Fuel 144 (2015) 274–286

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

Status of Flue Gas Desulphurisation (FGD) systems from coal-fired power

plants: Overview of the physic-chemical control processes of wet
limestone FGDs
Patricia Córdoba ⇑
Centre for Innovation on Carbon Capture and Storage (CICCS), Institute of Mechanical, Process and Energy Engineering (IMPEE), Heriot-Watt University, EH14 4AS, United Kingdom
Institute of Environmental Assessment and Water Research, Spanish National Research Council (IDÆA-CSIC), Jordi Girona 18-26, 28080 Barcelona, Spain

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents a general review of the Flue Gas Desulphurisation (FGD) technologies used to abate
Received 28 April 2014 sulphur emissions from coal-fired power plants, and exposes the major physic-chemical processes occur-
Received in revised form 11 December 2014 ring during wet limestone FGD. The abatement capacity of major, minor, and trace elements and the fate
Accepted 16 December 2014
of trace pollutants during wet limestone FGD, as well as the features of wet limestone FGD by-products
Available online 26 December 2014
are discussed. It can be stated that wet limestone FGD system is the FGD process most widely used
because of its high desulphurisation performance and low operating cost. Among control parameters
Keywords:
evaluated in this review, pH range > limestone reactivity and SO2 concentration > efficiency of particulate
Flue Gas Desulphurisation (FGD)
Trace elements
control devices > water re-circulation to the scrubber > entrainment of particles by the OUT-FGD gas, are
Outgoing FGD (OUT-FGD) gas the key factors of wet limestone FGDs. It is noted that, the enrichment of inorganic trace pollutants in
FGD-gypsum FGD waters because of the re-circulation of water to the scrubber from gypsum slurry filtration, and
Pulverised Coal Combustion (PCC) the entrainment of accumulated fly ash particles in gypsum sludge, those of unreacted limestone,
and the particles and droplets from gypsum slurry by the outgoing FGD (OUT-FGD) gas reduce
considerably the desulphurisation efficiency and the abatement capacity of trace pollutants by wet
limestone FGDs. The paper concludes with a number of issues to be investigated in depth in view of
the worldwide FGD market growth and the forthcoming implementation of one of the most promising
technologies to reduce CO2 emissions, oxy-fuel combustion, in Pulverised Coal Combustion (PCC)–FGD
processes at an industrial scale.
Ó 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
2. Flue Gas Desulphurisation (FGD) systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
2.1. Wet FGD systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
2.1.1. Wet limestone FGD system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
2.1.2. Wet lime and magnesium-lime FGD systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
2.1.3. Seawater FGD system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
2.1.4. Dual-alkali FGD systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
2.1.5. Ammonia FGD system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.2. Dry and/or semi-dry FGD systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.2.1. Spray dry FGD systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.2.2. Furnace sorbent injection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.2.3. Duct sorbent injection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.2.4. Circulating Fluid Bed (CFB) dry scrubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278

⇑ Address: Centre for Innovation on Carbon Capture and Storage (CICCS), Institute of Mechanical, Process and Energy Engineering (IMPEE), Heriot-Watt University, EH14
4AS, United Kingdom.
E-mail addresses: patricia.cordoba@idaea.csic.es, pc247@hw.ac.uk

http://dx.doi.org/10.1016/j.fuel.2014.12.065
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
 P. Córdoba / Fuel 144 (2015) 274–286 275

3. Operational conditions of wet limestone FGD systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278

3.1. Reactivity of limestone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
3.2. SO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
3.3. pH and temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
3.4. Hydrochloric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
3.5. Hydrofluoric acid. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
3.6. Use of additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
3.7. Efficiency of the particulate control devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
3.8. Liquid to gas ratio and residence time in FGD systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
3.9. Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
4. FGD-by-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
4.1. Filtered water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
4.2. FGD-gypsum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
5. Fate of trace pollutants in FGD systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
6. State of the FGD market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
7. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284

1. Introduction the sorbent reagent follows a regeneration step which gives rise
to SO2, H2SO4, or S0, and produces a sludge that may be sold to par-
The term Flue Gas Desulphurisation (FGD) system has tradition- tially offset the cost of operating the FGD system; whereas in the
ally referred to wet scrubbers that remove SO2 emissions from non-regenerable processes S permanently bounds with the sorbent
large electric utility boilers. The FGD systems emerged in the to form a new product that must be disposed of properly or used in
industrial field of the coal-fired power plants and on some indus- specific applications. Commercial power generation wet FGD sys-
trial processes in the early 1970s in United States (US) and Japan, tem uses limestone (CaCO3), slaked lime (Ca(OH)2), or a mixture
and expanded rapidly in the 1980s [1] in Europe. of Ca(OH)2 and alkaline Fly Ash (FA) sorbents, which react with
In the FGD process, the flue gas interacts with an absorbent SO2 to form a Ca–S compound [9].
medium in either an absorber or a scrubber vessel to produce high
solid S slurry. The US Environmental Protection Agency (US EPA) 2.1.1. Wet limestone FGD system
classifies FGD systems as non-regenerable and regenerable pro- The wet limestone FGD process (non-regenerable) is based on
cesses based on whether the S compounds are separated from complex acid-base reactions that take place under forced or natu-
the absorbent as a by-product, or discarded along with the absor- ral oxidation conditions. According to the reactions of the desulph-
bent as a waste product [2]; whereas Clarke and Sloss [3] classifies urisation process, two regions can be differentiated in most of
the FGD systems as regenerable and non-regenerable, and subdi- the scrubbers: the gas-to-liquid contact zone and the reaction tank.
vides the non-regenerable category into wet scrubber and spray In forced oxidation the following reactions [10] occur in the
dry systems. Other authors [1,4] propose the following four catego- gas-to-liquid contact zone with a pH range from 5 to 6:
ries for the FGD systems: wet scrubbers, spray dry scrubbers, sor- SO2ðgÞ $ SO2ðaqÞ Gas SO2 dissolution ðR1Þ
bent injection, and regenerable processes; and each major category
is divided into several subcategories depending on the specific SO2ðaqÞ þ H2 O $ H2 SO3ðaqÞ Hydrolysis of SO2 ðR2Þ
chemical reactions and flow conditions. Independently of the clas-
sification, most of specialised literature [1,5–8] agrees on the fact H2 SO3ðaqÞ $ HþðaqÞ þ HSO3
that the wet limestone FGD system is the FGD process most widely
used (87%) because of its high desulphurisation performance and $ HþðaqÞ þ SO2
3ðaqÞ Sulphurous acid dissociation ðR3Þ
low operating cost [9]. The objective of this paper is to present a
general review of the FGD technologies used to abate sulphur CaCO3ðsÞ þ HþðaqÞ $ Ca2þ 
ðaqÞ þ HCO3ðaqÞ Limestone dissolution ðR4Þ
emissions from coal-fired power plants, and expose the major
physic-chemical processes affecting the design and operation of HCO3ðaqÞ þ HþðaqÞ $ CO2ðaqÞ þ H2 OðaqÞ Acid-base neutralisation ðR5Þ
wet limestone FGDs, with particular reference those affecting the
(1) abatement capacity for major, minor, and trace elements by CO2ðaqÞ $ CO2ðgÞ Equilibrium : desorption ðR6Þ
wet limestone FGDs; (2) the fate of trace pollutants during wet
limestone FGD; and the (3) the features of wet limestone FGD The following overall reaction in the gas-to-liquid contact zone
by-products. The paper highlights the need to study in depth a is obtained by combining the equations expressed above:
number of issues in view of the worldwide FGD market growth CaCO3ðsÞ þ SO2ðgÞ þ 2H2 OðaqÞ ! CaSO3  2H2 OðaqÞ þ CO2ðgÞ ðR7Þ
and the forthcoming implementation of one of the most promising
technologies to reduce CO2 emissions, oxy-fuel combustion, in Reactions initiated in the gas-to-liquid contact zone are com-
Pulverised Coal Combustion (PCC)–FGD processes at an industrial pleted in the reaction tank. The reaction tank provides an adequate
scale. residence time for the complete oxidation of the SO2 3 to SO2
4
according to:

