Fuel 84 (2005) 1839–1848

www.fuelfirst.com

Mineralogical and engineering characteristics of dry flue gas

desulfurization products
Jerry M. Bighamb, David A. Kosta, Richard C. Stehouwera, Joel H. Beeghlyc,
Randy Fowlerb, Samuel J. Trainad, William E. Wolfee, Warren A. Dicka,*
a
School of Natural Resources, The Ohio State University, 1680 Madison Avenue, Wooster, OH 44691 USA
b
School of Natural Resources, The Ohio State University, Columbus, OH 43210, USA
c
Carmeuse North America, Pittsburgh, PA 15225, USA
d
Sierra Nevada Research Institute, University of California, Merced, CA 95344, USA
e
Department of Civil and Environmental Engineering, and Geodetic Science, The Ohio State University, Columbus, OH 43210, USA
Received 30 August 2004; received in revised form 16 March 2005; accepted 16 March 2005
Available online 18 April 2005

Abstract
Fifty-nine coal combustion products were collected from coal-fired power plants using various dry flue gas desulfurization (FGD)
processes to remove SO2. X-ray diffraction analyses revealed duct injection and spray dryer processes created products that primarily
contained Ca(OH)2 (portlandite) and CaSO3$0.5H2O (hannebachite). Most samples from the lime injection multistage burners process
contained significant amounts of CaO (lime), CaSO4 (anhydrite), and CaCO3 (calcite). Bed ashes from the fluidized bed process were often
dominated by CaSO4 but also contained CaCO3, CaO (lime), and MgO (periclase). Cyclone ashes were similar in composition to the bed
ashes but contained more unspent sorbent and CaSO4 and less MgO. Fly ash in all samples ranged from 10 to 79 wt%. Samples usually
exhibited two distinct swelling episodes. One occurred immediately after water was applied due to hydration reactions, especially the
conversion of CaO to Ca(OH)2 and CaSO4 to CaSO4$2H2O (gypsum). The second began between 10 and 50 d later and involved formation
of the mineral ettringite (Ca6[Al (OH)6](SO4)3$26H2O). The final pH after 112 d ranged from 10.0 to 12.1. If samples are incubated under
‘closed’ (i.e. incomplete recarbonation with atmospheric CO2) and alkaline weathering conditions, gypsum and portlandite are initially
formed followed by the conversion of the gypsum to ettringite. Closed, alkaline conditions typically can occur when FGD products are placed
in confined settings such as a road embankment or buried as a discrete layer as occurs in some surface mine reclamation projects.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: Coal ash; Ettringite; Flue gas desulfurization products

