering is caused by the change of the bed particle chemistry
because of the interaction with ash-forming matter. A number of
papers have been published on the chemical mechanisms of the
bed sintering.6,4553
The most used bed material is quartz or silica sand. With silica
bed particles, the most common particle surface compounds
when burning biomass fuels are silicates of potassium and
calcium. These alkaline silicates can form a molten viscous
glassy phase on the particle surfaces, thus making the particles
sticky.45,4951
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The detailed mechanisms of the silicate formation are still not
fully understood. The solidgas reaction between quartz and
alkali chloride vapors is one probable route.
SiO2 ðsÞ þ 2KClðgÞ þ H2 OðgÞ ¼ K 2 SiO3 ðlÞ þ 2HClðgÞ
A similar reaction could also take place with other alkali vapors,
such as hydroxides, which may be the dominant gaseous alkali
compounds when there is no chlorine available for the alkalis.
SiO2 ðsÞ þ 2KOHðgÞ ¼ K 2 SiO3 ðlÞ þ H2 OðgÞ
Reactions resulting in calcium silicate in the outer layer of sand
particles may take place via a calcium chloride intermediate.54
Rapid bed sintering has recently been reported also in
boilers using biomass fuels with high phosphorus content,
such a rapeseed cake or sewage sludge.1315,18,55 The composi-
tion of typical sewage sludge was shown in Figure 2. Today, there
is an increased interest in better understanding the chemistry of
phosphorus in biomass combustion.15,16,18,37,56 The formation of
alkali phosphates appears to be another important initiator of the
bed sintering. Calcium phosphates seem not to be reactive in the
same way.15,18
Another mechanism for bed sintering is due to reactions of the
lime in the bed with carbon dioxide and sulfur oxides.46
CaOðsÞ þ CO2 ðgÞ ¼ CaCO3 ðsÞ
2CaOðsÞ þ 2SO2 ðgÞ þ O2 ¼ 2CaSO4 ðsÞ
These reactions may cause the lime particles to agglomerate by a
process referred to as “reaction-induced sintering”.45,46 The
recarbonation reaction takes place at temperatures below about
800 °C, and sintering because of this reaction may take place if
the bed temperature is lower than normal for some reason
(partial load). Also, this sintering is known to initiate plugging of the
return leg at some applications with high lime use.46,57
This recarbonation-induced sintering may be further reinforced
by the sulfation reaction.57
The bed chemistry may become very complex when several
fuels are burned simultaneously. Figure 5 shows bed material
from 550 MWth CFBC using mixtures of peat, forest residue,
bark, and coal in different proportions and sequences.58 After
some weeks of operation, the bed contained particles originating
from each of the fuels but also agglomerates of particles from
different fuels and also particles from the limestone being added
in some sequences. The different particle identities in Figure 5
were deduced on the basis of the elemental composition and
particle shape and size.58 It is obvious that the potential sintering
of such a multi-component bed is difficult to foresee or theore-
tically predict.
Besides quartz, also many other refractory materials have been
suggested to be used as bed materials. These alternative bed
materials include a variety of other natural minerals,59 porous
alumina,60 blast furnace slag,43,61 olivine sand,43 etc. With these
materials, the formation of the molten, glassy silicates may be
eliminated.
Because of the extra cost of most of the alternative bed
materials, quartz is still today the dominant bed material even
with the high alkali biofuels, and the bed sintering is kept under
control by continuously replacing a sufficient part of bed material
with fresh sand.59
Energy & Fuels
Figure 5. Cross-section SEM images of bed particles from 550 MWth CFBC using mixtures of peat, forest residue, bark, and coal.58 Magnification: true
height of the images is 100 μm.
Figure 6. Calculated percentage liquid phase versus temperature
curves for a salt consisting of a given mixture of sulfate and chloride of
sodium and potassium, with the four characteristic melting temperatures
indicated.56,64
’ FOULING AND CORROSION PROPERTIES OF FLY
ASH
In CFBC, the cyclone separates the coarse particles from the
flue gases and only the finer fly ash passes to the flue gas duct.
Dependent upon the properties, this fly ash may form disturbing
ash deposits on tube surfaces in the superheater or economizer of
the flue gas duct. Also, condensing alkali vapors may contribute
to the fouling of the cooled heat-exchanger surfaces.27,28
These deposits may deteriorate the heat transfer to the steam
tubes and disturb or even plug the flow of the flue gases through
the heat-exchanger packages. They may also cause corrosion of
the heat-exchanger tube metal. Fouling and corrosion caused by
biomass fuel ashes has been a topic of active research during the
last 1015 years. Frandsen62 summarized this research, which
continues actively at the present moment. High-temperature
corrosion caused by the fly ash is the main reason why the
steam temperature and the power production efficiency in FBC
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installations using biofuels are significantly lower than in similar
boilers using coal.