2. Flue Gas Desulphurisation (FGD) systems CaSO3  2H2 OðaqÞ þ 1=2O2ðgÞ ! CaSO4  2H2 OðsÞ ðR8Þ
At a lower pH range (4.5–5.5), [10] the chemical reaction is dif-
2.1. Wet FGD systems ferent. As shown below, after SO2 absorption (R1), the primary
product of the neutralisation by limestone is Ca(HSO3)2:
The wet scrubbers produce a wet product that might be
regenerable or non-regenerable. In the regenerable processes [3] CaCO3ðsÞ þ SO2ðgÞ þ H2 O $ CaðHSO3 Þ2ðaqÞ þ CO2ðaqÞ þ H2 O ðR9Þ
276 P. Córdoba / Fuel 144 (2015) 274–286

OUT-FGD PM (8)
OUT-FGD GAS

Process water
Stack

Humidity eliminators

(2) Sprayers
Desulphurisation

IN-FGDPM Feeding of limestone slurry

(3) (1)
IN-FGDGAS

(4)
Air
CaSO4.2H2O
(5)
Limestone
Gypsum slurry filtration
Nebulizer collectors

Hydrociclons

(7) Filter water re-circulation

(6)

Dilution process

Limestone slurry
Aqueous phase of gypsum slurry
FGD-gypsum

(1) Feeding of limestone slurry to the scrubber

(2) Limestone slurry is pumped through the nebulizer collectors and sprayed into the scrubber
to react with SO2.

(3) Gas and PM input flow into the scrubber after combustion process.

(4) Formation of gypsum slurry as result of the desulphurisation process.

(5) Extraction of gypsum slurry for the filtration process by hydro-cyclones

(6) Production of gypsum slurry and FGD-gypsum.

(7) Re-circulation of filtered water after dilution process.

(8) Cleaned gas and PM flow OUT-FGD

Fig. 1. Conventional design and operation of a wet limestone Flue Gas Desulphurisation (FGD) system.

CaðHSO3 Þ2ðaqÞ þ O2ðgÞ þ 2H2 O ! CaSO4  2H2 OðsÞ þ H2 SO4ðaqÞ
Also in the reaction tank, the partly spent slurry is mixed with
fresh limestone slurry to replace the consumed CaCO3. The acidic
slurry is neutralised in the reaction tank. As shown below, CO2 is
produced which is later desorbed [10]:
CaCO3ðsÞ þ H2 SO4ðaqÞ þ H2 O ! CaSO4  2H2 OðsÞ þ CO2ðgÞ
Depending on the SO2 concentrations and the excess air in the
flue gas, as well as on the pH of limestone slurry, some systems
may be operated in the natural oxidation mode. However, for most
applications it is beneficial to control oxidation [10]. In natural
ðR10Þ oxidation mode, the main product is a mixture 50–60% of CaSO3½
H2O and CaSO42H2O in a sludge form which is difficult to dewater,
whereas in forced oxidation mode, the final end-product is around
90% CaSO42H2O [10].
According to the chemistry of the wet limestone desulphurisa-
tion process, in wet limestone FGD system with forced oxidation
(Fig. 1), limestone slurry is prepared in a closed ball mill (1) and
ðR11Þ pumped to the scrubber in controlled regime to maintain the pH
of the scrubber. In the gas-to-liquid contact zone, suspended slurry
drops containing sprayed (2) limestone react, depending on pH
2
conditions, with HSO 3 or SO3 resulting from the aqueous dissolu-
tion and hydrolysis of SO2 (3). The slurry drops fall down into the
reaction tank after reacting with flue gas. The oxygen injected in
 P. Córdoba / Fuel 144 (2015) 274–286 277

the reaction tank by bottom sprinklers reacts with any Ca(HSO3)2
or CaSO32H2O yielding a fully oxidised CaSO42H2O (4) product.
The slurry agitators around the reaction tank are used to disperse
the solid particles in the gypsum slurry. The generated gypsum
slurry may contain 15 wt.% of suspended solid material. In the fil-
tration process, gypsum slurry flows by means of hydro-cyclones
(5) to a vacuum filter in which solids are washed with fresh water
and concentrate to form the FGD gypsum by-product (6). The FGD-
gypsum end-product usually contains around 10% of moisture by
weight, and is then transported and deposited in landfills [11] or
used in different applications such as in the wallboard manufac-
ture or be used in the cement industry. In power plants where
water resources are scarce filtered water is re-circulated (7) to
the scrubber. Power plants with available water resources are usu-
ally designed with effluent treatment plants resulting in sludge
with a high pollutant load. The Particulate Matter (PM) and gas-
eous stream outgoing FGD (OUT-FGD) system are emitted through
the stack once water droplets are removed from the gaseous
stream via mist eliminators.
Wet limestone FGD system is capable of removing SO2 with
efficiencies from 92% to 98% [10].
dewatering characteristics than FGD-gypsum from wet limestone
FGD [14].
2.1.3. Seawater FGD system
Seawater FGD system utilises the natural alkalinity of seawater
2
to neutralise SO2. Due to the presence of HCO 3 and CO3 in seawa-
ter, the SO2 of the flue-gas is absorbed. The process is based on the
following chemical reaction:
SO2ðgÞ $ SO2ðaqÞ ðR12Þ
SO2ðaqÞ þ 2HCO3ðaqÞ þ 1=2O2 $ SO2
4ðaqÞ þ 2CO2ðaqÞ þ H2 OðaqÞ ðR13Þ
The acidified absorber effluent is mixed with additional seawa-
ter to ensure that the pH is at optimal level for the oxidation pro-
cess. The introduced air forces the oxidation of HSO 3 and removes
dissolved CO2. The water is nearly saturated with oxygen and the
pH value is restored to neutral before the seawater is discharged
back to the sea [10]. In this technique SO2
4 is completely dissolved
in seawater, therefore there is no waste product to dispose of.
Seawater FGD systems may achieve from 85% to 98% SO2
removal efficiency [10].

