Energy & Fuels 1999, 13, 379-389 379

Field Study on Ash Behavior during Circulating

Fluidized-Bed Combustion of Biomass. 1. Ash Formation
T. Valmari, T. M. Lind, and E. I. Kauppinen*,
VTT Energy and VTT Chemical Technology, Aerosol Technology Group, P.O. Box 1401,
FIN-02044 VTT, Finland
G. Sfiris and K. Nilsson
Vattenfall Utveckling AB, Energy Conversion, S-162 87 Stockholm, Sweden
W. Maenhaut
University of Gent, Institute for Nuclear Sciences, Proeftuinstraat 86, B-9000 Gent, Belgium
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Received April 17, 1998

Ash formation was studied experimentally during combustion of forest residue and willow in
a 35 MW circulating fluidized-bed co-generation plant. Ash particles and vapors were sampled
downstream of the process cyclone at flue gas temperatures of 810-850 C. Inorganic vapors
and fly ash particles were collected separately on filters. Size-classified fly ash particle samples
were collected with an impactor. Elemental analysis methods and electron microscopy were used
for ash characterization. During combustion of forest residue, about 30-40% of the total ash
and a similar percentage of Ca and P was attached on the bed-material particles and were
eventually removed from the bed along with bottom ash. K was retained with a higher efficiency
(about 50%). S and Cl were volatilized in the furnace and were not retained in the bed. During
combustion of forest residue, 80% of S had already reacted with species present in supermi-
crometer ash particles when detected after the process cyclone at 810-850 C. When willow was
combusted, about one-half of the sulfur remained as SO2. More than one-half of the particle-
phase S was present as alkali sulfate fine particles that were almost nonexistent during forest
residue combustion. Cl was present as gaseous species (KCl and presumably HCl) at 810-850
C with both fuels.

Introduction micrometer ash particles.2 During circulating fluidized-

The behavior of the ash-forming constituents is a
matter of interest when fluidized-bed combustion is
applied for heat and power production using wood-based
fuels. Ash-forming constituents have an effect on plant
operation and emissions from the combustion process.
Ash deposition on various parts of the boiler causes a
reduction in heat transfer as well as corrosion and
blockage, which may lead to plant shut downs. During
fluidized-bed combustion, a fraction of ash accumulates
on bed particles, causing a need for periodic bed
replacement to avoid bed agglomeration. Ash-related
problems are often associated with fuels with high
contents of alkali metals, chlorine, and sulfur.1 In the
case of biomass, the major alkali-metal species is usually
potassium and, to lesser extent, sodium. Alkali metals
present in biomass are mainly organically bound and
highly volatile.
The ash-forming constituents which are not volatil-
ized during the combustion process form coarse, super-
* Author to whom correspondence should be addressed.
VTT Energy.
VTT Chemical Technology.
(1) Miles, T. R.; Miles, T. R., Jr.; Baxter, L. L.; Bryers, R. W.;
Jenkins, B. M.; Oden, L. L. Boiler Deposits from Firing Biomass Fuels.
Biomass Bioenergy 1996, 10, 125-138.
bed com-
bustion, large ash particles depart from the furnace with
flue gases and are recycled back to the bed by the
process cyclone, until they deposit on the bed-material
particles or have fragmented to a size small enough to
avoid recycling.
The partial volatilization of alkali metals from bio-
mass chars has been observed to take place after the
fuel devolatilization stage, which is characterized by the
release of oxygen- and hydrogen-rich gases.3 KCl has
been identified as the dominant potassium compound
released to the vapor phase, with KOH present as a
secondary volatile species when switchgrass with a Cl/K
molar ratio of about 0.5 was burned.4,5 Potassium
compounds may also react with silicates and aluminum
(2) Flagan, R. C.; Seinfeld, J. H. Fundamentals of air pollution
Engineering; Prentice-Hall: Englewood Cliffs, NJ, 1988.
(3) Wornat, M. J.; Hurt, R. H.; Yang, N. Y. C.; Headley, T. J.
Structural and Compositional Transformations of Biomass Chars
during Combustion. Combust. Flame 1995, 100, 131-143.
(4) French, R. J.; Milne, T. A. Vapor phase release of alkali species
in the combustion of biomass pyrolysis oils. Biomass Bioenergy 1994,
7, 315-325.
(5) Dayton, D. C.; French, R. J.; Milne, T. A. Direct Observation of
Alkali Vapor Release during Biomass Combustion and Gasification.
1. Application of Molecular Beam/Mass Spectrometry to Switchgrass
Combustion. Energy Fuels 1995, 9, 855-865.

10.1021/ef980085d CCC: $18.00 1999 American Chemical Society

Published on Web 12/24/1998
 380 Energy & Fuels, Vol. 13, No. 2, 1999 Valmari et al.

silicates forming potassium silicates. KOH deposited on

the quartz surface produces a low-melting (i.e., 800 C)
eutectic.6
During fluidized-bed combustion, alkali vapors may
also react on the surface of the bed particles forming,
e.g., alkali silicates. The species attached on the bed
material will eventually be removed from the bed as the
material is periodically changed. For instance, Manzoori
and Agarwal studied fluidized-bed combustion of low-
rank coals with high sodium, sulfur, and chlorine
content.7,8 Sodium and chlorine were released dispro-
portionally from NaCl originally present in coal. Sodium
formed sodium sulfate on the char surface and was
transferred to the surface of the bed-material particles,
whereas chlorine was not detected on bed-material
particles.
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The inorganic vapors present in the flue gas are