1. Introduction
Coal continues to be the fuel of choice for power
generation throughout much of the world [1]. Burning coal
to generate energy releases SO2 from sulfur-bearing
impurities, and this SO2 has been linked to the formation
of acid rain that causes accelerated soil acidification and
forest degradation. Accordingly, the U.S. Clean Air Act
Amendments of 1990 limit the total amount of SO2 that can
be released to the atmosphere. The combustion of high-
sulfur coal from many parts of the United States causes
* Corresponding author. Tel.: C1 330 263 3877; fax: C1 330 263 3658.
E-mail address: dick.5@osu.edu (W.A. Dick).
0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.03.018
utilities and other coal users to be out of compliance with the
Clean Air Act unless remedial actions are taken. Environ-
mental restrictions have thus spurred the development of
various flue gas scrubbing processes.
Flue gas desulfurization (FGD) technologies are often
classified as either wet or dry processes [2,3]. Wet FGD
systems tend to utilize sorbent more efficiently than dry
processes and typically can reduce SO2 emissions by more
than 90% [4]. Dry FGD systems, however, are more easily
retrofitted onto existing combustion facilities. In both cases,
the removal of SO2 from flue gases results in a solid residue
that must either be disposed or utilized in a beneficial
manner.
In 2001, the amount of FGD material produced was 25.6
million Mg or 22.0% of the total coal combustion products
generated [5]. Approximately 7.55 million Mg (29.5% of
1840 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848
the total FGD produced in 2002) were used in various ways.
Beneficial uses included the production of wallboard,
flowable fill material, cement additives, and autoclaved
aerated concrete block [6,7]. FGD materials are also used in
waste stabilization, roadway/runway construction, mine
reclamation and as agricultural amendments.
Successful engineering applications depend heavily on
the mineralogical properties of FGD materials. Dry FGD
products are usually comprised of unreacted sorbent, coal
ash, and SO2 reaction products and thus have an overall
composition similar to cement, the hardening agent in
concrete. Because of the many dry FGD scrubbing
technologies available, by-products can be quite variable in
their characteristics, and detailed information is required in
situations where destructive expansion can occur. Extensive
data on the properties of coal fly ash/bottom ash are available
in the literature. Of note are papers published by Adriano et
al. [8], Carlson and Adriano [9], Querol et al. [10], Hower et
al. [11] and Martinez-Tarzona and Spears [12]. The
American Coal Ash Association (Aurora, CO, USA) also
hosts a library and web site (http://www.acaa-usa.org) where
much additional information can be obtained. In contrast,
much less data are available on the properties of FGD
products, especially dry FGD materials.
Quantitative mineralogical data for dry FGD samples is
particularly lacking. Several early mineralogical studies
were conducted on products from fluidized bed combustion
systems operated under atmospheric [13,14] and pressurized
[15,16] conditions and on samples from a spray dryer
system [17]. Laperche and Bigham [18] characterized a
mine grout prepared from FGD filter cake and fly ash. These
studies generally focused on only one type of FGD product
and did not consider the relationship to engineering uses.
Kost et al. [19] has recently summarized the chemical
and physical properties of 59 dry FGD product samples. Our
objectives here are to describe the mineralogical properties
of these same samples and to relate these properties to their
equilibrium solubility and swelling characteristics.
2. Materials and methods
2.1. Mineralogical methods
Mineralogical analyses were performed on dry FGD
products from six power plants representing different types
of scrubbing technologies (Table 1). The technologies were
duct injection, lime injection multistage burner (LIMB),
fluidized bed combustion and spray dryer. Detailed
descriptions of the technologies and samples are given in
Kost et al. [19]. Samples were stored dry in sealed
containers at room temperature until analyses were made.
A variety of analytical methods were used to obtain semi-
quantitative measures of mineralogical composition. X-ray
diffraction (XRD) patterns were obtained from randomly
oriented powder mounts using Cu Ka radiation and a Philips
Table 1
Dry FGD product samples and sample descriptionsa
Sample numbers Plant FGD processb
4–9 American Electric Power (AEP), Duct injection
Beverly, OH
10 FirstEnergy (Ohio Edison) Coolside spray
Edgewater, Lorain, OH dryer
11–22 FirstEnergy (Ohio Edison) LIMB
Edgewater, Lorain, OH
24–25 General Motors Corporation, AFBC
Pontiac, MI
30 EPRI High Sulfur Test Center, Spray dryer
Somerset, NY
33–41 Ohio State University Spray dryer
McCracken, Columbus, OH
49–55 American Electric Power Tidd, PFBC
Brilliant, OH
a
More complete description of samples is provided in Kost et al. (2005).
b
LIMB, lime injection multistage burners; AFBC, atmospheric fluidized
bed combustion (circulating unit); PFBC, pressurized fluidized bed
combustion (bubbling unit).
diffractometer equipped with a PW 1216/90 wide-angle
goniometer, a theta-compensating slit, and a graphite
monochromator. Diffraction patterns were recorded from 5
to 7082q with a step interval of 0.0582q and a counting time of
4 s per step. Instrument calibration was based on both low
(cholesterol) and high angle (NIST SRM 640b Si powder)
diffraction standards. Quartz was ubiquitous and was used as
an internal standard to verify the accuracy of diffractometer
readings from sample materials. Crystalline phase assign-
ments were based on published literature, searches of the
International Centre for Diffraction Data powder diffraction
file, and comparative analyses of reference mineral samples.
Thermal analyses were conducted using a Seiko
SSC5020 instrument that provided simultaneous thermo-
gravimetric (TGA) and differential thermal analysis (DTA).
Samples were heated from 105 to 1125 8C at a rate of
20 8C/min under a continuous flow (200 mL/min) of dry N2.
Calibration of the temperature signal was based on the