2.1.2. Wet lime and magnesium-lime FGD systems
Lime scrubbing uses CaO, usually 90%, to remove SO2 from the
gaseous stream. Lime is more reactive than limestone slurry, but
it is more expensive [12]. The Magnesium Enhanced Lime (MEL)
process [12] is a variation of the lime process that uses a special
type of lime, magnesium-enhanced lime (5–8% MgO) or
dolomitic lime (20% MgO). According to the greater solubility of
magnesium salts compared to the calcium sorbents [12], the
absorber slurry is significantly more alkaline in the first case.
Therefore, the MEL based process may achieve high SO2 removal
efficiencies in a significantly smaller scrubber than the limestone
scrubbers [13]. Furthermore, FGD MEL end-products have poorer
2.1.4. Dual-alkali FGD systems
Dual or double-alkali scrubbing is a third non-regenerable FGD
process that uses sodium based alkali solution to remove SO2 from
the gaseous stream [2]. In this process SO2 reacts with the alkaline
solution: NaOH, Na2CO3, and Na2SO3 to primarily form Na2SO3 and
NaHSO3. The sodium alkali solution absorbs SO2, and the spent
absorbing slurry is regenerated with CaO or CaCO3. It is for this rea-
son that this desulphurisation process is so-called dual or double-
alkali scrubbing. Calcium sulphite or sulphate is precipitated and
discarded as sludge; whereas the regenerated sodium solution is
returned to the absorber. The dual-alkali systems have the advan-
tage of reaching SO2 retention efficiencies up to 98% [2].

Dilution water

Lime silo Atomizer feed tank

(1)

Slaking water FF
Slaker (2)
FLUE GAS IN-FGD or
Spray dryer
ESP
absorber
Stack

Ca (OH) 2 slurry

(1)
Induced draft Fan

Waste product
Ca (OH)2 slurry holding tank (3)

Recycling system (optional)

(1) Feeding of lime to the atomizer feed tank

(1) Lime slurry is sprayed into the scrubber to react with SO2.

(2) Desulphurisation by-product is entrained in the flue gas and carried downstream toward a
particulate collection device.
(3) Residue is recycled and mixed with fresh CaO slurry to enhance CaO utilisation