subject to chemical reactions and gas-to-particle conver-
sion. As the gas temperature is decreased, ultrafine ash
particles are formed by nucleation of vapors with low
saturation vapor pressure.2 This may take place already
inside the thermal boundary layer of the burning char
particle. Gases with higher saturation vapor pressure
are condensed later on the ash particles. Condensed
species are enriched on the fine ash particles. For
instance, during grate combustion of straw at an
industrial-scale plant, condensation of potassium as KCl
and K2SO4 (formed from reactions of KOH and KCl with
SO2) caused a high mass concentration of submicrome-
ter ash particles (up to 2 g/Nm3, depending on the straw
type).9,10 KCl and K2SO4 were also found in submi-
crometer particles formed during fluidized-bed combus-
tion of willow.11 Condensed K2CO3 is expected to be
formed when there is not enough S and Cl to bind all
the potassium. Vapors may also form particle-phase
compounds via chemical surface reactions instead of
condensation.
Potassium sulfate is formed via kinetically limited
reactions. The formation of solid sulfates (CaSO4,
K2SO4, Na2SO4) has been found to be sensitive to the
operating conditions, such as oxygen concentration and
bed temperature.12 The saturation vapor pressure of
KCl is higher than that of K2SO4. The condensation of
KCl takes place at temperatures (typically around 600
C, depending on the KCl concentration) that are
present at the convective back pass, where the flue gas
is cooled by the heat-exchanger tubes.
(6) Bryers, R. W. Fireside slagging, fouling and high-temperature
corrosion of heat-transfer surface due to impurities in steam-raising
fuels. Prog. Energy Combust. Sci. 1996, 22, 29-120.
(7) Manzoori, A. R.; Agarwal, P. K. The fate of organically bound
inorganic elements and sodium chloride during fluidized bed combus-
tion of high sodium, high sulphur low rank coals. Fuel 1992, 71, 513-
522.
(8) Manzoori, A. R.; Agarwal, P. K. The role of inorganic matter in
coal in the formation of agglomerates in circulating fluid bed combus-
tors. Fuel 1993, 72, 1069-1075.
(9) Christensen, K. A. The Formation of Submicron Particles from
the Combustion of Straw. Dissertation, Department of Chemical
Engineering, Technical University of Denmark, 1995.
(10) Christensen, K. A.; Livbjerg H. A Field Study of Submicron
Particles From the Combustion of Straw. Aerosol Sci. Technol. 1996,
25, 185-199.
(11) Valmari, T.; Kauppinen, E. I.; Kurkela, J.; Jokiniemi, J. K.;
Sfiris, G.; Revitzer, H. Fly Ash Formation and Deposition During Flu-
idized Bed Combustion of Willow. J. Aerosol Sci. 1998, 29, 445-459.
(12) Nordin, A. Optimization of sulfur retention in ash when
cocombusting high sulfur fuels and biomass fuels in a small pilot scale
fluidized bed. Fuel 1995, 74, 615-622.
Figure 1. Schematic view of the circulating fluidized bed
boiler. Filter samples and BLPI-samples were collected from
the sampling location 1. SEM samples were collected from
location 1 (willow) and location 2 (forest residue).
Detailed information about ash transformation mech-
anisms is desirable while developing methods to de-
crease ash deposition problems both in the bed and in
the convective back pass. The fly ash particle charac-
teristics and alkali vapor concentrations upstream of the
superheaters are important when studying ash deposi-
tion on the superheater surfaces. The present paper is
one of a series describing the experimental results on
ash behavior during circulating fluidized-bed combus-
tion (CFBC) of wood-based fuels in an utility-scale plant
during 1996 and 1997. The fuels include forest resi-
due, a commonly used fuel in fluidized-bed boilers, as
well as willow (Salix), which is increasingly being
cultivated for an energy resource in Sweden. Ash
formation and retention in the bed as well as fly ash
characteristics upstream of the convective back pass are
presented here. Fly ash behavior in the convective back
pass is described elsewhere.13,14 Results concerning the
behavior of toxic trace metals have been reported by
Lind et al.15
Experimental Section
Process Description. Measurements were carried out in
a CFBC co-generation plant with a capacity of 26 MW heat
and 9 MW electric power (Figure 1). The furnace cross-section
was 2.7 4.2 m, and its height was 13.5 m. Quartz sand with
a particle size of approximately 0.25 mm was used as the bed
material. The CFBC plant is equipped with a cyclone to recycle
(13) Lind, T. M.; Kauppinen, E. I.; Sfiris, G.; Nilsson, K.; Maenhaut,
W. Fly Ash Deposition Onto the Convective Heat Exchangers During
Combustion of Willow in a Circulating Fluidized Bed Boiler. Presented
at an Engineering Foundation Conference on The Impact of Mineral
Impurities in Solid Fuel Combustion, Kona, Hawaii, November, 2-7,
1997.
(14) Valmari, T.; Lind, T. M.; Kauppinen, E. I.; Sfiris, G.; Nilsson,
K.; Maenhaut, W. A Field Study on Ash Behaviour During Circulating
Fluidized Bed Combustion of Biomass. 2. Ash Deposition and Alkali
Vapour Condensation. Energy Fuels 1998, 13, 390.
(15) Lind, T. M.; Valmari, T.; Kauppinen, E. I.; Sfiris, G.; Nilsson,
K.; Maenhaut, W. Volatilization of the Heavy Metals During Circulat-
ing Fluidized Bed Combustion of Forest Residue. Environ. Sci. Technol.
1998, accepted for publication.
 Ash Formation Energy & Fuels, Vol. 13, No. 2, 1999 381