melting points of In and Sn. Calibration of the thermal
balance used a reference weight provided by the instrument
manufacturer. Thermal events observed with heating of
samples were assigned to phase transitions based on
published literature and analyses of standard mineral
samples. A reference calcite (CaCO3) was analyzed after
every twenty samples to assure instrument standardization.
Weight losses induced by thermal decomposition of the
standard were maintained within C5% of calculated (ideal)
values.
Calcite and dolomite could not be consistently distin-
guished from each other by thermal analysis. When both
were present in a sample, contents were measured by a
gasometric method using a Chittick apparatus [20]. The
amount of CO2 evolved from the sample after adding 20 mL
of 6 M HCl (containing 0.6 g FeCl2) was measured after
30 s for calcite and 30 min for dolomite. Gas volumes were
corrected for temperature and pressure and then regression
 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848
equations were used to calculate percent calcite and
dolomite [20].
Ash contents were measured by mixing weighed samples
(10–20 g) of FGD product with sodium acetate–acetic acid
buffer (pH 5.0) to form thick slurries. The slurries were
treated with 30% H2O2 to convert CaSO3$0.5H2O (hanne-
bachite) to more soluble CaSO4$2H2O (gypsum). Following
oxidation, and heating at 60 8C to decompose excess H2O2,
the samples were quantitatively transferred to cellulose
dialysis bags and submerged in sodium acetate–acetic acid
buffer (pH 5.0) for 4–6 d to remove acid-soluble materials.
The samples were then dialyzed against distilled H2O to
remove excess salt and to dissolve residual CaSO4$2H2O.
Removal was considered complete when a negative test for
dissolved SO2K
4 was obtained with BaCl2. The samples were
then quantitatively transferred to tared beakers, dried at
100 8C, and weighed to determine residual ash contents.
2.2. Swelling tests
Swelling properties were dependent on the densities and
moisture contents of the samples being tested. Thus, each
measurement was made on samples compacted at the
optimum moisture content and density as determined by the
Standard Proctor Test, ASTM D-698 [21]. The Standard
Proctor mold yields a cylindrical sample 10.2 cm in
diameter by 11.7 cm high. From this cylinder, a test
specimen of 6.4 cm diameter and 2.5 cm height was
trimmed, and the specimen was allowed to swell in
accordance with Method A of ASTM Standard D-4546
[21] except that the swelling pressure (pressure required to
return a sample to its original height after primary swelling
is complete) was not determined. The specimen was given
free access to water and volume change was measured in the
vertical direction. These one-dimensional swelling tests
were performed for up to 561 d on eight specimens (10, 14,
15, 16, 18, 22, 30, and 35), and the mineralogical
compositions of three samples were determined by XRD
analysis at several stages during the process to identify the
cause of swelling.
2.3. Long-term equilibration studies
Long-term solubility studies were performed on five
samples (4, 22, 35, 51, 52). Eight gram of sample and 40 g
of distilled water (1:5 sample/water ratio) were placed in a
50 mL polypropylene centrifuge tube and capped. Sufficient
replicates of each sample were prepared to allow destructive
sampling for eight events during a 4-month period. The
samples were stored in an incubator at 25 8C and were
shaken and aerated weekly. Concentrations of elemental
constituents released to solution were measured in duplicate
tubes at each sampling event (1, 7, 21, 36, 56, 70, 84, and
112 d). The solutions were centrifuged at 5000 rpm for 1 h,
filtered (except for solutions used to measure conductivity,
pH, and Eh ) through 0.2 mm polycarbonate filters,
1841
and analyzed. The solid residues were quick-frozen with
liquid N2 and freeze-dried for subsequent XRD analysis.
Filtered solutions were analyzed for Al, B, Ba, Be, Ca,
Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, S, Si, Sr,
and Zn using inductively coupled plasma emission spec-
trometry as described in Kost et al. [19]. Solutions from
days 1 and 36, and from days 56 and 70 were analyzed at 1:2
and 1:1 sample/diluent ratios, respectively. Solutions from
days 84 and 112 were not diluted before analysis. Aqueous
concentrations of ClK, SO2K 2K
3 , and SO4 were determined
according to Method 429 of Standard Methods for the
Examination of Water and Waste Water [22] using a Dionex
2000i ion chromatograph equipped with an AS4A anion
separator column and an AG4A guard column. Solution pH
values were measured by glass electrode using an Orion
Research Expandable Ion Analyzer EA920 while degassing
the electrode head space with nitrogen gas.
2.4. Equilibrium geochemical modeling
The aqueous-phase geochemical speciation for sample
solutions collected at 56 and 112 d was calculated with
the geochemical speciation programs Soilchem [23] and
MinteqA2 [24]. Molar solution composition data were
input into the Soilchem model to predict the chemical
species that occur under closed conditions (no reaction
with atmospheric CO2) and with precipitation prohibited.
The predicted equilibrium solution concentration of free
cations and anions and the calculated values of ionic
strength (based on the Soilchem results) were recorded.
The total solution composition data and the values of
ionic strength (calculated by the Soilchem program) were
input into MinteqA2. The solution concentrations of free
cations and anions from Soilchem were used as the
initial ‘guesses’ for the ‘free’ ion concentrations in the
MinteqA2 calculations. All MinteqA2 calculations
were conducted with precipitation prohibited. Log
saturation index values (log SI) were calculated by
MinteqA2 using
log SI Z log IAP K log Ksp
where IAP is the activity product of the solution
concentrations of ‘free’ cations and anions present in a
given solid, and Ksp is the solubility product for that
solid. Given a general solid AaBb(s), the Ksp for each
solid is given by
Aa Bb ðsÞ Z aAbCðaqÞ C bBaKðaqÞ
Ksp Z ðaAbCÞðbBaKÞ
where information within each pair of parentheses
denotes ion activities. The ion activity product is given
by
IAP Z ðaAbCÞðbBaKÞ:
1842 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848