The stickiness and corrosion properties of the fly ash are
connected to its melting properties. Salt mixtures, such as the
mixtures in the fly ash, melt in stages when heated. Figure 6
shows an example of a melting curve for a salt consisting of a
mixture of sulfates and chlorides of potassium and sodium. The
figure is based on the Åbo Akademi thermodynamic multi-
component melt model, by which one can calculate the percen-
tage of the liquid phase as a function of the temperature for a
given mixture of typical inorganic salts in biomass ashes.6365
Backman et al. originally defined four characteristic tempera-
tures based on such theoretical melting curves:64 (1) T0 is the
temperature at which the first molten phase appears, also called
the first melting temperature or solidus temperature. This
temperature may be of interest when discussing superheater
corrosion. If the superheater tube metal temperature is higher
than the T0 of the fly ash particles deposited on the tube, the tube
metal will be exposed to some liquid phase of the salt deposit. (2)
T15 is the temperature at which 15% of the mixture is molten, also
called sticky temperature. By the time when this was introduced,
it was assumed that roughly 15% of the molten phase is required
to make the particles sticky. (3) T70 is the flow temperature, at
which a sample body made of the mixture will be so heavily
molten that it loses its shape and collapses (similar to the “radical
deformation point” sometimes referenced). (4) T100 is the
temperature at which the last crystalline phase is dissolved in
the liquid phase, the temperature of complete melting.
These melting curves and characteristic temperatures have
been shown to be useful, and many boiler designers are using
them to obtain a first impression of the quality of the fly ash. In
particular, the sticky temperature has been shown to clearly
indicate the extent and location of severe fouling in the flue gas
duct. The stickiness criterion of the 15% molten phase has been
tested experimentally for particles of the alkali salt mixture. Tran
et al.66 used an entrained flow reactor and synthetic alkali salt
mixtures. Figure 7 shows the deposition rate of synthetic ash
particles on a cooled steel probe (500 °C surface temperature) as
function of the percentage of the liquid phase in each of the fly
Energy & Fuels
Figure 7. Deposition rate of alkali salt particles of a variety of compo-
sitions as a function of their percentage of the liquid phase at the tem-
perature of deposition. The deposit probe temperature is 500 °C, and
the entrained flow reactor temperature is 7001000 °C.66
Figure 8. Thickness of corrosion product oxide layers on six steel
qualities after exposure for 1 week to alkali salt mixtures with increasing
chloride content (see the text): (top) only alkali sulfates, (middle) alkali
sulfate with 0.3% Cl added as alkali chloride, and (bottom) alkali sulfate
with 1.3% Cl added as alkali chloride.67
ash mixtures tested. The particles were entrained by hot combus-
tion gases through a reactor with a temperature of 7001000 °C
before hitting on the cooled probe. The figure shows that the
10
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deposition rate jumps from the baseline (indicating that the
particles become sticky) when the share of the liquid phase in the
particles exceeds 1520%. At liquid contents higher than 20%,
practically all particles hitting the probe stay on the surface. The
deposition rate at those conditions is simply limited by the
amount of particles hitting the surface.
The first melting temperature T0 has been suggested as an
important parameter when discussing high-temperature corro-
sion of boilers. If the tube surface temperature is higher than the
T0 of the deposited salt, the heat-exchanger steel surface is
directly exposed to a molten salt phase. This contact results in
a heavy increase of the corrosion rate.
Figure 8 shows laboratory corrosion test results by Skrifvars
et al. 67 In these tests, coupons of six steel qualities were
exposed to alkali salt mixtures at different temperatures. After an
exposure of 1 week, the oxide layers formed between the salt layer
and metal were measured as indications of the corrosion rate.
The steels 1 and 2 were carbon steels; the steels 3 and 4 were
stainless steels, and the steels 5 and 6 were high nickel alloys
(see details by Skrifvars et al.67).