Table 1. Values of Selected Process Parameters during the Measurements

forest residue willow (Salix)
day 1 day 2 day 1 day 2 day 3
power (th), MW 16.5 16.0 18.6 18.8 19.0
power (el.), MW 6.5 6.5 5.9 4.4 4.9
fuel feed, kg/h (dry basis) 5160 5330 4780 4610 4720
sand feed, kg/h 239 322 8 53 64
bottom ash removal rate, kg/h 283 228 43 93 80
flue gas, Nm3/h 39 800 45 100 44 600 43 700 44 200
total air flow, Nm3/s 8.0 8.8 8.3 8.5 8.3
T, bed, C 750-830 780 782 757 762
T, CFB top, C 880 870 873 868 877
T, after cyclone, C 850 830 810 807 814
T, after heat exchangers, C 145 150 150 149 145
CO, ppm 100-200 100-200 >500 >500 >500
NO2, ppm 61 105 71 62 62
SO2, ppm 6.7 6.0 12 12 9
O2, % 3-4 4 4.5 4.6 4.3
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large particles (i.e., bed material, large char and ash particles)
back to bed.
Measurements with forest residue fuel were carried out
during 2 days in April 1996. Forest residue was burned for
the entire period. The second campaign was held during 3 days
in March 1997. Willow was burned during the daytime when
the measurements were carried out. At night, fuel was changed
to forest residue to avoid any ash-related problems during the
preliminary test run with willow. The different fuel burned
at night affected the bottom ash composition. All the fly ash
measurements with willow were carried out at least 5 h after
the fuel change. However, the fly ash composition may have
been affected by the volatilization of forest residue-originated
ash from the bed-material particles during the daytime. Values
of selected process parameters are given in Table 1. The gas
temperature in the bed was not quite stable during the first
day with forest residue. It increased during the day from 750
to 830 C. The temperature was 800-830 C during the
measurement period.
Elemental Mass Flows of the Ash-Forming Constitu-
ents. The amount of ash-forming constituents retained in the
bed was evaluated by calculating the elemental mass flows.
The mass flows studied included feed into the furnace due to
fuel and sand as well as the output from the furnace due to
fly ash and bottom ash. The calculation is presented only for
forest residue, as the bottom ash composition during the willow
measurements was disturbed by the other fuel burned at night.
Besides, the sand feed and bottom ash removal rates were
stable only during the forest residue measurements (Table 1).
The fuel feed rate was calculated from the plant operational
data. The bottom ash mass flow rate was evaluated by
weighing the bottom ash container on scales. Sand feed was
taken into account indirectly by extracting the sand-originated
ash-forming constituents from the bottom ash fraction. The
indirect approach was used because the sand feed rate may
not be equal to the sand removal rate with the bottom ash
over a short period of time. The fly ash flow rate was based
on the filter measurements carried out downstream of the
process cyclone and on the flue gas flow rate calculated from
the operational data. SO2 measured continuously at the plant
was included in the sulfur mass balance.
Particle- and Vapor-Phase Concentrations. Gas- and
particle-phase concentrations of ash-forming compounds down-
stream of the process cyclone were determined with a sampling
system that consisted of a precyclone and two filters (Figure
2). The flue gas temperature at the sampling station was 830-
850 C during combustion of forest residue and 810 C with
willow.
Two measurements were carried out with each fuel. The in-
duct precyclone-collected particles had an aerodynamic diam-
eter >3 m. Particles that were small enough to escape from
the cyclone were collected on a 47 mm quartz fiber filter
(Munktell MK360) also located in-duct. After the quartz fiber
filter, the flue gas sample was quenched with cool air (dilution
ratio 1:3) in a dilution probe made out of a porous steel tube.
Dilution air was introduced through the walls of the porous
tube to minimize the sampling losses by thermophoretic
deposition, diffusion, and vapor condensation on to the tube
surfaces. During quenching, vapors formed fine particles by
nucleation. These particles were collected on a 47 mm poly-
carbonate (Nuclepore) filter with a pore size of 0.2 m. To avoid
water vapor condensation, the sample gas was not allowed to
cool below 100 C prior to the filter, which was also heated to
100 C. Only a fraction of the diluted gas was directed through
the polycarbonate filter to avoid overloading. The rest was
aspirated through a bypass line. Sample collection times were
42-50 min.
Fly Ash Size Distributions. Fly ash particle mass size
distributions downstream of the process cyclone were evalu-
ated with a multijet Berner-type low-pressure impactor
(BLPI).16,17 The BLPI was preceded by the same precyclone
and dilution probe that were used during filter sample
collections (Figure 3). The BLPI was located outside the duct
and heated to 110-120 C. While the BLPI was not sampling,
a bypass flow with approximately the same flow rate was used
to maintain a constant flow rate through the precyclone.
The BLPI classifies aerosol particles into 11 size fractions
according to the aerodynamic diameter of the particles. Each
size fraction was collected on a polycarbonate (Nuclepore)
collection substrate. The substrates were greased with Apiezon
L vacuum grease to minimize particle bouncing. The sample
mass was determined by weighing the substrates before and
after sampling. The measurement method is described in more
detail by Kauppinen and Pakkanen.18
The size distribution of the precyclone-collected particles
was measured using a laser-diffraction method (Coulter LS
130). For the analysis, the precyclone sample was homog-
enized, weighed, and dispersed in sodium pyrophosphate
solution to create a stable dispersion.
Two measurements were carried out with each fuel. The
measurements with willow were carried out on two consecutive
days. With forest residue, the interval between the BLPI
measurements was 2 h and the sampling with the precyclone
was continued without any breaks between the BLPI mea-
surements. Sample collection times were 6-10 min for the
BLPI, 30-40 min for the precyclone with willow, and 151 min
for the precyclone with forest residue.
(16) Hillamo, R. E.; Kauppinen, E. I. On the performance of the
Berner Low-Pressure Impactor. Aerosol Sci. Technol. 1991, 14, 33-
47.
(17) Kauppinen, E. I. On the determination of continuous submi-
crometer liquid aerosol-size distributions with low-pressure impactors.
Aerosol Sci. Technol. 1992, 16, 171-197.
(18) Kauppinen, E. I.; Pakkanen, T. A. Coal Combustion Aerosols:
A Field Study. Environ. Sci. Technol. 1990, 24, 1811-1818.
Purchased by San Carlos Clean Energy Inc 382 Energy & Fuels, Vol. 13, No. 2, 1999 Valmari et al.

Figure 2. Filter sampling system for ash-forming constituents. Particles were collected on a precyclone (aerodynamic diameter
> 3 m) and on the quartz fiber filter (<3 m). Sample gas was quenched after quartz fiber filter, and condensed vapors were
collected on a polycarbonate filter.