Equality between the Ksp and the IAP indicates that a
solution may be at equilibrium with a given solid and
has a log SI value of 0.
Values of log SI for the solids ettringite and
Ca-molybdate (CaMoO4) were calculated manually using
the aqueous activities of the cations and anions obtained
from the geochemical computer modeling. A value of
111.32 was used for the log Ksp of ettringite and K7.94 for
the log Ksp of Ca-molybdate [25].
3. Results and discussion
3.1. Mineralogical characterization
interpretation of other forms of data leading to mineral
quantification.
The XRD results showed that FGD products from the
duct injection and spray dryer processes were similar and
consisted primarily of Ca(OH)2 (portlandite) and
CaSO3$0.5H2O (hannebachite). Portlandite was derived
from the use of excess sorbent, and calcium sulfite was the
primary product of sorbent reaction with SO2 in the flue gas.
Both phases are indicative of low reaction temperatures
(150–200 8C). The coolside sample (10) and those duct
injection samples (6, 8, and 9) produced by recycle of FGD
product contained less sorbent and showed more evidence
of the mineral phases (glass, quartz, mullite, hematite, and
magnetite) associated with fly ash.

Mineralogical analyses of the dry FGD products were Table 2

initiated with the identification of crystalline phases using Crystalline phases detected by X-ray diffractiona
XRD. For many samples, such as the LIMB samples shown FGD process Sample Major mineralsc Minor
in Fig. 1, analyses were made of the original sample and the that generated numberb mineralsc
same sample after removing the water-soluble and acid- sampleb
soluble components. Proportions of crystalline components Duct injection 4 P, H Q, F
could only be estimated from the relative peak intensities 5 P, H C, Q
6 P, H F, M, Q, U
(Table 2). X-ray amorphous phases, such as the glass
7 P Q, F
associated with fly ash, could not be readily detected in 8 P, H F, Q, U
these heterogeneous FGD samples. Nevertheless, a quali- 9 P, H F, Q, U
tative identification of all phases was essential for reliable Coolside 10 Q, P, H C, F, M, U
LIMB 11 L, C, A, P F, M, Q, U
12 R, C, A Q, F, M, U, L
13 B, P, L, A, C, G, R Q, M, F, U
14 R, A, L, C F, M, Q, U, P
15 R, A, C, L P, F, M, Q, U
16 L, Q, A, C P, F, M, U
17 R, L, A, C P, Q, F, M, U
18 A, Q, L, C P, U, F, M
19 A, C, L P, Q, F, M, U
20 L, A, Q, C F, M, U
21 L, A, C F, M, Q, P, U
22 L, A, C P, F, M, Q, U
AFBC 24 A, L, F, Q C
25 A, L, P Q, F, C
Spray dryer 33 C, P, H F, M, Q, U
34 P, H C, F, Q, U
35 P, H C, F, Q, U
37 P, H C, F, M, U
41 P, H Q, U
PFBC 49 D, A, R, C Q, F
50 C, A, R L, Q
51 D, A, R, C Q, F
52 R, A, C L, Q
53 D, A, Q F, L, U
54 D, A, P, Q, C F, L
55 A, R, C L, Q
a
A, Anhydrite (CaSO4); U, Mullite (Al6Si2O13); F, Hematite (Fe2O3); B,
Brucite [(Mg(OH)2]; P, Portlandite [Ca(OH)2]; M, Magnetite (Fe3O4); L,
Lime (CaO); C, Calcite (CaCO3); R, Periclase (MgO); G, Gypsum
(CaSO4$2H2O); Q, Quartz (SiO2); D, Dolomite [CaMg(CO3)2]; H,
Hannebachite (CaSO3$0.5H2O)
b
Fig. 1. Representative X-ray diffraction patterns for LIMB Sample 14. (A) FGD process abbreviations and sample numbers are as shown in
Original sample and (B) fly ash residue after removing water and acid Table 1.
c
soluble components. Listed in order of estimated abundance.
 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848 1843

Most of the samples (Table 2, samples 11–22) from the
LIMB process contained significant amounts of CaO (lime),
CaSO4 (anhydrite), and CaCO3 (calcite) (Fig. 1A). Sorbent in
the LIMB process was injected directly into the upper part of
the boiler at temperatures of 1100–1260 8C. The sorbent
calcines at that temperature to form CaO, which then reacts
with SO2 and O2 in the flue gas to form CaSO4. If a dolomitic
sorbent is used, MgO (periclase) may also form by calcination.
The presence of portlandite and gypsum (CaSO4$2H2O) in
some samples indicates partial rehydration of the FGD
products. The presence of CaCO3 in the same samples
indicates re-carbonation of Ca(OH)2 by reaction with
atmospheric CO2. Similar to the Coolside sample (10) and
the duct injection samples (6, 8 and 9) discussed above, the ash
residue component of the LIMB samples was dominated by
quartz, hematite, magnetite and mullite (Fig. 1B).
By-products from the fluidized bed process (Table 2,
samples 50, 52, 55) were often dominated by CaSO4 but
also contained CaCO3, CaO, and MgO (periclase). The
latter two phases were produced by calcination of dolomite
[(CaMg(CO3)2] sorbent at temperatures of 815–870 8C. The
cyclone ashes (Table 2, samples 49, 51, 54) were similar in
composition but contained more unspent sorbent and CaSO4
and less MgO.
No single analytical technique was adequate for
‘quantifying’ the full range of mineral phases present in
the dry FGD products. To obtain a measure of quantification
(Table 3), data from multiple procedures were used
whenever possible to support or verify the analytical
procedure of choice. Thermal analysis was an excellent
tool for measuring those compounds that were susceptible to
phase transitions with heating. Standard reference materials
were used to develop a basic understanding of the thermal
reactivity of each phase, but the thermal characteristics of
the FGD products were never identical to standard speci-
mens. Variations in thermal behavior resulted from