Fig. 2. Conventional design and operation of a Spry dry-lime Flue Gas Desulphurisation (FGD) system.
278 P. Córdoba / Fuel 144 (2015) 274–286
2.1.5. Ammonia FGD system
In the ammonia FGD system, SO2 is absorbed by aqueous NH3,
resulting in (NH4)2SO4 with a high potential application as a fertil-
izer by-product [15]. However, the high cost and the marked
excess of this fertilizer from other sources in industrialised coun-
tries constitute limitations for the use of this process.
2.2. Dry and/or semi-dry FGD systems
In dry and/or semi-dry FGD systems, SO2-containing flue gas
reacts with an alkaline sorbent typically Ca(OH)2 or CaO [10]. As
a result, dry waste is produced, which is generally easier to dispose
of than waste produced from wet FGD processes.
2.2.1. Spray dry FGD systems
Spray dry absorption is the second most popular FGD system
worldwide (11%) and mostly used for relatively small to medium
capacity boilers using low to medium S (1.5 wt.%) coal [16]. In
the dry FGD systems (Fig. 2), SO2 reacts with CaO or Ca(OH)2 sor-
bent, which is mixed with an excess of water or is slaked to pro-
duce lime slurry. Lime slurry is atomized (1) to a cloud of fine
droplets in the spray dry absorber where SO2 is also removed from
the flue-gas. Given that water is evaporated by the heat of the
flue-gas; waste water treatment is not required in this process.
The primary reactions during the spray dry FGD systems are given
below:
CaðOHÞ2 þ SO2 $ CaSO3 þ H2 O ðR14Þ
CaðOHÞ2 þ SO3 $ CaSO4 þ H2 O ðR15Þ
The SO2 in the flue gas is absorber into the liquid and react as
shown above for a lime slurry process. In addition to these primary
reactions, the following secondary reaction also occurs:
CaSO3 þ 1=2O2 $ CaSO4 ðR16Þ
The resulting by-product (Fig. 2), a dry mixture of CaSO3½H2O,
CaSO42H2O, unreacted lime, and fly ash, is entrained in the flue gas
and carried downstream towards a particulate collection device
(2), usually electrostatic precipitator or fabric filter. The residue
is subsequently recycled (3) and mixed with fresh CaO slurry to
enhance CaO utilisation. The dry spray technique has relatively
low costs and energy consumption, approximately 30–50% less
than the wet limestone process. However, operational costs are
higher due to higher sorbent costs [17]. The Spray dry FGD systems
may attain SO2 removal efficiencies from 85% to 95% [10].
2.2.2. Furnace sorbent injection
Furnace sorbent injection involves the direct injection of a dry
sorbent into the gaseous stream from the boiler [17]. Typical sor-
bents include CaCO3 and CaCO3MgCO3. In the furnace, the calcina-
tion of the sorbent produces reactive CaO particles. The surface of
these particles reacts with the SO2 in the flue gas to form CaSO3
and CaSO4. These reaction products are then captured along with
the FA by the particulate control device, typically an electrostatic
precipitator of fabric filter. The dry solid residue does not require
a further treatment before being discharged to a landfill or being
used as a construction material.
About 50% of SO2 removal efficiency can be achieved at a sor-
bent molar ratio (Ca/S) of 4–5 when limestone is injected into
the boiler furnace at near optimum operation. However, SO2
removal efficiencies can be increased from 70% to 80% by recycling
the reaction product [10].
2.2.3. Duct sorbent injection
Duct sorbent injection is a dry FGD system based on the injec-
tion of Ca(OH)2 or NaHSO3 into the flue-gas between the air’s
pre-heater and electrostatic precipitator or fabric filter. However,
water may be injected into the flue gas upstream of the sorbent
to enhance the SO2-sorbent reaction [17]. A proportion of the
resulting residues, fly ashes, reaction products, and any unreacted
sorbent collected in the particulate control device are re-circulated
into the duct to increase sorbent utilisation, while the remaining
proportion is disposed. Approximately 50–60% SO2 capture may
be expected with the duct sorbent injection using Ca(OH)2, and
up to 80% with NaHSO3 [18]. Reported costs of the duct sorbent
injection process vary depending on the S content of the fuel and
on the plant size [10].
2.2.4. Circulating Fluid Bed (CFB) dry scrubber
The CFB process is a type of dry scrubber in which in addition to
coal, CaO, Ca(OH)2, or CaCO3 are injected directly into the CFB reac-
tor to enable SO2 removal. In CFBC, air is blown into the bottom of
the furnace giving rise to the formation of a bed of an inert mate-
rial. The bed provides a long contact time between the sorbent and
flue gas since that sorbent passes through the bed several times.
Entrained reaction products are carried by flue gas to a particulate
control device [10].
The circulating bed systems increase the potential reaction time
and the level of gas mixing, therefore generally leading to a more
efficient combustion and fixation of S. The retention of SO2 reaches
to 98% [10].
3. Operational conditions of wet limestone FGD systems
The two most significant factors in wet limestone FGD systems,
for economic reasons, are the desulphurisation efficiency (SO2
retention) and the residual limestone level of the FGD-gypsum
[19]. Although the most relevant parameters affecting the design
and operation of a wet limestone FGD system are physical parame-
ters such as the liquid-to-gas (L/G) ratio, the absorber gas velocity,
and the oxidation fraction [20], chemistry factors of wet limestone
FGD systems such as the reactivity of limestone, SO2 concentration
in flue gas, the reaction tank pH, temperature of the scrubber, HCl,
HF, and use of additives; and operational conditions of FGD system
efficiency, such as the particulate control device efficiencies, resi-
dence time in FGD systems, water treatment or recycling, and oxi-
dation process, may also affect the operation of a wet limestone
FGD. As regards the above controls, overviews of parameters that
may affect on the desulphurisation efficiency, the abatement capac-
ity of major, minor, and trace pollutants, and the quality of FGD-
gypsums in wet limestone FGD systems are outlined in this paper.
3.1. Reactivity of limestone
Some properties of limestone such as particle size distribution
(PSD), porosity, and the impurities of limestone may play a signif-
icant role in the efficiency of desulphurisation process. These
parameters can be considered as key factors of the reactivity of
the limestone. The reactivity of limestone is defined as a capacity
for providing alkalinity and reacting with the acid resulting from
the dissolution of SO2 into water [21].
In the conventional wet limestone FGD system, limestone is
usually used after being pulverised to an average size of 5–
20 lm, which consumes a great deal of energy [22]. Kikkawa
et al. [22] used granular limestone of 1 mm particle size directly
as desulfuring reagent. The performance of wet FGD process using
granular limestone was confirmed to be equal to or higher than
that of conventional process in various tests. However, the L/G
reached values much higher than that of conventional process,
which accounted for the increase of power consumption for pump-
ing the circulation slurry. Shenyu et al. [23] proposed the use of
granular limestone with acetic acid additives to save on both
 P. Córdoba / Fuel 144 (2015) 274–286
power required for pulverisation of limestone and also pumping
the circulation slurry. The results of the SO2 removal efficiency,
SO2 absorption rate, limestone utilisation, and FGD system stability
were in line with those of the conventional FGD in the same
absorption equipment under the same experimental conditions.
These studies demonstrated de feasibility and reliability of the
postulated new wet FGD process.
Mathematical modelling has been proven to be a useful tool for
investigation and design complex wet FGD systems and other
parameters such as the PSD of limestone. Model predictions devel-
oped by Kikkawa et al. [24] were found to be qualitatively in good
agreement with experimental data without any use of adjustable
parameters. Deviations between measurements and simulations
were attributed primarily to the PSD of the limestone particles,
which were not representative of the limestone samples because
agglomeration phenomena took place when the particles were sus-
pended in a liquid solution. The results of this work showed that a
representative PSD is essential in order to model the rate of disso-
lution of limestone particles accurately.
Modification of reactivity of the nonreactive limestones by
changing the porosity and thereby increasing the quantity of S cap-
ture has also been investigated. Pore size and particle size together
determine the extent to which the interiors of individual particles
react. Particles smaller than 100 lm with pores larger than 0.1 lm
react throughout their internal pore structure at a rate directly pro-
portional to the surface area as measured by the Brunauer–
Emmett–Teller (BET) method [25]. Small pores result in a high
reaction rate, but if the particles are large, their capacity is low.
Hartman and Coughlin [26] developed a simple structural model
in order to correlate their experimental results for the reaction of
porous limestone particles with SO2 gas. The model incorporated
parameters such as porosity, true density, CaCO3 content of the
natural rock, and the rate of conversion to SO2
4 . Comparison
between the model and the experimental results indicated that
the reaction is strongly influenced by the reduction in porosity