Figure 3. Particle mass size distribution measurement system. Particles >3 m were collected on a precyclone. Sample gas was
quenched after the precyclone. Particles <3 m and condensed vapors were collected with a Berner-type low-pressure impactor
(BLPI) after quenching.
The precyclone became overloaded during the sample col- of 0.2 m. The flue gas was diluted with a two-stage, ejector-
lection with forest residue. Particles that were not retained based dilution system19 with a total dilution ratio of 1:80. At
in the overloaded precyclone were observed in the coarsest the first stage, flue gas was diluted with air heated to the duct
BLPI-size fractions during the second BLPI sample. The temperature to prevent water-vapor condensation. The volume
experimental inaccuracy in the total mass concentration due of the sampled flue gas was optimized to avoid particles
to the cyclone overloading was estimated to be about (10%. touching each other so that individual particles could be
The estimate is based on the fact that the mass concentration, studied. Samples were coated with platinum.
calculated as a sum of the second BLPI sample and the During combustion of willow, samples were collected up-
precyclone, was 22% higher than if calculated using the first stream of the convective back pass. Particles were collected
BLPI sample added to the precyclone sample. on a small copper grid which was coated with a thin carbon
Particle Morphology. Fly ash samples for scanning layer. The grid was cooled with pressurized air while inserting
electron microscopy (SEM) were collected using two methods.
During combustion of forest residue, samples were collected (19) Koch, W.; Lodding, H.; Molter, W.; Munzinger, F. Verdun-
downstream of the convective back pass (flue gas temperature nungssystem fur die Messung hochkonzentrierter Aerosole mit optis-
) 150 C) on polycarbonate (Nuclepore) filters with a pore size chen Partikelzahlern. Staub-Reinhalt. Luft. 1988, 48, 341-344.
 Ash Formation Energy & Fuels, Vol. 13, No. 2, 1999 383