Table 3
Semiquantitative mineralogy of FGD products

FGD processa Sample Weight percent

numbera Fly ash Calcite Lime CaO Portlandite Anhydrite CaSO3$0. Dolomite Periclase Total
CaCO3 Ca(OH)2 CaSO4 5 H2O CaMg(CO3)2 MgO
Duct injection 4 28 9 38 21 96
5 23 12 40 24 99
6 46 8 10 33 97
7 30 4 36 26 96
8 46 8 11 29 94
9 48 5 5 28 86
Coolside 10 71 13 5 7 96
LIMB 11 49 22 12 10 11 104
12 57 16 4 14 16b 107
13 35 15 9 21c 23d 104
14 48 10 5 3 21 16 103
15 42 14 4 2 24 18 104
16 79 7 7 2 7 102
17 38 14 10 4 18 21 105
18 71 8 6 3 13 101
19 51 10 10 5 25 101
20 67 9 8 3 15 102
21 52 14 11 5 22 104
22 30 15 28 5 25 103
AFBC 24 49 3 12 31 95
25 19 1 21 3 51 7 102
Spray dryer 33 29 33 10 29 101
34 18 18 28 31 95
35 21 17 29 31 98
37 28 15 22 28 93
41 12 15 27 44 98
PFBC 49 33 9 20 31 11 104
50 10 29 4 36 26 105
51 32 12 22 25 12 103
52 10 27 4 1 36 27 105
53 40 3 46 17 4 110
54 40 13 22 17 18 110
55 11 17 6 47 26 107
a
FGD process abbreviations and sample numbers are as shown in Table 1.
b
Includes 10% Mg(OH)2.
c
Includes 11% CaSO4$2H2O.
d
Includes 19% Mg(OH)2.
1844 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848
Fig. 2. Representative thermograms of two different samples types. (A)
Duct injection Sample 4 where A, B, and C show the decomposition of
hannebachite, portlandite, and calcite, respectively, and (B) PFBC cyclone
ash Sample 51 where A and B show the decomposition of dolomite and
anhydrite, respectively. TGA, thermogravimetric analysis; and DTA,
differential thermal analysis.
differences in particle size, crystallinity, and the presence of
other phases. Spiked samples, selective dissolution, XRD
analysis, and the technical literature were used to guide
interpretations. Representative thermogravimetric/differen-
tial thermal analysis (TGA/DTA) results are shown in
Fig. 2.
A 12% stoichiometric weight loss, due to the dehydrox-
ylation of Ca(OH)2 to form CaO, was used to measure the
portlandite (Ca(OH) 2) content of relevant samples
(Fig. 2A). This thermal event occurred across the tempera-
ture range of 375–500 8C and could be defined with little
interference from other thermal transitions. Most FGD
samples contained some portlandite, but the greatest
amounts (Table 3) were in samples 33–41 (OSU spray
drier, 10–30 wt% portlandite) and samples 4–9 (Beverly
duct injection, 5–40 wt% portlandite). The effect of recycle
in the Beverly materials (samples 6, 8, 9) was shown by
reduced quantities of portlandite compared to non-recycle
samples (4, 5, 7).
Concentrations of CaSO3$0.5H2O (hannebachite) were
determined by weight loss associated with the evolution of
water across a temperature range of 300–370 8C (Fig. 2A).
This compound was restricted to samples from the low
temperature, high humidity FGD processes (Table 3), such
as spray dryer (samples 33–41), coolside (sample 10), and
duct injection (samples 4–9). It was present at slightly
greater levels where recycle was used.
Reference specimens of CaSO4 (anhydrite) were ther-
mally stable across the temperature range and experimental
conditions employed, but decomposition was observed in
most of the FGD products containing anhydrite. These FGD
samples may have decomposed because elemental char
carbon is often present and acts as a reducing agent.
Weight losses observed in the range of 850–1050 8C
(Fig. 2B) were in good agreement with total elemental
analysis of S. Because a limited number of anhydrite-
bearing samples did not exhibit a weight loss in this range,
the CaSO4 concentrations in Table 3 were calculated from
total S. In general, the highest quantities of CaSO4 were
associated with the PFBC bed ashes.
The concentration of either CaCO3 or [(CaMg(CO3)2],
when found in a sample alone, could readily be determined
by weight loss from CO2 evolution during thermal analysis.
Although calcination temperatures varied from 600 to
850 8C, the analysis was straightforward when only one of
the two carbonate phases was present. In materials contain-
ing both calcite and dolomite, such as sample 51, the weight
loss resulting from dolomite decomposition was not
completed prior to the onset of calcite decomposition
(Fig. 2B). In these samples, calcite and dolomite were
measured by the gasometric Chittick technique. Variable
amounts of calcite were present in all samples, and dolomite
was also found in the FGD samples when it was used as a
sorbent (Table 3).
Both CaO and MgO are thermally inert and could not be
measured by thermogravimetric analysis. The concentration
of CaO was estimated by first allocating Ca from total
chemical analysis [14] to all other Ca species in the sample
and then converting the remaining Ca to CaO. Periclase
(MgO) was common in samples where dolomite was used as
a sorbent (Table 3). If both periclase and dolomite were
present, the dolomite was measured by the Chittick
technique and a corresponding amount of Mg was allocated
based on a 1:1 Mg to Ca ratio. The remaining Mg was
assigned to MgO.
Fly ash concentrations in the FGD products varied from
10 to 79 wt% (Table 3). No attempt was made to quantify
the fly ash mineralogy, but XRD analyses of the acid-
insoluble residues showed that all contained glass, quartz
(SiO2), hematite (Fe2O3), mullite (Al6Si2O13), and a
magnetic phase similar to partially oxidized magnetite
(Fe3O4) (Fig. 1B). A detailed mineralogical analysis of a
typical fly ash is given in Laperche and Bigham [18] and
Vassilev et al. [26].
 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848 1845