caused by sulfation. Both reaction rate and porosity become very
small at conversions of 50%.
Concerning limestone purity, when the proportion of limestone
is increased to improve the SO2 removal efficiency, the quality of
the FGD-gypsum may decrease to valueless level owing to the
impurities of limestone and the residual limestone amounts in
the FGD gypsum end-product. A work on the partitioning in a
wet limestone FGD system [27] demonstrated that Al and Si were
supplied by the highly insoluble aluminosilicate fraction of lime-
stone (93% CaCO3) and other elements such as F and Mn and were
retained as impurities in the FGD-gypsum sludge. Therefore, it is
highly recommended the use of a limestone with purity higher
than 95% and the concentration of limestone in FGD-gypsum to
be a level under a predetermined value (3–4 wt.%) to be saleable
[28,29].
Other factors such as the pH of the scrubber, chloride concen-
tration, and CO2 stripping may also affect the reactivity of lime-
stone [30]. In accordance with the chemistry of wet limestone
FGD systems (2.1.1 section), the pH range may play a significant
role in the dissolution rate of limestone. Low pH values promote
the dissolution rate of limestone whereas high pHs may produce
the precipitation of Ca(HCO3) or CaSO3 decreasing its dissolution
rate. Since the concentration of Cl is electronically balanced with
Ca2+ ions in the solution, a high concentration of Cl in the bulk
phase would lead to high concentration of Ca2+ in this phase, which
would result in a reduction of the concentration gradient of Ca2+
between the particle surface and bulk phase; the driving force
for the dissolution of CaCO3. By contrast, the stripping of CO2 from
the aqueous to the gas phase would favour the dissolution rate of
CaCO3 as a result of a reduction of H2CO3 concentration in the
aqueous phase of limestone slurry.
279
3.2. SO2
Depending on the concentration of S in coal and on the opera-
tional conditions of the power plant, the content of SO2 in the gas-
eous stream that reaches the FGD system may vary greatly [29]. In
wet FGD processes, SO2 diffuses through the gas phase to the aque-
ous surface, where it dissolves and is transferred by diffusion or
convective mixing into the aqueous phase. The rate at which SO2
is transferred depends on factors such as the solubility of SO2
and its displacement from equilibrium [31]. The SO2 equilibrium
can be expressed as follows [11]:
C 0  103  ½Hþ 
y ¼ ð1Þ
k1 ðk2 þ ½Hþ Þ
where k1 (mol/L atm) is the equilibrium constant of SO2(g) M
SO2(aq); k2 (mol/L atm) is the equilibrium constant of CaCO3(s) + H+ M
Ca2+  0
(aq) + HCO3(aq); C (mol/L) is the total dissolved concentration of
SO2; [H+] is the concentration of protons at equilibrium; and y⁄ is
the vapour pressure (N m2) of SO2 (mg/L). Under acidic conditions
(4.0 > pH), the equilibrium pressure of SO2 increases and as a
consequence the absorption into limestone is diminished. However,
the pSO2 can be restored and the absorption rate of SO2 maximised
by the use of buffer additives [11].
The absorption of SO2 into absorbent slurry has also been sub-
ject of investigation via simulation and modelling processes. It is
generally known that the absorption of SO2, that is to say, desulph-
urisation efficiency, increases by increasing the limestone slurry
volume into the scrubber. However, the chemical absorption of
SO2 in the absorber is the most complex and important step in
scrubber [32]. Many researchers have adopted different gas–liquid
mass transfer theory to built different wet limestone FGD models.
Gage [33], Argawal and Rochelle [34], Brogren and Karlson [35],
and Eden and Lucka [36] modelled spray scrubbing systems,
whereas Lancia et al. [37] modelled the absorption of SO2 in a bub-
bling reactor. Gerbec et al. [38] introduced the unsteady-state the-
ory by including parameters such as the falling dispersed drops of
liquid phase, chemical equilibrium of SO2 2 2
3 , SO4 , CO3 , and Ca
2+
in
solution, and the dissolution, precipitation, and oxidation of SO2 3
and SO2 4 . Brogren et al. [39] in a built model of spray absorber
of wet limestone FGD estimated the impact of the reactions with
finite rate of SO2 mass transfer. Warych et al. [40] created a model
to predict the variation of SO2 removal efficiency influenced by
ratio of volume of liquid to that of flue gas (Ra), pH, flow rate,
etc. Xiang et al. [41] and Kiil et al. [42] also developed model pre-
dictions of wet limestone FGD processes. However, it should be
highlighted that other parameters, usually more difficult to con-
trol, such as (1) the inlet SO2 concentration may vary greatly,
sometimes twice or three times as that of design value; (2) the flux
of the flue gas may vary with the variation of load of boiler; and (3)
the desulphurisation process may vary for economic reasons, may
also have a significant role in the desulphurisation efficiency.
3.3. pH and temperature
The concentration of H+ has a strong impact on the dissolution
rate of limestone and on the SO2 removal efficiency. FGD systems
are designed to operate at optimal pH in the range of 5.0–6.0. At
lower pH values, limestone dissolution rate is considerably higher
but both SO2 dissolution into the slurry and its removal efficiency
are lower [30]. High pH values result in higher efficiencies of SO2
removal. There are, however, limitations such as; reaching high
pH values requires addition of excess limestone. The excess of lime-
stone as well as raising the pH tend to increase the scrubber scale.
Moreover, in the gas-to-liquid contact zone, CaSO3 remains in disso-
lution only when the concentration of H+ exceeds its equilibrium
280 P. Córdoba / Fuel 144 (2015) 274–286
value [11]. The equilibrium pH of CaSO3 is 6.3 with a partial CO2
pressure of 0.12 atm. Therefore, the dissolution state of CaSO3 is
possible for pH values <6.3; pH values >6.3 may give rise to the
scrubber scale problems by precipitation of CaSO3 [11]. However,
it is important to note that with a pH range from 4.5 to 5.5 the pri-
mary product of the neutralisation by limestone is Ca(HSO3)2, which
is considerably more soluble than CaSO3 and more easily oxidised to
SO2 2
4 than SO3 [43]. Therefore, in theory, operating with a lower pH
range has less risk of scaling and plugging of the scrubber, but the
desulphurisation efficiency decreases. This also means that the pH
value in the scrubber is dependent of the desulphurisation stage.
In wet FGD processes, as aforementioned, the rate at which
SO2(g) is transferred depends on the solubility of SO2 and its dis-
placement from equilibrium [31]. Under acidic conditions, the
equilibrium pressure of SO2 increases and as a consequence the
gas absorption rate decreases and approximates to zero [11]:
SO2ðaqÞ þ H2 O $ H2 SO3ðaqÞ ðR17Þ
H2 SO3ðaqÞ $ HþðaqÞ þ HSO3ðaqÞ $ HþðaqÞ þ SO2 ðR18Þ
3ðaqÞ
The evaluation of desulphurisation efficiency and abatement
capacity of inorganic trace pollutants during two consecutive
campaigns at a co-combustion power plant equipped with a wet
limestone FGD [42], revealed a relatively low retention for SO2
(82–88%), in comparison with that of other FGD system (94%) of
similar capacity [27], as a consequence of the acidic conditions of
the aqueous phase of gypsum slurries (4.6–5.1 pH) and the low
porosity of limestone used for the desulphurisation process.
Reactions (17) and (18) illustrate that an increase of H+ may reduce
the absorption of SO2 from the gaseous to the aqueous phase with
the consequent desorption of SO2.
With respect to the effect of the temperature on desulphurisa-
tion efficiency (scrubber and flue gas), a lower desulphurisation
efficiency is expected due to the lower solubility of SO2 in lime-
stone slurry at high temperatures [42]. Indeed, experimental stud-
ies by Zheng et al. [44] confirm a decrease of the SO2
desulphurisation efficiency when increasing the temperature of
the scrubber. However, the diffusion rates of H+ towards the lime-
stone particles are enhanced at high temperature. Similarly, CO2
stripping from the aqueous phase of limestone slurry and the rate
of the chemical reactions involved in the desulphurisation process
are increased at high temperature [30].
3.4. Hydrochloric acid
Coal combustion can generate harmful acidic gases other than
SO2. The two most important, disregarding NOx which is typically
removed in a separately catalytic process, are hydrogen chloride
(HCl) and hydrogen fluoride (HF).
According to Davison [45], a typical concentration of Cl concen-
tration of coal is 0.1 wt.% (1000 mg/L) with the observed concen-
tration range of 0.005–0.2 wt.%. During combustion, coal chlorine
is released primarily as HCl in the high temperature zone of a
boiler [46]. As the combustion gases cool (430–475 °C), a
proportion of HCl can be partially oxidised to Cl2 by the Deacon
Process [47] reaction in the presence of O2 and H2O:
2HClðgÞ þ 1=2O2ðgÞ $ Cl2ðgÞ þ H2 OðgÞ ðR19Þ
However, the presence of SO2 can inhibit the formation of Cl2
through the following gas-phase reaction [48]:
Cl2ðgÞ þ SO2ðgÞ þ H2 OðgÞ $ 2HClðgÞ þ SO3ðgÞ ðR20Þ
The predominance of the reactions 19 and 20 will, therefore,
dependent on the relative ratios of the S and Cl species. If the
S/Cl ratio is high, R20 will predominate over reaction R19 in the
gas phase. In wet limestone FGD, HCl can be absorbed simulta-
neously with SO2 in the aqueous phase of the absorbent slurry,
whereby they dissociate to form Cl ions according to:

HClðgÞ $ HClðaqÞ $ HþðaqÞ þ ClðaqÞ ðR21Þ
Most of studies focussing on the role of HCl in FGD systems deal
with the influence of HCl on desulphurisation efficiency and on Hg
gas speciation. Yoo and Kim [49] and Frandsen et al. [19] found
that Cl enhances the SO2 removal efficiency by an increase of
the gas–liquid surface area due to foaming caused by the increase
of the limestone slurry level in the reactor when Cl is added. By
contrast, Kiil et al. [26] reported that the HCl contributes to (1) a
pH drop in the absorber, which decreases the SO2 removal
efficiency; (2) increase the residual limestone level in the
FGD-gypsum by reduction of limestone dissolution rate; and (3)
decrease the quality of FGD-gypsum owing to high concentrations
of Cl in the FGD-gypsum produced make it useless for commercial
purposes. In this regard, the removal of HCl in the flue gas prior to
the wet limestone FGD scrubber has been proposed by installing a
prescrubber which will capture most of the HCl and thereby ensure
a good and constant gypsum quality [40]. However, it is not the
usual trend; at most of power plants HCl is absorbed directly in
the scrubber.
Fundamental studies based on Hg behaviour during FGD [50–
53] indicate that its gaseous speciation is highly dependent on
HCl concentration in the post-combustion flue gas. It is generally
accepted that during post-combustion, and with decreasing tem-
perature, Hg0(g) may remain as a monatomic species or may oxidise
to Hg2+ 2 and Hg
2+
compounds. Galbreath and Zygarlicke [54] and
Senior et al. [55] stated that the reaction of Hg0(g) with HCl(g) or
Cl2(g) to form HgCl2(g) is generally considered to be the dominant
Hg transformation mechanism in coal combustion flue gas. In FGD
systems the re-emission of Hg0 OUT-FGD is the common pathway
of gaseous Hg, and only a high input of Cl may reduce and/or inhibit
the mechanism of Hg0 re-emission by the formation of Hg–Cl com-
plexes. Most Hg–Cl species are highly volatile and may also be re-
emitted OUT-FGD as Hg2+. Wo et al. [56] in an evaluation of the influ-
ence of different experimental parameters on Hg removal efficiency
found that Cl slowed the decomposition rate, thereby the re-emis-
sions of Hg0 OUT-FGD, by the formation of Cl—Hg–S species. Córdoba
et al. [57] found that the different speciation of gaseous Hg OUT-FGD
between two coal-fired power plants was governed by the input of
SO2 and especially of Cl in the FGD system. FGD batch experiments
[57] in accordance with the Hg0/Hg2+ gas ratio observed during the
sampling campaigns at these power plants, proved that the different
S/Cl ratios and pH values in the FGD between power plants were the
determining factors in the different speciation of gaseous Hg OUT-
FGD for the two systems. This is in agreement with the results of
Blythe et al. [58], Currie et al. [59], and Omine et al. [60].
3.5. Hydrofluoric acid
A typical concentration of F in coal is 0.015 wt.% (150 mg/kg)
and the observed concentration range is 0.002–0.05 wt.% [55]. Coal
fluorine is released primarily as HF and its concentration in the flue
gas IN-FGD is relatively high, but lower in comparison of HCl
[55,27]. The dissolution of HF in the aqueous phase also leads to
the decrease of the pH value, reducing thus the SO2 removal
efficiency.
Hydrofluoric acid contained in the flue gas may be dissolved in
the aqueous phase of the sprayed droplets of limestone slurry giv-
ing rise to the formation of CaF2. However, in the presence of Al-
bearing compounds, HF may also react with limestone to form
Al–F species, typically represented by CaAlF3(OH)2–CaF2 [22,61].
In addition, a highly acid insoluble Al-fluoride ralstonite
 P. Córdoba / Fuel 144 (2015) 274–286
(NaMgAlF6H2O) [62] is formed instead of CaF2, probably because
ralstonite forms an iso-structural solid solution between hydrated
Al-fluoride complexes rich in Na and Mg compounds [63]. These
compounds can coat the surfaces of the limestone particles and
consequently cause a decrease the reactivity of limestone [64–67].
Font et al. [62] reported that the speciation of F also plays a cru-
cial role in the leaching potential of the FGD gypsum end-product
as a consequence of the precipitation of F solid species on FGD-
gypsum surface. Álvarez-Ayuso et al. [61,68] found that FGD gyp-
sum risks its characterisation as a waste acceptable at landfills
for non-hazardous wastes due to its F leachable content. To avoid
this, the use of additives, as it will be outlined below, has been pro-
posed as measure, in addition to optimise the SO2 removal effi-
ciency; to reduce the precipitation of F solid species and stabilise
F in FGD-gypsum [69,70], respectively. On the other hand, it has
also been demonstrated that HF and Al may interact to form highly
soluble Al–Fx complexes [62,70]. In this regard, a case study [71] on
the influence of the Al-additive on the speciation and partitioning
of inorganic trace pollutants in the re-circulated water streams
revealed that the use of an Al-additive modify the aqueous and
solid speciation of Al, Ca, Mg, and F, among other elements in a
wet limestone FGD system.
3.6. Use of additives
As stated above, the use of additives has been proposed as mea-
sure for the optimisation of wet FGD efficiencies. Sulphur dioxide
removal efficiency of wet FGD systems using limestone can be
improved by the addition of various organic acids. A number of
studies [72–74] have shown that organic acids with buffering
capacity provide an optimal tool for enhancing of the desulphurisa-
tion efficiency. When SO2 dissociates in the liquid between gas and
liquid phase, H+ is produced. Organic acids promote transport of H+
between gas-aqueous and aqueous-solid phase. The transport of H+
from the aqueous film to the bulk aqueous phase promotes the dis-
sociation of SO2, increasing the overall removal rate [19]. However,
if the pH value is excessively low, buffer additives may act as scav-
enging systems for H+. Although the use of organic acids has been
demonstrated an optimal measured to boost the SO2 efficiencies,
the effect of organic additives on the retention efficiency of pollu-
tants other than SO2 has been questioned. Heidel et al. [75] in a
recent study based on the chemical reduction and re-emission of
Hg compounds from slurries of a lab-scale wet FGD system,
revealed a negative impact on Hg retention by addition formic
and adipic acids as a result of the role of formic acid as strong
reducing agent.
Additives such as MgO and Na2CO3 can also be used to improve
the desulphurisation efficiency. The role of these compounds is
based on the capacity of providing alkalinity. The concentration
of alkaline compounds dissolved in the aqueous phase of limestone
slurry (CO2  2 
3 , HCO3 , SO3 , and OH ) is defined as dissolved alkalin-
ity [11].
Currently, the implications of the use of additives, not only to
increase the SO2 removal efficiency and to reduce the leaching of
F in FGD-gypsum [61,68,69], but also to modify the chemistry of
wet limestone FGD systems [26,43,76] has been subject of detailed
investigation. The findings of Álvarez-Ayuso et al. [68,69] pointed
to a high feasibility of coal fly ash and amorphous aluminium oxide
for reducing the leaching of F in FGD-gypsum, and for stabilising
FGD-gypsum for its disposal in landfills, respectively. Córdoba
et al. [70] noted that the use of Al2(SO4)3 caused (1) the acidificat-
ion of the aqueous phase of gypsum slurry via aluminium hydroly-