Table 2. Composition of Fuels Table 3. Composition of Sand and Bottom Ash during
Measurements with Forest Residue
forest residue willow (Salix)
bottom ash, %
moisture, % 44-49 51-52
dry Sample, wt % sand, % day 1 day 2
C 52 50
S 0.02 0.06 0.07
H 6.3 6.2
Cl 0.01 0.01 0.01
N 0.6 0.4
Ca 0.24 2.92 3.31
ash 2.1 1.7
Si 44 40.8 40.1
S 0.04 0.03
K 1.99 3.00 3.29
Cl 0.025 0.01
Mn 0.02 0.43 0.43
Ash Prepared at 550 C, wt % Mg 0.04 0.42 0.45
Ca 20.8 21.2 P 0.03 0.32 0.34
Si 8.3 2.1 Na 1.10 0.95 0.92
K 7.1 14.3 Al 2.42 2.18 2.21
Mn 3.0 0.8 Fe 0.32 0.20 0.17
Mg 2.7 3.6
P 2.2 4.8 The molar ratio (K + Na)/(Cl + 2S) was 3 in willow,
Na 0.8 0.4
Al 0.7 0.21 indicating that at least two-thirds of the alkali metals
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Fe 0.4 0.15
(K + Na)mol/(Cl + 2S)mol 1.4 3.0
the probe into the duct, and the air stream was turned off for
the sampling time (a few seconds). After sampling, the air
stream was again turned on and the probe taken out from the
duct. The sample grid was mounted on a SEM sample holder,
and the analysis was made without coating the sample.
Samples were analyzed with a field-emission scanning
electron microscope (FE-SEM, Leo DSM 982 Gemini) equipped
with an energy-dispersive X-ray analyzer (EDS, Noran Voy-
ager 3). A low acceleration voltage (0.7-5 kV) was used for
imaging in order to observe the surface morphology of particles
in detail.
Analytical Methods. The elemental contents of Ca, Si, P,
K, Na, S, and Cl were analyzed with particle-induced X-ray
emission (PIXE) and instrumental neutron activation analysis
(INAA) from precyclones, polycarbonate filters, and size-
classified BLPI samples. The methods are described by Maen-
haut et al.20,21 PIXE was used for Si, P, and S, INAA for Na,
and average results from these two methods for Ca. In the
cases of K and Cl, precyclone samples were analyzed with
INAA, and the average of the two methods was used for
polycarbonate filters and BLPI samples. One-quarter of the
filters and the BLPI-collection substrates were used for each
analysis. The BLPI size fraction d > 11 m was not analyzed
due to negligible mass loading on that stage.
Fuel, quartz sand used as the bed material, bottom ash, and
the quartz fiber filters (forest residue only) were analyzed with
inductively coupled plasma atomic emission spectroscopy
(ICP-AES). Quartz fiber filters from combustion of willow
were analyzed with inductively coupled plasma mass spec-
troscopy (ICP-MS). The contents of water-soluble Ca2+,
HPO42-, K+, Na+, SO42-, and Cl- ions were determined from
precyclone (forest residue only) and quartz fiber samples with
ion chromatography (IC).
Results
Compositions of Fuels, Sand, and Bottom Ash.
The elemental composition of dried fuels and of labora-
tory-prepared ashes is given in Table 2. The main ash-
forming elements were calcium, silicon (only in forest
residue), and potassium. The silicon concentration in
willow was 25% of the concentration in forest residue.
Potassium was the dominant alkali metal in both fuels.
(20) Maenhaut, W.; Ryset, O.; Vadset, M.; Kauppinen, E. I.; Lind,
T. M. Analysis of size-fractionated coal combustion aerosols by PIXE
and other analytical techniques. Nucl. Instrum. Methods Phys. Res.
1993, B75, 266-272.
(21) Maenhaut, W.; Kauppinen, E. I.; Lind, T. M. Study of size-
fractionated coal-combustion aerosols using instrumental neutron
activation analysis. J. Radioanal. Nucl. Chem. 1993, 167, 259-269.
must have been present in other forms than as chlorides
and sulfates. Also during the combustion of forest
residue, chlorides and sulfates cannot have been the
only significant alkali compounds (the molar ratio was
1.4). The composition of the sand and the bottom ash
during forest residue tests are given in Table 3.
Ash Retention in the Bed during Combustion of
Forest Residue. The ash-forming constituents fed into
the furnace with the fuel end up either in the bottom
ash with the removed bed material or in the flue gas
duct as fly ash and vapors. The bottom ash fractions of
each element X were calculated as quotients of the
amount of X removed with the bottom ash and of the
total output of X (bottom ash + fly ash). Only the ash
originating from the fuel is considered in the bottom ash
fractions, thus the amount originating from the quartz
sand is subtracted, i.e.
QbCb(X)
BFout(X) ) (1)
QbCb(X) + QflCfl(X)
where
Cb(X) ) Cb(X) - Cb(sand)Cs(X)
BFout(X) ) bottom ash fraction of element (X) as
calculated from eq 1, Qb ) bottom ash removal rate (kg/
h), Qfl ) fly ash mass flow rate (kg/h), Cs(X) ) concen-
tration of element X in the quartz sand fed to the
furnace (wt %), Cb(X) ) concentration of element X in
the bottom ash (wt %), Cb(sand) ) concentration of
quartz sand in the bottom ash (wt %), and Cfl(X) )
concentration of element X in the fly ash (wt %). In the
case of sulfur, the contribution from the gaseous SO2
was added to the term QflCfl(X).
Cb(sand) was evaluated assuming that the percentage
of ash removed with the bottom ash was the same as
the percentage of the most common ash-forming element
(calcium) removed. Thus, Cb(sand) was calculated from
Cb(Ca) ) Cs(Ca)Cb(sand) + Cfu(Ca)[1 - Cb(sand)]
(2)
where Cfu(X) ) concentration of element X in the fuel
(wt %).
The bottom ash fractions were also calculated as a
fraction from the total amount of element X fed into the
reactor with fuel
 384 Energy & Fuels, Vol. 13, No. 2, 1999
QbCb(X)
BFin(X) ) (3)
QfuCfu(X)
where BFin(X) ) bottom ash fraction of element X as
calculated from eq 3, Qfu ) fuel feed rate (kg/h). Values
for BF(X) determined using eqs 1 and 3 would be the
same if the mass balance of the furnace was determined
with absolute accuracy
QfuCfu(X) + QbCb(sand)Cs(X) )
QbCb(X) + QflCfl(X) (4)
where the left-hand side includes fuel and sand feed into