3.2. Swelling tests

Standard Proctor tests yielded optimum moisture

contents and maximum densities ranging from 28 to 63%
and 0.79–1.30 g/cm3, respectively, for the eight FGD
samples examined (data not shown). The maximum density
was not particularly sensitive to slight variations in
moisture content near the moisture optimum. Swelling
amounts for the same eight FGD samples used to
determine optimum moistures and maximum densities
were highly variable with some samples exhibiting
virtually no measurable swelling and others experiencing
volume changes approaching 60% over the time period
monitored (Table 4). Changes in volume as a function of
time revealed two distinct swelling episodes (Fig. 3). The
first episode occurred almost immediately after water was
allowed to react with the FGD material, produced a 0.1–
14% change in volume, and was usually completed within
24 h (Fig. 3A). The second swelling episode usually began
in 10–50 d. Some samples (e.g. Sample 18, a LIMB
material) did not show the initial swelling episode, but did
show a distinct later swelling event after about 10 days
(Fig. 3B). In contrast, Sample 35C (spray dryer) exhibited
a first but not a second swelling episode (Fig. 3A). Sample
35A showed both an initial and a second swelling episode.
The swelling eventually stopped in most cases, and the
samples reached an equilibrium volume. Fig. 3. Swelling versus incubation time for replicates of two different dry
Quantitative correlations between swelling and miner- FGD samples. (A) Sample 35 is a spray dryer sample and (B) Sample 18 is a
LIMB sample.
alogy changes were not possible, but comparisons of
mineral peak intensities over time showed that the initial swelling phase was due to the continued hydration of
swelling phase was mostly likely due to the hydration of calcium sulfate (CaSO4) to gypsum (CaSO4$H2O) and the
lime (CaO) to form portlandite (Ca(OH)2), and anhydrite formation of new, more expansive minerals such as
(CaSO4) to form gypsum (Fig. 4A). Carbonation of ettringite (Ca6[Al (OH)6](SO4)3$26H2O) and thaumasite
Ca(OH)2 also occurred to form calcite (CaCO3). The second (Ca6[Si(OH)6]2(CO3)2(SO4)2$24H2O). The presence of
Table 4
ettringite was clearly observed by XRD analysis (Fig. 4B).
Summary of swelling tests results All chemical components necessary for ettringite formation
(calcium, aluminum, sulfate, high pH) are present in FGD
FGD processa Sample numbera Duration of Amount of swell
swell test (% of original
materials, and the geochemical modeling work, discussed in
(days) volume) the next section of this paper, indicates that ettringite
formation may occur under many conditions where dry
Coolside 10A 543 13.2
10B 169 11.1 FGD materials could be used (e.g. as an embankment
10Cb 64 0.12 material or road fill). In general, greater ettringite formation
LIMB 14 544 1.02 and swelling were observed in samples produced with
15 425 2.46 calcium-based sorbents that also contained anhydrite or one
16A 425 9.60
of its hydrates. FGD products produced with dolomitic
16B 404 1.31
18A 423 5.90 sorbent or that contained hannebachite had the least total
18B 184 3.20 swelling. The variability in results suggests that all dry FGD
22A 246 59.3 products should be tested and/or pretreated to allow for
22B 184 12.0 swelling to be completed before being used in applications
Spray dryer 30 423 1.97
where swelling will create problems.
35A 272 2.56
35B 82 1.60
35C 243 0.58 3.3. Long-term equilibration
a
FGD process abbreviations and sample numbers are as shown in Table 1.
b
Sample was cured (i.e. allowed to react with the water added at time of All samples exhibited initial pH values in the range of
compaction) for seven days before start of the swelling test. 11–12 (Fig. 5). With the exception of Sample 51, this pH
1846 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848

