A COMPARISON STUDY OF ACFB AND PCFB ASH

CHARACTERISTICS

K.M. Sellakumar and R. Conn

Foster Wheeler Development Corporation,
12 Peach Tree Hill Road, Livingston, NJ 07039, USA

A. Bland
Western Research Institute, 365 N. 9th St, Laramie, WY, 82070, USA

6th International Conference on Circulating Fluidized Beds

Wurzburg, Germany

August 22-27, 1999

A COMPARISON STUDY OF ACFB AND PCFB ASH CHARACTERISTICS

K.M. Sellakumar and R. Conn
Foster Wheeler Development Corporation, 12 Peach Tree Hill Road, Livingston, NJ 07039, USA

A. Bland
Western Research Institute, 365 N. 9th St, Laramie, WY, 82070, USA
Abstract - The advent of fluidized bed combustion technology has provided avenues
for environmental issues-free use of all types of fossil fuels. With the potential
commercial application of Pressurized Circulating Fluidized Bed Combustion (PCFB)
technology in the very near future, there is a need to understand the similarities and
differences in the characteristics of solid by-products from the conventional
Atmospheric Circulating Fluidized Bed Combustion (ACFB) and the PCFB. Similar to
ACFB residues, the main components in PCFB residues are from:
-

the inorganic constituents in the coal and incorporated sediments (Al, Fe, and Si),
sorbent derived elements (Ca, from limestone, or Ca and Mg if dolomite is used),
and
sulfur released from the coal during combustion that is captured by the sorbent.

However, the concentration of each component in the residues may show great
variations, depending on the feeds and operating conditions in the unit. In general,
the residues discharged from PCFB units with the same types of feeds and sulfur
retention should have a relatively lower content of calcium but a higher content of
coal-derived constituents than those from ACFB units, because a lower sorbent feed
is required for pressurized systems. Also, the sorbent-derived components in the
residues from both systems are different due to the various sulfation mechanisms
under atmospheric and pressurized conditions.
Ash samples from the commercial ACFB plants and the Foster Wheeler 10 MWth
PCFB pilot plant in Karhula have been used in this study. In this paper, the ash
characteristics and where one type of ash- ACFB ash or PCFB ash has better
application over the other are described.
INTRODUCTION
CFB combustion has proven to be one of the most promising technologies for burning a wide range
of coals and other fuels and handling wide variations in fuel quality, while still achieving strict air
emission requirements. Low-grade fuels that have large ash content and very high sulfur do not
normally find acceptance in pulverized coal (p.c.) units. These fuels are burned efficiently in CFB
systems. However, if the sulfur content is large, then necessary sorbent has to be added to capture
SO2 in solid form.
CFB boilers generate two major waste streams, fly ash and bottom ash, which are a mixture of fuel
ash, unburned carbon residues, and lime particles coated with sulfate layers. The ash properties are
substantially different from the p.c. ashes typically marketed as ASTM Class C and F fly ashes. The
operating conditions for CFBC units, in addition to the fuel and sorbent characteristics, directly
contribute to the chemical characteristics of the ashes. CFB ashes generally contain a higher
content of calcium as an oxide and as a sulfate, but a lower content of silica and alumina than ashes
generated from p.c. boilers. One notable exception is ashes resulting from the firing of low sulfur
anthracites and bituminous coals; these by-products are composed primarily of fuel ash
constituents, since sorbent does not dominate ash chemistry. Consequently, the utilization options
for CFB ashes are somewhat more diverse than p.c. ash, due to the effect of sorbent on the overall
ash chemistry.