Within the range of temperatures tested, pure alkali sulfate
(top in Figure 8) did not cause any measurable corrosion for any
of the steels, except for the carbon steel number 1. However, even
small additions of alkali chloride in the salt dramatically triggered
corrosion (middle and bottom in the figure). The T0 for the
sulfate salt in the test (mixture of Na2SO4 and K2SO4) was
around 620 °C. The addition of alkali chlorides decreased the T0
to around 525 °C. As expected, above some 500525 °C, there
was a clear increase in the measured corrosion rates in the tests
with chloride present. This was true for the carbon steel but also
for the austenitic stainless steel tested. However, additional tests
have shown that salt mixtures containing chlorides can cause
corrosion at temperatures clearly below the T0.68
Alkali-chloride-induced high-temperature corrosion has been
studied already for more than 30 years. In fact, this corrosion is
the main reason for the significantly lower superheated steam
temperatures that can be applied in boilers burning biomasses.
Since the excellent review by Nielsen et al.,69 a lot of research has
been carried out. However, still many open questions remain
concerning the details of the mechanisms of this corrosion, and
the research continues actively.70,71
’ FUEL MIXTURES
One of the advantages of the FBC technology is that it makes it
possible to burn different types of solid fuels simultaneously in a
simple way. In fact, most of the new FBC installations in Europe
are today designed for mixed fuel operation. However, mixtures
of fuels may cause surprises. In particular, the ashes from the
different fuels may interact with each other, thus resulting in fly
ashes with completely different behavior than any of the compo-
nent fly ashes.29
Consequently, the interaction of fuel ashes from two or more
fuels being burned in FBC has become a very important research
topic. During the last 5 years, more than 20 papers per year have
been published on the issue of fuel mixtures in the FBC. Several
recent studies, including pilot- and full-scale FBC tests have
shown that both chemical and physical interactions may take
place.8,13,14,7275
Chemical interaction is most often connected to the fate of the
alkalis and chlorine.39,76,77 Alkali chlorides formed with one fuel
can be converted to less harmful compounds by introducing a
dx.doi.org/10.1021/ef201169k |Energy Fuels 2012, 26, 4–14
Energy & Fuels
Figure 9. In situ measurement of gaseous KCl at the exit from the
cyclone during firing of (left) wood alone, (middle) wood together with
straw, and (right) wood and straw together with PVC.42
Figure 10. Deposit formation on a cooled sampling probe exposed to
fly ash from combustion of rice husk together with two types of
eucalyptus bark in different proportions. Entrained flow reactor tests.
The reactor temperature is 1000 °C, and the probe surface temperature
is 500 °C.8
second fuel with suitable other reactive compounds.76,78,79 The
introduction of sulfur will convert the alkali chlorides into
sulfates, thus releasing hydrochloric acid. Alkali chlorides may
also react with silicates or aluminum silicates and kaolin in the
other ashes, thus forming alkali silicates of various kinds.49,76,80,81
The reactions are similar to the reactions discussed above in the
context of the bed sintering.
Further, calcium in some ashes (or as a sulfur-capture ad-
ditive) will also interact with the alkali chloride chemistry by
competing by reactions of its own with sulfur oxides (forming
calcium sulfate) or the silicates (forming calcium silicates). Both
of these reactions may decrease the extent to which the alkali
chlorides react with the same reactants.
Recent studies using an online KCl analyzer at the exit from
the cyclone have given valuable information of the ash and flue
gas chemistry in CFBC during burning of fuel mixtures of various
kinds.42 Figure 9 shows an example of a test campaign burning
wood, straw, and polyvinyl chloride (PVC) waste introduced
stepwise. The boiler is first fired with wood, containing little alkali
11
REVIEW
and practically no chlorine, and the concentration of gaseous KCl
is 12 ppm. At 62 min, the feeding of straw pellets starts, which
increases the input of both potassium and chlorine and the
concentration of KCl increases to about 20 ppm. At 96 min, the
PVC is added, increasing the chlorine input by a factor of almost 5.
This does not introduce any more potassium. However, the PVC
addition raises the concentration of KCl to about 70 ppm. Here,
the added chlorine seems to strongly facilitate the volatilization
of potassium.