Fig. 4. X-ray diffraction patterns from LIMB sample 22 (A) initially and (B)
after 275 days of swelling.

level remained unchanged at the end of 112 d of incubation.

For Sample 51, the solution pH decreased more than 1 unit
to approximately 10.0. The high pH values for all samples
indicated that little or no recarbonation of Ca(OH)2 occurred
during the equilibration period. Samples were capped and
only aerated once weekly and this could have prevented the
recarbonation reactions from proceeding at a very fast rate.
The decline in pH for Sample 51 was attributed to the
presence of dolomite and partial recarbonation of the lime in
this sample.
The concentration of dissolved Ca declined in all samples,
except for Sample 52, during the first 36 d of incubation;
remained roughly constant until day 70; and then decreased
again to a low at 112 d (Fig. 5). Sample 52 showed a rapid Fig. 5. Changes in pH, Ca, S and B concentrations when various dry FGD
increase in Ca solubility followed by a plateau at 20–70 d, samples were incubated with water for up to 112 days. Sample descriptions
with a subsequent decline to a low at 112 d. Sample 52 was a are given in Table 1.
PFBC product and had an average particle size that was much
coarser than the other materials used in the long-term Ca and S concentrations were both controlled by minerals
equilibration study. It was also possible that the pressurized containing these elements.
burner resulted in greater calcination of the particle surfaces. All samples except Sample 22 showed short-term
Both factors could lead to different dissolution rates, and may increases in solution B concentrations followed by
have contributed to the behavior of dissolved Ca for Sample decreases in solubility with increasing reaction time
52. Dissolved S concentrations for each sample followed the (Fig. 5). Solution B for Sample 22 decreased sharply
same patterns as those observed for Ca (Fig. 5) indicating that until day 21 and remained at background levels thereafter.
 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848 1847

Table 5
Values of log saturation indices (SI) for FGD sample suspensions after 56 and 112 days of equilibration with water

Mineral FGD process and sample numbera

Duct injection LIMB Spray dryer PFBC fly ash PFBC bed ash Sample mix
(Sample #4) (Sample #22) (Sample #35) (Sample #51) (Sample #52) (Samples #51 and #52)
56 days of incubation
Anhydrite K2.35 K0.03 K0.22 0.03 K0.05 0.04
Barite K0.53 1.11 1.46 1.36 0.82 2.31
Brucite 1.56 1.78 2.01 0.79 2.70 0.51
Calcite 1.89 1.73 1.69 1.22 1.51 1.46
Celestite K2.50 K0.20 K0.52 K0.59 K0.96 K0.59
Dolomite K1.30 K1.09 K1.42 K0.62 K0.89 K0.37
Ettringite 14.11 21.53 17.45 29.90 20.36 29.98
Gypsum K2.34 K0.02 K0.21 0.04 K0.04 0.05
Portlandite 0.81 0.49 0.97 K1.98 0.77 K2.03
Strontianite 0.70 0.51 0.34 K0.45 K0.44 K0.22
112 days of incubation
Anhydrite K2.24 0.10 K0.24 0.03 0.07 0.01
Barite 0.14 1.19 1.19 1.31 0.66 1.27
Brucite K5.41 K5.52 K5.46 K2.37 K5.49 K1.75
Calcite 1.09 1.00 1.10 0.66 0.89 0.83
Celestite K2.40 K0.06 K0.61 0.43 K0.95 K0.55
Dolomite K8.19 K8.54 K8.36 K1.54 K8.78 K1.59
Ettringite K0.83 7.03 4.24 K3.48 5.16 K1.88
Gypsum K2.23 0.11 K0.23 0.04 0.08 0.02
Portlandite K0.87 K0.81 K0.75 K5.33 K0.76 K4.34
Strontianite K0.12 K0.21 K0.32 0.01 K1.18 K0.78
a
FGD process abbreviations and sample numbers are as shown in Table 1.