sis, which was related with the relatively low efficiencies of
desulphurisation; (2) the occurrence of the Al–Fx and SO4–metal
complexes in the aqueous phase of the gypsum slurry modifying
the speciation of these elements; (3) the protonation of the
281
FGD-gypsum surface, which accounted for the absence of signifi-
cant leaching of heavy metals from the FGD-gypsum; and (4) the
different retention efficiency of gaseous Hg2+, as a result of differ-
ent dosages of the Al2(SO4)3. The acidification of the gypsum slurry
induced by the addition of Al2(SO4)3 in consistent with prior stud-
ies carried out by Ochoa-González et al. [77].
3.7. Efficiency of the particulate control devices
Despite the high efficiency of electrostatic precipitators (>90%)
[78–81], a small fraction of fly ashes escapes and goes into the
FGD system. Once in the FGD, fly ash components may be dissolved
in the aqueous phase of the absorbent slurry or retained in the
solid fraction (gypsum sludge).
Elements dissolved in the aqueous phase of the absorbent slurry
may react to form aqueous complexes and solid species and/or act
as catalytic of oxidation–reduction reactions of gaseous pollutants,
which could modify the behaviour and partitioning of trace ele-
ments in streams involved in the FGD process. Fly ashes not dis-
solved in the aqueous phase of the absorbent slurry may be
retained in the solid fraction (gypsum sludge) and subsequently
extracted from the system by the FGD-gypsum, and/or may firstly
be retained in the solid fraction and subsequently entrained with
the outgoing flue gas FGD (OUT-FGD) as PM.
The accumulated fly ash particles in gypsum sludge as well as
the entrained particles from this material and those of gypsum
and limestone slurry by the gas OUT-FGD are limiting factors for
an increase of PM emissions and for an accurate determination of
the retention efficiency of PM by wet scrubbers. In FGD systems,
under operational conditions of water re-circulation, an accumula-
tion of fly ashes into the scrubber also occurs, which could give rise
to technical and environmental problems by increasing PM emis-
sions OUT-FGD. Given the accumulated fraction of PM into the
scrubber cannot be determined, an estimation of the retained pro-
portion of PM is usually measured by considering the retention
efficiency as PM OUT/PM IN ratio [42].
In Europe, experiences with wet FGDs have indicated collection
efficiencies of PM by wet FGDs 90% [42,61]. In Netherlands, after
1990, wet FGD systems were introduced as a result of which the
particulate loads (PLs) were further reduced to <10 mg/m3 [79].
However, an intensive sampling (7 sampling campaigns) and char-
acterisation program [82] executed at two Spanish, three Greek,
and one Dutch power plants, fed with different fuels and with dif-
ferent designs of wet FGD systems, reported PM collection efficien-
cies in the range of 47–79% as a consequence of the entrainment of
droplets (containing S, Ca, Mg, Sr, Hg, As, or Se) from gypsum slurry
and/or from corrosion of the steel (mainly Fe, Cr, Ni, Zn or Pb) by
the OUT-FGD gas [81]. It can therefore be stated that the actual
removal efficiencies of fly ashes by wet limestone FGDs are usually
underestimated because of the entrainment of unreacted lime-
stone and gypsum slurry particle episodes.
3.8. Liquid to gas ratio and residence time in FGD systems
The mol ratio of liquid/gas (L/G) has been found to be one of the
most important criterions for reporting the reactor performance
from an economic point of view [83]. In FGD systems, L/G values
tends to the minimum values (1.1–2.0) to reduce the cost. How-
ever, experimental results found an increase of the SO2 efficiency
with increasing the L/G ratio [36,29,30,38,83,84]. An increase of
the L/G rate creates a larger mass transfer area, whereas a decrease
may create better conditions for gas/liquid mass transfer at the
interface because of increased turbulence and better gas distribu-
tion, which thereby increase the mass transfer driving force [9].
However, decreasing L/G may decrease the SO2 removal efficien-
cies because of the shorter residence time in the scrubber. Indeed,
282 P. Córdoba / Fuel 144 (2015) 274–286
studies have recently shown that the SO2 removal efficiencies
greatly improved by decreasing the gaseous flow rates or increas-
ing the liquid flow rates [30]. Providing an adequate residence time
of the flue gas into the scrubber to make ensure maximal SO2
absorption by the alkali slurry is one of the major objective of
the FGD optimising tasks [10].
3.9. Oxidation
As previously stated, FGD systems may operate under natural or
forced oxidation conditions. In forced oxidation mode, air is
injected in the reaction tank by bottom sprinklers to react with
any Ca(HSO3)2 or CaSO3 to ensure fully oxidised gypsum product.
In the oxidation process, the pH value also plays a significant role.
HSO 2 2
3 is more easily oxidised to SO4 than SO3 [42]. Thus, low pH
values are also advantageous for the gypsum production. In natural
oxidation mode, CaSO3 is partly oxidised by the oxygen contained
in the flue-gas. The main product is a mixture 50–60% of CaSO3½
H2O and CaSO42H2O in a sludge form.
Forced oxidation systems dewatering is relatively easy because
the gypsum crystals are large (1–100 lm) in comparison with the
crystal size reached by natural oxidation (1–5 lm). Additionally,
aeration functions can eliminate CO2 from the water, thereby
increasing pH during the neutralisation reaction [10]. There is a
current trend to convert natural oxidation systems to forced
oxidation ones because the gypsum end-product is of a better
quality (even for landfill disposal) than the sulphite–sulphate
sludge from natural oxidation [10]. Forced oxidation gives rise to
90% CaSO42H2O [10].
4. FGD-by-products
The FGD process at coal-fired power plants entails the produc-
tion of solid and aqueous by-products, FGD-gypsum and filtered
water (effluent) from gypsum slurry filtration, respectively.
Depending on the characteristics and properties of the by-products
and the availability and resources of the power plant, the fate of
FGD-gypsum and filtered water can be the disposal in landfills
and water treatment or recycling, respectively.
4.1. Filtered water
Filtered water is the effluent produced as a result of the gypsum
slurry filtration. The fate of this water stream depends on the avail-
ability of water near the power plant. As stated before, power
plants with available water resources are usually designed with
effluent treatment plants producing sludge with a high pollutant
load. Where water resources are scarce, the re-circulation of the
water to the scrubber from gypsum slurry filtration is preferred
owing to the economic and environmental benefits of recycling.
A typical water treatment is based on increasing the pH in order
to precipitate metals by formation of metal hydroxides. The use of
additives to promote coagulation-flocculation processes are also
common measures to deal with the water treatments. As a result
of coagulation-flocculation processes, the sludge produced is first
sedimented, drained, and disposed of or recycled to the floccula-
tion stage where the sludge particles serve as initial crystallization
nuclei promoting more rapid flocculation [10].
As regards recycling possibilities of water, water streams may
act as retention sinks for some metals as a result of partial or total