Figure 10 shows an example of the fouling tendency of fly
ashes from eucalyptus bark and rice husk, respectively. The
results come from entrained flow reactor tests using an air-cooled
sampling tube of about 25 mm in diameter (similar to the tests in
Figure 7). Eucalyptus bark alone showed a high degree of fouling,
while rice husk alone appeared non-fouling. The high fouling rate
of the fly ash from the eucalyptus bark was steeply reduced by the
introduction of the rice husk as the secondary fuel. This effect was
interpreted as being more physical than chemical. The coarse rice
husk ash particles (see Figure 3) are not only non-fouling
themselves, but they also seem to be able to keep the tube
surface clean from the more sticky bark ash.8 Later, a similar
“cleaning interaction” has been found with some other fuel pairs
as well.73
’ CONCLUSION AND FUTURE RESEARCH NEEDS
Bed sintering, superheater fouling, and high-temperature
corrosion are crucial factors to take into account when fuels
are selected for FBC, especially when biomass or waste-derived
fuels are considered. It is of great interest to find ways of
predicting the degree of ash-related problems for various fuels
or fuel mixtures.
Fuel characterization techniques have advanced significantly.
Chemical fractionation and microscopic analysis of ash samples
produced by gentle (low-temperature) ashing give deeper a
understanding of the presence of the ash-forming matter in fuels.
This may be one basis to better estimate the release and behavior
of the ash-forming elements during combustion.
Quantitative prediction of the release of the ash-forming
matter in combustion is not possible just based on laboratory
analysis of the fuel samples. Much more laboratory work is
needed to establish the connection between the detailed com-
position of the fuels and the release of their ash-forming elements
under various FBC conditions.
Bed sintering is mostly connected to formations of molten or
glassy alkaline silicates on the surfaces of the quartz particles used
as bed material. The reactions between alkali or alkaline earth
metals and silica in the quartz are influenced by several compet-
ing reactions, thus making the prediction of bed sintering quite
demanding. Phosphorus-induced sintering has recently been
reported when high-phosphorus biomasses are burnt. The details
of the high-temperature chemistry of phosphorus are still unclear
and require more fundamental studies.
Alternative bed materials that do not contain quartz have
become very interesting. More systematic work of the materials
in connection with the different critical ash-forming matter is
needed.
Fouling and corrosion properties of the fly ash are strongly
connected to the melting behavior of the ash. Thermodynamic-
phase calculations allow for quite accurate prediction of the
melting curves of ash mixtures containing various alkali salts
typical for biomass ashes. The melting curves can be used to
dx.doi.org/10.1021/ef201169k |Energy Fuels 2012, 26, 4–14
Energy & Fuels
estimate stickiness and corrosion properties of the fly ash.
However, more work is needed to establish the connection of
the presence of a molten phase in the ash deposit and high-
temperature corrosion.
Ash behavior in boilers using more than one fuel simulta-
neously may cause additional challenges. Ashes from different
fuels may interact with each other. This can lead to surprising
nonlinear behavior of the ash behavior as a function of the fuel
mixture. Chemical interactions of this kind include reactions
where alkali compounds from one fuel react with sulfur or maybe
aluminum silicates from the other, thus leading to a major change
in the alkali-chloride-induced problems, such as bed sintering or
superheater corrosion. A general understanding of the ash
chemistry in many fuel mixtures has increased significantly
during the last 5 years or so. However, the interactions of the
ashes from different biomasses or waste fuels with each other or
with ashes from fossil fuels may be extremely complex. To make
progress in the understanding of these interactions, ingenious
systematic studies would be very welcome.
Theoretical predictions of ash-related problems based on fuel
characterization and modeling are under development. However,
for completely unknown fuels or fuel mixtures, pilot- or full-scale
FBC tests are still necessary before safe operation can be guaranteed.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: mikko.hupa@abo.fi.
’ ACKNOWLEDGMENT
I thank all of my present colleagues and Ph.D. students at Åbo
Akademi for the inspiring and productive collaboration in the
many research activities behind this review. Further acknowl-
edgements go to my many important colleagues outside of Åbo
Akademi: Bo Leckner, Kim Dam-Johansen, Johan Hustad,
Flemming Frandsen, Honghi Tran, Rainer Backman, Benco
Skrifvars, Mischa Theis, Jatta Partanen, Vesna Barisic, and
Edgardo Coda Zabetta. Åbo Akademi combustion research is
supported by the National Technology Agency (Tekes) and the
industrial consortium of the companies Andritz Oy, Metso
Power Oy, Oy Mets€a-Botnia Ab, Foster Wheeler Energia Oy,
UPM-Kymmene Oyj, Clyde Bergemann GmbH, International
Paper, Inc., and Top Analytica Oy Ab. Their support is warmly
acknowledged. This work is part of the activities of the Åbo
Akademi Process Chemistry Centre within the Centres of Excellence
Program by the Academy of Finland.
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14 dx.doi.org/10.1021/ef201169k |Energy Fuels 2012, 26, 4–14