Saturation index calculations (data not shown) indicated
that B was very undersaturated (in excess of 2 log units)
with respect to likely solid phases.
3.4. Equilibrium geochemical modeling
Table 5 contains values of log saturation indices (SI) for
selected solids after 56 and 112 d equilibration of each FGD
product with deionized water. Values of log SIO0 indicate
that the sample solutions were supersaturated with respect to
the specified mineral, so that precipitation of this solid could
have occurred. Values of log SI!0 indicate undersaturation
with respect to a given solid, generally precluding its
precipitation. At 56 d (Table 5), all samples except Sample
4 were near equilibrium with gypsum (CaSO4$2H2O),
and highly supersaturated with respect to ettringite (Ca6
Al2(SO4)3(OH)12$26 H2O); however, no ettringite was
detected by XRD at this sampling time. At 112 d, the SI
values for gypsum showed little change while those for
Samples 35, 4, 22, and 52 were all near equilibrium or
supersaturated with ettringite. Ettringite was detected by
XRD in Sample 22 at 112 d.
Both the XRD data and the SI values indicate that Ca
weathering reactions in Sample 22 resulted in the interim
precipitation of gypsum as a major Ca-phase. This caused
the rapid decrease and then plateau in dissolved Ca from
21 to 70 d, and possibly was responsible for the decrease
in total dissolved S at 36 d as well (Fig. 5). The exact
weathering scenarios may vary somewhat in other
dry FGD products, but the geochemical modeling
suggests that in the absence of significant re-carbonation,
ettringite will form as the final reaction product in most
samples. Sample 51 had a significantly lower solution pH
(final pH 10.4) that would likely inhibit ettringite
formation.
The geochemical modeling also suggested that the
solutions were near equilibrium with anhydrite (Table 5),
but it is unlikely that this phase was present because all
samples were well hydrated and anhydrite was not detected
by XRD. All samples were supersaturated with calcite
(Table 5), which was confirmed by XRD for all samples
except Sample 4. There was good agreement between the SI
values and the XRD analyses with respect to the presence
and absence of portlandite. Several minor phases (barite,
celestite, and strontianite) predicted by geochemical
modeling were not detected by XRD. Because the total
concentrations of Ba and Sr were low relative to Ca, it is
possible that these phases were not present in quantities
sufficient to be identified.
The XRD and SI results for the long-term equilibration
study suggest that ‘closed’ (incomplete re-carbonation with
atmospheric CO2), highly alkaline weathering conditions
will lead to interim formation of gypsum and portlandite
followed by the conversion of gypsum to ettringite. Such
conditions may occur if FGD products are placed in
confined settings such as road embankments or buried as a
discrete layer at depth, such as occurs in some surface mine
reclamation projects.
1848 J.M. Bigham et al. / Fuel 84 (2005) 1839–1848
4. Conclusions
Before beneficial uses of dry FGD products can move
forward, their mineralogical properties must be known. This
knowledge should include the composition of the materials
immediately after generation and the potential changes that
can occur once these materials are placed in the environ-
ment. For ecological and agronomic purposes, the types of
mineral liming agents impact how quickly the materials will
react to increase the soil pH. In addition, the long-term
solubility of minerals to form salts and plant growth
inhibiting elements, such as B, also will impact the optimum
soil application rates that may lead to positive plant growth
responses. We found that the initial release of B will need to
be carefully watched as concentrations increased to levels as
high as 10 mg LK1 after the first 7 d of incubation; however,
concentrations rapidly decreased thereafter and application
of FGD to the soil several months prior to when a crop is
grown should eliminate most problems. Another potential
problem associated with agronomic uses of dry FGD
products, is heavy metals and this is addressed in a
companion paper [19].
For engineering uses, swelling is one of the most
important parameters of concern. Although some dry FGD
samples showed little or no tendency to swell, several
exhibited substantial expansion immediately upon wetting
and/or later, usually after 10 or more days. The delayed
swelling could be a problem when these dry FGD materials
are stored under ‘closed’ systems where reaction with
atmospheric carbon dioxide is restricted. Under highly
alkaline conditions, interim formation of gypsum and
portlandite occurred followed by conversion of the gypsum
to ettringite. The conditions most conducive to ettringite
formation would likely be in confined settings such as road
embankments where associated swelling would also be most
destructive. It is therefore very important that these mineral
reactions be evaluated for the potential to swell and, when
expansion is indicated, it be allowed to occur and go to
completion before the dry FGD materials are used in
applications where volume change could be a problem.
Acknowledgements
This research was conducted as a cooperative project of
The Ohio State University—The Ohio Agricultural
Research and Development Center, The US Geological
Survey and the Dravo Lime Company. Funding support was
obtained from the Ohio Coal Development Office
(Columbus, OH), US Department of Energy (Morgantown,
WV), Dravo Lime Company (Pittsburgh, PA), American
Electric Power Research Institute (Palo alto, CA), American
Electric Power Company (Columbus, OH), Ohio Edison
Company (Akron, OH), and The Ohio State University
(Columbus and Wooster, OH).
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