the furnace and the right-hand side includes the output
from the furnace with bottom ash and fly ash. However,
since the accuracy was not absolute, both eqs 1 and 3
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are considered. The bottom ash fraction for total ash
was calculated from eqs 1 and 3 by setting Cb(ash) )
Cs(ash) ) Cfl(ash) ) Cfu(ash) ) 1.
Error estimates were calculated based on the repro-
ducibility of the measured values. The error estimate
for Cfu(X) was the standard deviation of the four samples
analyzed. Only one sand sample was analyzed. The
error estimates for Cs(X) were chosen to be the same as
the ones for Cfu(X). This is presumed to have been a
conservative estimate, since sand is considered to have
a more stable composition than the forest residue. The
error estimates for the parameters with one value per
day (Cb(X), Cfl(X), Qb, Qfl, and Qfu) were taken to be (0.5
times the deviation between the two values.
The influence of the experimental inaccuracy is
reduced when the bottom ash fractions are presented
as relative to that of calcium
BFout(X) Qb/Qfl + Cfl(Ca)/Cb(Ca)
) (5)
BFout(Ca) Qb/Qfl + Cfl(X)/Cb(X)
BFin(X) Cfu(Ca) Cb(X)
) (6)
BFin(Ca) Cfu(X) Cb(Ca)
About 30-40% of the fuel-originated ash was retained
in the bed and removed with bottom ash (Table 4). The
value for Cb(sand) was 86 ( 2%, indicating that 14 (
2% of the bottom ash was fuel-originated ash. Calcium
and phosphorus were retained in the bed with a similar
efficiency as the overall ash. The bottom ash fraction
was largest for potassium (about 50%). On the other
hand, less than 10% of sulfur as well as less than 2% of
chlorine were found in the bottom ash.
The mass balance, determined as a quotient of the
evaluated total output (fly ash + fuel-originated fraction
of the bottom ash) and input (fuel feed) flow rates, was
80% for overall ash. The elemental mass balances were
between 78% and 120% for all the other elements except
chlorine. The chlorine input into the furnace was 6 times
the detected output, since the output fraction did not
include the gaseous chlorine (most likely as HCl) that
was not condensed inside the filter sampling system.
The difference can be seen in Table 4 by the fact that
the upper limit for BFout(Cl) without gaseous Cl was 6
times the upper limit for BFin(Cl) (11% vs 1.7%).
The experimental inaccuracy of the bottom ash frac-
tion of K was larger than that of Ca and P. This is due
to the fact that about one-third of K originated from the
Valmari et al.
Table 4. Fractions of the Ash-Forming Constituents
Removed with the Bottom Ash during Combustion of
Forest Residuea
BFout(X), % BFin(X), % BFout(X)/ BFin(X)/
X eq 1 eq 3 BFout(Ca) eq 5 BFin(Ca) eq 6
ash 40 ( 6 31 ( 7 0.97 ( 0.12 1.00 ( 0.58
Ca 41 ( 5 31 ( 7 1 1
P 31 ( 5 31 ( 5 0.76 ( 0.11 1.00 ( 0.16
K 57 ( 11 45 ( 12 1.39 ( 0.30 1.44 ( 0.46
S 5 ( 2b 5(2 0.13 ( 0.06b 0.17 ( 0.06
Cl <11c <1.7 <0.3c <0.05
a The fractions were calculated according to eqs 1 (BF
out(X), X
in the bottom ash divided by X in the total output from the furnace)
and 3 (BFin(X), X in the bottom ash divided by X in the input into
the furnace with fuel). b SO2 is included in the fly ash fraction.
c Gaseous Cl (e.g., HCl) is not included.
sand, whereas Ca and P originated almost entirely from
the fuel. As Table 3 shows, the potassium concentration
in the sand was 2.0% and in the bottom ash 3.15 (
0.15%. The increase in potassium concentration was,
thus, quite clear, and the bottom ash composition is
expected not to have rapid fluctuations since only a
small fraction of the bed material is changed each day.
We believe that our conclusion of BF(K)/BF(Ca) > 1 is
justified, even if a choice of more conservative error
estimates would have enabled BF(K)/BF(Ca) to be e1.
It should also be noted that the analysis presented above
was based on the assumption that sand-originated
potassium was not released to the fly ash fraction. If
this effect took place, then the values for BF(K) and
BF(K)/BF(Ca) would be expected to be even higher than
the ones presented in Table 4, as BF(X) considers only
fuel-originated ash.
Sodium was observed to have been released from the
sand. The Na feed rate was 3.1 kg/h with the sand and
0.9 kg/h with the fuel. The Na mass flow from the
furnace was 2.4 kg/h with the bottom ash and 1.4 kg/h
with the fly ash. Thus, the rate of sand-originated Na
ending up in the fly ash was about 0.5-0.7 kg/h larger
than the rate of fuel-originated Na ending up in the
bottom ash.
Fly Ash Characterization. The fly ash mass con-
centration downstream of the process cyclone was 1200
mg/Nm3 during combustion of forest residue and 600
mg/Nm3 with willow (Tables 5 and 6). About 1% of the
ash-forming constituents with forest residue and 0.4%
with willow were in the vapor phase, as determined with
the filter system (Table 5). It should be noted that the
vapor fractions may be underestimated if some vapors
reacted with quartz fiber filter and became erroneously
counted as particles.
The fly ash particle size distribution consisted of two
distinct modes (Figure 4). The border between the two
modes was located at 0.4 m with forest residue and at
0.7 m with willow. The coarse mode contained over
90% of the mass in both cases. Fine-mode particles
contributed 2% of the total fly ash mass with forest
residue and 8% with willow (Table 6).
The coarse-mode fly ash particles, as detected with
SEM, were mainly agglomerates of primary particles
whose size varied from less than 0.05 m to ap-
proximately 0.5 m (Figure 5). The temperature during
the combustion process was not high enough for com-
plete coalescence of coarse particles into compact,
spherical particles. Coarse particles also contained some
 Ash Formation Energy & Fuels, Vol. 13, No. 2, 1999 385