Pressurized fluidized bed combustion (PFBC) represents one of the most promising emerging Clean
Coal Technologies (CCT). Circulating PFBC technology is being demonstrated at the pilot-scale at
Foster Wheeler Energia Oy in Karhula, Finland. Western Research Institute (WRI) has completed a
three-year project under sponsorship of the Electric Power Research Institute (EPRI), Foster
Wheeler Energy International, Inc., and the U.S. Department of Energy (DOE) Federal Energy
Technology Center (FETC) that addressed ash use markets and options for PFBC technologies.
FW supplied representative ash samples from the Karhula PCFB pilot combustor operation for this
study. The overall objectives of this study were to determine the market potential and the technical
feasibility of using PFBC ash in high-volume use applications.
The Environmental Protection Agency (EPA) made a final rule that effective September 2, 1993,
four large-volume fossil fuel combustion (FFC) waste streams from electric utility power plants are
exempted from RCRA (Resource Conservation and Recovery Act of 1976) Subtitle C for hazardous
waste regulations (Federal Register 1993). The waste streams include fly ash, bottom ash, boiler
slags, and flue gas desulfurization (FGD) sludge. Nevertheless, the fluidized bed combustion (FBC)
waste streams were not included in this final regulatory determination due to the lack of information.
Since early 1990s, extensive studies have been conducted on the ACFB and PCFB ashes (Young,
1996; Conn and Sellakumar, 1997, Conn, Wu, and Sellakumar 1997; Bland, 1998).
In this paper, a review of the ACFB and PPCFB processes, key changes in the by-product
constituents, and attendant differences in the physical and chemical properties are described. In
addition, the current and potential uses of the by-products are outlined.
ACFB AND PCFB PROCESSES
In fluidized bed combustors, limestone is added in the bed for sulfur capture. Probable sulfur
capture mechanisms in the ACFB and PCFB combustors have been summarized earlier (Koskinen
et al., 1993). Numerous studies have confirmed that at atmospheric conditions, the first step in the
sulfur capture process is the calcination of CaCO3.
CaCO3 (s) CaO (s) + CO2 (g)
(1)
The calcination reaction proceeds significantly faster than the next step that is the sulfur capture
step, called the sulfation reaction.
CaO (s) + SO2 (g) + 1/2 O2 (g) CaSO4 (s)
(2)
Under pressurized fluidized bed combustion conditions, the high partial pressure of CO2 that exists
by virtue of the high combustor pressure, prevents the decomposition of CaCO3. At high O2 partial
pressures, the desulfurization reaction in pressurized conditions is via the "direct" sulfation of
CaCO3.
CaCO3(s) + SO2(g) + 1/2 O2(g) CaSO4(s) + CO2(g)
(3)
However, in the presence of some catalysts SO2(g) can be converted to SO3(g), and the following
reaction is also possible (Hajaligol et al. 1988):
CaCO3(s) + SO3(g) CaSO4 (s) + CO2(g)
(3a)
Thermal decomposition of CaSO4 in normal pressurized fluidized bed combustion conditions is not
probable because of low temperatures and high pressures in the reactor. However, according to
Lygnfelt and Leckner (1989) significant amounts of SO2 may be released from the sorbent in the
pressurized fluidized bed combustion if conditions become reducing in the reactor.
In summary, it can be concluded that under PCFB conditions:
the sulfation of sorbents takes place by a direct reaction between CaCO3 and SOx..
the sulfation rate increases with temperature and
the total pressure in the combustor does not limit the sulfur capture by the sorbent.
The surface structure of the ash particles from the PCFB process is likely to be different from
that of the ash from the ACFB process.