Table 5. Mass Concentrations of Ash-Forming Species

after the Process Cyclone According to Filter
Measurements (average of two measurements)a
vapors, mg/Nm3 vapors, % total, mg/Nm3
(a) Forest residue
ash 14.3 1.1 1230
Ca 0.03 0.01 243
Si 0.09 0.08 115
P <0.01 <0.02 39
K 4.2 6.9 62
Na 0.2 1.5 15.3
S 0.5 1.1 39.5
Cl 4.3 >85 4.4-5.1
(b) Willow (Salix)
ash 2.2 0.4 599
Ca 0.007 0.005 131
Si 0.006 n.a.b n.a.
P 0.003 0.008 37 Figure 4. Fly ash particle mass size distributions down-
K 0.6 0.9 68
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stream of the process cyclone at flue gas temperature of 810-

Na 0.02 0.3 5.9 850 C. The size range d < 2 m was measured with the BLPI.
S 0.006 0.04 14 The size range d > 2 m is presented as a sum of BLPI and
Cl 0.7 88 0.8
precyclone contributions.
a The flue gas temperature at the sampling station was 830-

850 C during measurements with forest residue and 810 C with 2.1% in the laboratory prepared willow ash (Tables 2
willow. SO2 contained 9.1 and 15.7 mg/Nm3 of gaseous sulfur
during combustion of forest residue and willow, respectively. SO2 and 6). This suggests that during combustion of willow,
contribution is not included in the numbers given above. b n.a. ) the Si in the fly ash originated mainly from fragmented
not analyzed. SiO2 bed material. In the case of forest residue, the Si
concentrations were close to each other (7.5% in fly ash
Table 6. Fly Ash Particle Mass Concentrations Measured
with the BLPI-Sampling System (average of two
and 8.3% in laboratory-prepared ash).
measurements)a Chlorine was found predominantly in the vapor phase
fine mode, mg/Nm3 fine mode, % total, mg/Nm3
downstream of the process cyclone. The total Cl con-
centrations observed with the BLPI were much higher
(a) Forest Residue
than the ones observed during the filter measurements
ash 24 2.0 1178
Ca 0.5 0.2 238 (Tables 5 and 6). This suggests that chlorine compounds
Si 0.08 0.1 88 reacted with quartz fiber filter, resulting in a Cl
P 0.10 0.3 33 compound that was not condensed during quenching
K 8.5 16.5 51 (HCl). Vapor condensation did not take place only on
Na 0.8 6.4 13
S 0.7 1.2 59 the fine particles. In fact, 29-36% of the chlorine was
Cl 7.9 71 11 observed in the coarse-mode ash, as determined with
(b) Willow (Salix) the BLPI (Table 6, Figure 6).
ash 47 8 577 Sulfur was not found in significant amounts in the
Ca 1.5 1.3 123 vapor-phase downstream of the process cyclone (Table
Si 0.07 0.1 55 5). According to this result, sulfur could have been
P 0.4 1.4 29
K 17 32 52 present in the particle phase and as gases that were
Na 0.6 13 4.2 not condensed during quenching (SO2). An interesting
S 6.3 55 11.5 difference between the two fuels was found for sulfur.
Cl 2.1 64 3.2 With forest residue, SO2 contributed 20% of all the
a In the case of forest residue, the same precyclone sample was sulfur downstream of the process cyclone. Particle-phase
used with both BLPI samples. sulfur was found almost entirely in the coarse mode.
When willow was burned, about 50% of the sulfur was
solid, larger structures with irregular surface structure. present as SO2, 25% in the fine-mode particles, and only
No differences between forest residue and willow were 25% in the coarse-ash particles.
found in the morphology of coarse fly ash particles. A majority of K and Na was found in the particle
The fine-mode particle morphology is dominated by phase downstream of the process cyclone. A larger
species (alkali chlorides) that were condensed at tem- fraction of K (7% with forest residue and 1% with
peratures lower than 800 C (during quenching or in willow) than of Na (1.5% and 0.3%, respectively) was
the convective back pass, depending on where the found in the vapor phase. The molar ratio (K + Na)/Cl
sample was collected). Therefore, their morphology is was close to unity in the vapor fraction, indicating that
not included in the present paper but in another paper the elements were present as alkali chlorides (KCl and
of this series.14 NaCl). The dominating vapor-phase compound was KCl
Vapor- and Particle-Phase Elemental Concen- (8 mg/Nm3 with forest residue and 1.3 mg/Nm3 with
trations. According to filter measurements, over 99.9% willow).
of Ca, Si, and P were in the particle phase after the Elemental Concentrations in Fly Ash. Si was
process cyclone (Table 5). These elements were almost enriched on the coarsest particles (precyclone fraction),
entirely present in coarse particles downstream of the whereas the concentrations of Ca and P in fly ash were
process cyclone (Table 6, Figure 6). Si concentration in fairly constant throughout the size range d > 1 m
fly ash was 9.5% during combustion of willow but only (Figure 7). Detailed elemental size distribution informa-
Purchased by San Carlos Clean Energy Inc 386 Energy & Fuels, Vol. 13, No. 2, 1999
Figure 5. SEM micrographs of coarse fly ash particles collected during combustion of (a) forest residue and (b) willow (Salix).
tion is not available in the size range of d > 10 m. This
is due to the fact that the precyclone sample was
analyzed as a whole, without size classification. The size
range d > 2 m (which is dominated by the precyclone
contribution) in Figure 6 was deduced assuming that
the composition of the precyclone-collected particles do
not depend on their size. For most of the elements this
seems to be a reasonable assumption, as their concen-
trations in the coarsest analyzed BLPI-size fraction (5-
10 m) were similar to the ones in precyclone. However,
the enrichment of Si in the precyclone fraction suggests
that Si was concentrated in larger particles than were
the other species in the coarse mode.
Cl was enriched in fine particles, which is character-
istic for species that have volatilized followed by con-
densation.2 The concentration curve of S in fly ash
followed that of Cl during combustion of willow. This
suggests that S was also introduced to the particle phase
mainly via condensation. When forest residue was
burned, sulfur was depleted in particles with d < 0.3
m.
In the size range d < 1 m, the concentration curve
of K followed that of Cl (forest residue) and that of S
(willow), suggesting that K was present mainly as KCl
and K2SO4, respectively. Sodium was not quite as
clearly correlated with S or Cl as was potassium. In the
coarse-particle size range, the concentrations of alkali
metals did not follow the concentrations of S or Cl.
Fly Ash Water Solubility. Water-soluble fractions
of Ca, Na, and K in the fly ash collected in the
precyclone (d > 3 m) during combustion of forest
residue are shown in Table 7. Soluble sulfate (SO42-)
concentration was compared to total sulfur concentra-
tion and the soluble phosphate concentration (detected
as HPO42-) to total phosphorus concentration. Ca, K,
and Na were present mainly in a water-insoluble form.
All the phosphates were water insoluble, whereas most
of the sulfates were water soluble.
Water-soluble fractions were also detected from quartz
fiber filters (d < 3 m) with both fuels. It should be
noted that the possible vapor reactions with quartz fiber
material may have distorted the data. In addition,
samples collected on the quartz fiber filters during
combustion of forest residue were dissolved in nitric acid
before analysis, so that the compounds not soluble in
that solvent, e.g., some of the silicates, were not
observed. However, two observations can be made.
Valmari et al.
Alkali metals (K and Na) were present in the d < 3 m
fraction mainly in a water-soluble form, unlike in the
precyclone fraction. On the other hand, practically all
the phosphates were water insoluble, also in the d < 3
m fraction.
Discussion
Volatilization and Ash Retention in Bed. Ca, P,
and Si were not found in the vapor phase after the
furnace nor were they found in submicrometer particles
formed from condensed species. On the basis of these
results, it is likely that they were not volatilized during
the process. Therefore, the 30-40% of Ca and P found
in the bottom ash during combustion of forest residue
is concluded to have been retained via ash particle
collisions and attachment on the bed-material surfaces.
The fraction of potassium retained in the bed was
clearly higher than that of Ca and P, indicating that
the retention mechanism described above is not enough
to explain the retention of potassium. Also, a significant
fraction of potassium was volatilized and condensed on
the fine-mode particles. The behavior of potassium could
be explained assuming that a fraction of potassium
vapors reacted with the quartz sand bed material,
resulting in retention of K in the bed as potassium
silicate.22
Sulfur was not retained in the bed. It must have been
released as gaseous species either from the fuel/ash
particles before they were attached on bed-material
particles or afterward from the bed material. About 80%
of SO2 released from the furnace had chemically reacted
with ash species already after the process cyclone during
combustion of forest residue. Only 1% of sulfur was
found in the fine-mode particles. The behavior of sulfur
was clearly different when willow was burned. About
50% of sulfur remained as SO2, and 25% was found as
fine alkali sulfate particles. Alkali sulfate had condensed
already before our sampling station (flue gas tempera-
ture 810 C), since the vapor-phase fraction of sulfur
was practically nonexistent. Only 25% of S was found
in the coarse ash.
(22) Latva-Somppi, J.; Kurkela, J.; Tapper, U.; Kauppinen, E. I.;
Jokiniemi J. K.; Johanson, B. Ash deposition on bed material particles
during fluidized bed combustion of wood-based fuels. Proceedings of
the International Conference on Ash Behavior Control in Energy
Conversion Systems 1998, Yokohama, Japan, 119-126.
Purchased by San Carlos Clean Energy Inc Ash Formation Energy & Fuels, Vol. 13, No. 2, 1999 387

Figure 6. Elemental mass size distributions downstream of the process cyclone. Elemental analysis was not carried out separately
from each of the precyclone size fractions. Therefore, the precyclone contributions (d > 2 m) are deduced as products of the
measured total mass size distribution curves (Figure 4) and the analyzed contents of each element in the non size-classified
precyclone samples.