CHARCTERIZATION OF ACFB ASH

Chemical Properties: Key oxides of interest for ash use in typical ACFB bottom ash and fly ash
are presented in Table 1. The chemical characterization testing included major element
composition, as well as phase analysis. There is a general decrease in CaO and SO3 with
decreasing sulfur content of the fuel burned. Fuel ash contributes silica, alumina, and certain
amounts of alkalis. The fly ash and the bed ash were also analyzed by X-ray diffraction (XRD) for
phase composition. The data confirm the observation that the ashes are composed principally of
anhydrite[CaSO4], lime [CaO], quartz [SiO2], and associated oxides of iron, magnesium, and
dehydroxylated clays originating from the fuel ash components.
Physical Properties: The general physical properties of the ashes were also determined, including
poured and packed bulk densities, specific gravity, particle size distribution, and moisture. The fly
ashes all were relatively fine with greater than 80% passing a 200-mesh screen (74m). As a
result, these ashes can readily be made into cement-type pastes without further milling. The poured
bulk density of the fly ashes ranged from about 540 (low S fuel) to 916 (high S fuel) kg/m3; the
compacted bulk density of the fly ashes were slightly higher and ranged from 840 (low S) to
1167(high S) kg/m3. The specific gravity ranged from 2.2 (low S) to 2.7 (high S) for the fly ashes.
CHARACTERIZATION OF PCFB ASH
The study of PFBC ash use options has included two different ashes: ash from the combustion of
low-sulfur Powder River Basin subbituminous coal (Black Thunder) with limestone sorbent and the
combustion of high-sulfur Illinois Basin coal with a limestone sorbent. (Bland, 1998).
General Chemistry: With the exception of relatively high mineral carbon, the chemistry of the
PCFB ashes is typical of ashes from ACFB of low-sulfur and high-sulfur coals using limestone and
dolomite sorbents. Phase analyses of the ashes by X-ray diffraction show that the PCFB ashes are
composed principally of anhydrite (CaSO4 ), calcite (CaCO3 ), coal ash oxides, and dehydroxylated
clays. The lack of lime (CaO) in the PFBC ashes is distinctly different from AFBC ashes, which
contain large amounts of lime. As stated earlier, in PFBC systems, the partial pressure of CO2
favors both calcination and recarbonization. This results in low lime and high carbonates (calcite) in
pressurized FBC ash. Key oxides of interest for ash use are presented in Table 1. The loss on
ignition (LOI) is composed of the moisture and the organic carbon. The LOI in the PFBC ashes has
been corrected for mineral carbon. Moistures are less than 0.1% and the organic carbon contents
are less than 2%. The free lime (CaO) content of the PFBC ashes was determined by ASTM C-25
to be in the range of 0.5 to 1.0%. The majority of the lime appears to still be carbonated in the form
of CaCO3.
Physical Properties : The general physical properties of the ashes were also determined, including
bulk densities, specific gravity, and particle size distribution. The PCFB fly ashes measured pouredbulk densities of 795 to 948 kg/m3 and specific gravities of 2.73 to 2.34 for high sulfur and low sulfur
fuels respectively. This is just opposite of the ACFB fly ash characteristics.
DISCUSSION
Ash Characteristics: Leachate characteristics of the ashes were tested according to the U.S. EPA
Toxicity Characteristics Leaching Procedure (TCLP) (EPA CFR Part 241). The ash leachate data
substantiate that none of the leachates generated from the ACFB and PFBC ashes exceeded the
1976 RCRA limits. As such, these ashes would not be classified as hazardous. Ashes from other
coal-fired power systems are already categorized as nonhazardous and have been given an
exclusion from these RCRA requirements (Table 2).
Ash Utilization Studies: Diverse utilization options have been studied for ACFB and PCFB coal
ashes. The potential applications include:
- construction applications: cement substitute, concrete block production, brick production, soil
stabilizer, roadbase/subbase materials, structural fill materials, and
synthetic aggregates;

- agricultural applications:
- waste stabilization:

liming and soil amendment;

acidic waste stabilizer and sludge stabilizer.

The key fuel and sorbent properties, which can influence ash characteristics, are sulfur content, ash
content, and ash composition including the form of Ca (CaCO3 or CaO). Other important fuel
properties influencing ash characteristics are the size and friability of the fuel minerals. These
properties will impact on how these minerals will exit the CFB in the fly or bottom ash stream, which
can have a significant effect on the utilization of these streams. Extensive literature is now available
on the ACFB ash use options based on the studies since early 1980s. (Anthony et al. 1995, Kilgour
et al, 1991, Sun et al. 1980, Tavoulareas et al. 1987; Conn et al. 1997; Bland, 1998; Bland, 1999).
Details on PCFB ash use has been reported since 1993 (Bland et al. 1994; Bland, 1998). A
summary of the current know-how is given below.
Ash Use in Construction Applications: ACFB and PCFB fly ashes cannot be classified as Class
F or C, because of low FAS (ferric oxide, alumina, and silica) and high SO3 content (Table 1). Even
though CFB fly ash may not qualify as a Portland cement admixture, it may have the potential for
use in concrete blocks. Bottom and fly ash can be used as an aggregate and pozzolan in concrete
blocks. The bottom ash used as an aggregate has a lower unit weight than many naturally
occurring aggregates, thus reducing the weight of the block. CFB fly ash with properties of Class C
and F can be used as a partial replacement for Portland cement in some block plants. Generally,
the carbon content of the fly ash must be limited to less than 5%, since segregation can occur
during handling and result in nonuniform blocks.
The free lime and sulfate contents of CFB ashes can limit their utilization in concrete block
production. Free lime present in ash will form water-soluble calcium hydroxide, resulting in
weakening of the block from contact with moisture. As with Portland cement concrete, ettringite can
form in concrete blocks due to high ash sulfate levels resulting in mechanical weakening of the
block. It is possible that CFB ash may replace some Class C or F fly ash or Portland cement in
more moderate strength blocks. Such materials may not be preferred for heavy construction
applications, but more for residential uses (Conn et al. 1997). Testing of PCFB ash has indicated
that PFBC ash, when mixed with low amounts of lime, develops high strengths, suitable for soil
stabilization applications and synthetic aggregate production. Synthetic aggregate produced from
PFBC ash is capable of meeting ASTM/AASHTO specifications for many construction applications
(Bland 1998).
Soil/Mine Spoil Amendment: The technical feasibility of ACFB/PFBC ash as a soil amendment
was examined for acidic problem soils and spoils encountered in agricultural and reclamation
applications. The results of the technical feasibility testing indicated the following:

Ash streams from CFB boilers firing low sulfur semi-anthracite and anthracite waste would not
be good candidates for agricultural liming due to very low free lime ( and CaCO3 equivalent)
contents. On the other hand, ash streams from CFB boilers firing bituminous coals may be
suitable for liming, depending upon how calcium is partitioned between the fly ash and bottom
ash.
PFBC fly ashes were effective acid spoil and sodic spoil amendments though they have low
CaO content. In a comparison with ag-lime, the fly ashes reacted with the acidic spoil at a
slower rate and the final pH of the treated material was slightly lower (i.e., fly ash treated, pH 7
and the ag-lime treated 8).
the greenhouse studies demonstrated that PFBC fly ash amended spoils resulted in higher plant
productivity than the ag-lime-amended spoils. These results possibly are due to pH and
nutritional issues, but root penetration was undoubtedly a factor.

CFB ash streams can also be used to stabilize waste streams from a variety of processing
operations. This stabilization includes solidification and fixation of sludge materials for landfilling,

neutralization of acidic wastes, and municipal sludge waste sludge. For each of these applications,
the suitability of CFB ash is enhanced by its free lime content
CONCLUSION
In-house and literature data show that ash streams from CFB boilers firing diverse fuels have the
potential for use in one or more applications. FW has studied the ACFB bottom ash and fly ash
characteristics from both an environmental impact and by-product utilization standpoint. First, the
risk screening criteria and exposure analysis results indicate that these CFB wastes are as clean or
better than those generated from conventional combustors such as p.c. boilers. As a result, CFB
by-products can be used in various applications without impacting the environment. The exact
utilization options for ACFB by-products will depend primarily on the type of fuel being fired, and to a
lesser extent the type of sorbent utilized for sulfur capture. The PCFB ash differs from the ACFB in
the uncalcined CaCO3 in the by-product.
As with ACFB ashes, there is a significant market potential for PFBC ash in the construction and soil
amendment industries. In particular, PFBC ash represents a technically viable material for use in
these currently established applications for conventional coal combustion ashes. It is possible to
modify the hydration reaction chemistry of the PFBC ashes through such processes as lime
enhancement to produce the geotechnical properties required for construction applications. As a
result, PFBC ash should be viewed as a valuable resource, and commercial opportunities for these
materials should be explored for future PFBC installations.

REFERENCES
Anthony, E.J., Iribane, A.P., and Iribane, J.V., Proc. of the 13th Intl. Conf. on Fluidized Bed
Combustion, Orlando, FL, (1995), Vol. 1, pp. 523-533.
Bland, A.E. US DOE Contract DE-FC21-93MC30126, Final Report (Western Research Institute
Report WRI-98-R017), June, (1998).
Bland, A.E., Proc., 1998 Advanced Coal-Based Power and Environmental Systems 98 Conference,
US Department of Energy, Morgantown, WV, (1998).
Bland, A.E., Proc. of the 15thIntl. Conf. on Fluidized Bed Combustion, Savannah, GA, (1999).
Conn, R.E., and Sellakumar , K.M., Proc. of the 14th Intl. Conf. on Fluidized Bed Combustion,
Vancouver, Canada, (1997), pp. 507-518
Conn, R.E., Wu, S., and Sellakumar, K.M., 1997 Pittsburgh Coal Conf., Taiyuan, China (1997).
Conn, R.E., Sellakumar , K.M. and Bland, A.E., Proc. of the 15th Intl. Conf. on Fluidized Bed
Combustion, Savannah, GA, (1999).
Federal Register, Part V, United States Environmental Protection Agency, 40 CFR Part 261, Vol.
58, No. 151, August 9, 1993.
Hajaligol, M.R., Longwell, P.J., Sarofim, A.F, Ind. Eng. Chem. Res. 27, (1988), pp.2203-2210.
Kilgour, C. L., and McGowan, K.I., Electric Power Research Center, Iowa State University, Final
Report, October (1991).
Koskinen, J., Lehtonen, P., and Sellakumar , K.M., Proc. of the 13th Intl. Conf. on Fluidized Bed
Combustion, Orlando, FL, (1995), pp. 369-378
Lygnfelt, A., and Leckner, B., Proc., 10th International Conference on Fluidized Bed Combustion,
Manaker, A., ed., ASME, New York, (1989), pp. 675-684
Sun, C. C., and Peterson, C. H., Proc. Sixth Intl. Conf. on Fluidized Bed Combustion, Philadelphia,
PA, (1980), Vol. 3, pp. 900-912.
Tavoulareas, S., Howe, W., Golden, D., and Eklund, G., Proc. of the 9th Intl. Conf. on Fluidized Bed
Combustion, (1987), Vol. 2, pp. 916-926.
Young, L., Fifth Intl. Conf. on Circulating Fluidized Beds, Beijing, (1996), Pr5

Table 1 Typical Ash Chemistry of Fly Ashes from Different Fuels

Fuel

ACFBHigh
sulfur Bit.

ACFB Low
sulfur Bit.

12.19

7.32

Ash %

Pozzolan in Portland
Cement

PCFBHigh
sulfur Bit.

PCFB - Low
sulfur Bit.

11.3

7.9

3.39

0.48

Class
S, %

4.60

0.55

Ash, wt. %

FA (1)

FA

FA

FA

SO3

7.4

8.0

5 max

5 max

20.83

12.27

FAS (3)

68.8

49.2

70 min

50 min

50.63

57.57

Free CaO

13.7

28.5

<1

<1

Moisture

0.47

na

3 max

3 max

0.15

0.09

LOI

2.8

na

6(2) max

6 max

0.82

0.81

>325 mesh (max)

35.2

na

34 max

34 max

37.83

25.58

Note:

1.
2.
3.

FA= Fly Ash; na= not available

Use of Class F Pozzolan containing up to 12% LOI may be approved by user if acceptable
performance records or test results exist.
FAS= Fe2O3+Al2O3+SiO2

Table 2 Typical Ash Leachate Data for Fly and Bottom Ashes from Different Fuels
Regula
tory
Limit,
mg/L

ACFB- High sulfur

Bit.
FA

BA

ACFB - Low
sulfur Bit.
FA

BA

PCFB- High
sulfur Bit.
FA

BA

PCFB - Low
sulfur Subbit.
FA

BA

0.003

0.001

<0.04

<0.04

0.041

<0.04

0.36

0.18

0.19

0.26

0.32

0.395

0.241

<0.001

<0.001

0.007

<0.001

<0.01

<0.01

<0.01

<0.01

<0.001

<0.001

0.016

<0.001

0.12

<0.05

<0.05

<0.05

<0.5

<0.5

<0.5

<0.5

<0.1

<0.1

<0.1

<0.1

Mercury

0.2

<0.002

<0.002

0.005

<0.002

<0.002

<0.002

<0.002

<0.002

Selenium

<0.2

<0.2

<0.2

<0.2

<0.2

<0.2

<0.2

<0.2

Silver

<0.01

<0.01

<0.01

<0.01

<0.1

<0.1

<0.01

<0.01

Arsenic

0.004

Barium

100

0.41

Cadmium

Chromium
Lead

0.013