Chlorine was not retained in the bed and was found
almost entirely in the vapor phase after process cy-
clone. Thus, it was volatilized in the furnace and did
not react with bed material. A fraction of alkali chlor-
ides may have reacted with quartz fiber filter or ash
particles that were previously collected on the filter.
This would have resulted in condensed alkali com-
pounds retained on quartz fiber filter and gaseous
chlorine (HCl). That would also explain the observed
2-fold (forest residue) or 4-fold (willow) total chlorine
concentration during BLPI measurements as compared
to the filter samples.
Fly Ash Compounds. Potassium and sodium were
mainly found in a water-insoluble form in the precyclone
fraction (d > 3 m) during combustion of forest residue
but as a water-soluble form in smaller particles (d < 3
m). The insoluble alkali metals were presumably
bound mainly in silicates. Insoluble potassium and
sodium were found mainly in the precyclone, where also
93% of silicon was detected. Sodium species seem to
have reacted more with fuel-originated silicates than
potassium, as the water-soluble fraction of sodium in
fly ash was lower than that of potassium. The lower
vapor fraction of Na as compared to K (Table 5) and
the lower fine-mode fraction (Table 6) also suggest that
sodium vapors reacted more efficiently with silicate
species than potassium vapors. In addition to alkali
chlorides, the water-soluble alkali-metal fraction could
include, e.g., sulfates, carbonates, or oxides.
Most of the sulfur in coarse particles must have been
in forms other than alkali sulfates in the case of forest
residue, since the molar ratio (K + Na)/2S was only 0.4.
However, it is likely that a substantial fraction of S in
supermicrometer particles was present as CaSO4 as
suggested by XRD-data.15 During combustion of willow,
substantial condensation of alkali sulfates is also ex-
Purchased by San Carlos Clean Energy Inc 388 Energy & Fuels, Vol. 13, No. 2, 1999 Valmari et al.

Figure 7. Elemental fly ash composition (mass of element X/total mass) as a function of particle diameter. The precyclone sample
(collected prior to quenching) is plotted at 20 m.

Table 7. Water-Soluble Fractions (%) in Fly Ash and attachment to the bed material. The higher reten-
Collected Upstream of the Convective Back Passa tion efficiency of potassium can be explained by a
forest residue willow chemical reaction between vapor-phase potassium and
quartz quartz quartz sand. K and Na were mainly present in water-
precyclone fiber filter fiber filter insoluble form in fly ash formed during combustion of
d > 3 m d < 3 m d < 3 m forest residue, presumably bound in silicates.
sample 1 2 3 2 3 4 5 Sulfur and chlorine were volatilized in the furnace.
Ca 30 28 22 40 25 6 12 After the process cyclone at 810-850 C, chlorine was
Pb 0 0 0 0 0 1 0 present almost entirely in gaseous form as KCl and
K 35 17 17 >77 >86 81 99 presumably also as HCl. During combustion of forest
Na 17 6 8 50-60 80 56 70 residue, 80% of sulfur had already reacted with species
Sc 71 63 60 51 92 79 101
present in the coarse ash particles before the sampling
a Fractions are determined as the ratio of the water-soluble
station located after the process cyclone. CaSO4 was a
concentration detected with IC and total concentration detected
major product of these reactions. When combusting
with PIXE, INAA, or ICP-AES. b Water-soluble P includes only P
bound in phosphates (detected as HPO4). c Water-soluble S in- willow, about 50% of the sulfur remained as SO2. More
cludes only S that was bound in SO4. than one-half of the particle-phase sulfur was present
as alkali sulfates in fine particles, which were almost
pected to have taken place on the coarse particles, as nonexistent during forest residue combustion. The
was the case with alkali chlorides. behavior of sulfur was more sensitive to changes in the
The concentration of P as a function of particle size process than that of the other elements. A larger
resembles that of Ca, suggesting that phosphorus could fraction of SO2 reacted with alkali metals when a fuel
have been associated mainly with calcium (Figure 7). with a higher (K + Na)/(Cl + 2S) molar ratio (willow)
Phosphorus was not present as water-soluble phos- was used. However, the fraction of SO2 that did not react
phates, but the existence of insoluble calcium phos- with any ash species was also higher with willow. SO2
phates such as Ca2P2O7 is possible based on our data. reacted more with species present in coarse ash (cal-
cium) in the case of forest residue. A more detailed
examination involving the effects of process conditions
Summary
(inorganic compounds present in fuel, temperatures,
The behavior of Ca, Si, P, K, Na, S, and Cl during oxygen concentrations, etc.) would probably be needed
circulating fluidized-bed combustion of forest residue to explain the differences in sulfur behavior observed
and willow was studied experimentally in a 35 MW co- between the fuels.
generation plant. During combustion of forest residue,
30-40% of ash was retained in the furnace attached to Acknowledgment. This study was funded by the
quartz sand bed particles and was eventually removed Finnish Technology Development Center (TEKES), VTT
from the bed along with bottom ash. Ca and P were Chemical Technology, and Foster Wheeler Energia via
retained with a similar efficiency as the total ash, indi- the LIEKKI 2 national combustion research program
cating that they were retained via ash particle collisions as well as by the Commission of the European Com-
 Ash Formation
munity, Vattenfall Utveckling AB, and VTT Chemical
Technology via Joule 3 (Contract No. JOR3-CT95-0001).
We acknowledge the contribution of Mr. Raoul Jarvinen
during the measurements with willow, the discussions
with Dr. Jouko Latva-Somppi and Dr. Jorma Jokiniemi
from the VTT Aerosol Technology Group, Dr. David P.
Brown for carefully revising the manuscript, as well as
Purchased by San Carlos Clean Energy Inc
Energy & Fuels, Vol. 13, No. 2, 1999 389
the contribution of the power plant operating staff. W.M.
is indebted to the Fonds voor Wetenschappelijk Onder-
zoek-Vlaanderen for research support. He is also
grateful to J. Cafmeyer and K. Beyaert for assistance
in the chemical analyses.
EF980085D