dissolution processes, the efficiency of which largely depends on
chemical properties such as the pH and temperature of the solvent
and/or the solubility constant of the specific element, among other
parameters [76]. In the FGD systems, under operational conditions
of water re-circulation, inorganic trace pollutants initially in
sub-saturation in FGD waters may reach equilibrium and a
subsequent saturation in the water stream after a number of water
re-circulations in the scrubber. The gradual increase in the
concentration of inorganic trace pollutants from the sub-saturation
to equilibrium and/or saturation because of continuous water
re-circulation in the scrubber, accounts for enriched inorganic
trace pollutants in the re-circulated water [76]. This process may
increase the concentration of trace pollutants in re-circulated
waters up to very high levels compared with that of the original
input water, which could result in environmental and/or technical
problems, especially if the re-circulation of the water streams is
interrupted and/or a water treatment is necessary for hypothetical
and eventual discharges to the environment [76]. Other
elements retained in high proportions by gypsum sludge and/or
FGD-gypsum do not pose this problem because they are extracted
from the system by the gypsum by-product that is used for
different applications or for landfilling.
The high concentration of major, minor, and trace elements in
the aqueous phase of the gypsum slurries and filtered waters from
two coal-fired power plants, prompted a detailed study of the
enrichment of inorganic trace pollutants in re-circulated water
streams [76]. According to this study, the enrichment of inorganic
trace pollutants because of continuous water re-circulation in the
scrubber was promoted by the operational conditions affecting
the wet limestone FGD-system. Results demonstrated that the
emission of particles and droplets from gypsum slurry by the
OUT-FGD gas was the most important consequence of the high
enrichment of inorganic trace pollutants in the re-circulated
waters [26,43].
4.2. FGD-gypsum
FGD-gypsum is a synthetic solid by-product obtained by the
absorption of SO2 in the absorbent slurry [85].
According to the European Coal Combustion Products Associa-
tion [87], in 2009 FGD-gypsum (21%) was the second largest by-
product generated in the EU15 countries (Fig. 3). FGD-gypsum
finds applications in the wallboard manufacture or be used in the
cement industry. Other uses such as agricultural lime substitute,
amendment for improving soil properties, construction material
for roads, and waste stabilisation product have been suggested
[88–92]. Nevertheless, a great proportion of the global production
is sent to landfills for its disposal [61].
The amount of FGD-gypsum produced in Europe (EU15) was
approximately 11 million tonnes in 2008. More than 80% of this
FGD-gypsum was utilised by the gypsum and cement industry. In
total, about 3% of the FGD-gypsum produced was temporarily
stockpiled as a raw material base for future utilisation, mostly
for plasterboard production, and about 7% was disposed of [86].
FA FGD-gypsum BA BS FBC Ash SDA product
2% 1%
2%
8%
21%
66%
Fig. 3. Production (%) of Coal Combustion by-products in 2009 (ECOBA, 2012).
 P. Córdoba / Fuel 144 (2015) 274–286
Table 1
Quality standard characteristics for FGD-gypsum.
Properties Requirement
Free moisture <10 (% by weight)
CaSO42H2O >95* (% by weight)
MgO <0.1 (% by weight)
Cl <0.01 (% by weight)
Na2O <0.06 (% by weight)
SO2 <0.25 (% by weight)
pH value 5.0–9.0
Colour White**
Odour Neutral
Toxicity Non-toxic
*
The reduction of CaSO42H2O content by inert constituents is not detrimental to
the different areas of applications.
**
Different colour values may apply depending on the use of the FGD-gypsum and
the final products.
According to ECOBA [87], in 2009 the main use of FGD-gypsum
(
was the plaster boards (5:043 kt ), followed by levelling floor scre-
( (
eds (1363 kt ), projection plaster (729 kt ), set retarder for
( (
cement (660 kt ), gypsum blocks (258 kt ), and other uses
(
(64 kt ). Apart from the uses, FGD-gypsum has also been
employed in fire resistant panels [93] and as a material for the
sequestration of CO2 by mineral carbonation [94].
The properties of FGD-gypsum should be at least comparable to
that of natural gypsum, since stringent specifications on the prop-
erties of the gypsum used for building purposes are required. In
order to obtain high-quality FGD-gypsum from Flue Gas Desulph-
urisation, the FGD process must attain (1) a high efficiency of par-
ticulate controls; (2) causing a low Cl and F in FGD-gypsum; (3)
a high efficiency of the forced oxidation process to oxidise the
CaSO32H2O and/or Ca(HSO3)2 to CaSO42H2O; (4) using a high-
purity limestone to reduce FGD-gypsum impurities; and (5)
obtaining a high CaCO3 to CaSO42H2O conversion efficiency [10].
The specification and quality standards [86] for the FGD
gypsum product by are shown in Table 1. The disposal of FGD
by-products in landfills requires the assessment of the long-term
environmental impact of the leachates generated. In such cases
the leaching of elements of environmental concern are controlled
according to the Council Decision 2003/33/EC [95].
The Council Decision establishes the criteria and procedures for
the acceptance of waste at landfills, their application being compul-
sory (by 16 July 2005) by EU Member States. The procedure to
determine the acceptability of waste at landfills consists in a char-
acterisation, compliance testing, and on-site verification. Basic
characterisation of the waste constitutes the determination of its
type and origin, composition, consistency, leachability, and where
necessary and available, other characteristic properties. In accor-
dance with the Council Decision 2003/33/EC, the EN standards
must be used for the determination of the basic waste properties.
Thus, the standards EN-12457/1-4 [96] must be employed as leach-
ing tests for granular waste materials and sludge. According to this
characterisation, a waste is deemed acceptable for a landfill class.
Apart from the characteristics of FGD-gypsum (Table 1), general
patterns in the leaching behaviour of certain elements have been
identified. According to the literature [61,62], the leachable con-
tents of inorganic components established to be evaluated in the
aforementioned Council Decision in general elements remain
below the required limit values for wastes being accepted at land-
fills for non-hazardous wastes. Only the leachable content of F has
been identified of environmental concern [61,62,68,69,76]. As
aforementioned, HF in the FGD may form CaF2 and CaAlF3(OH)2–
CaF2 species, which can coat limestone and FGD-gypsum surfaces.
To avoid this, in addition to the use of additives, coal cleaning prior
to combustion could be an option for removing F from the feed fuel
to reduce high F inlets in the FGD.
283
The comparison of the leaching results of two FGD-gypsums and
the waste acceptance criteria at landfills revealed that operational
conditions of the FGD process may affect the leaching behaviour
of some elements [76]. In this study, all FGD-gypsum samples were
accepted at non-hazardous waste landfills. Only the leaching values
of F were well above the inert range in the FGD-gypsum but
close to non-hazardous waste. The leaching value of SO2 4 in the
FGD-gypsum samples fell in the range of non-hazardous materials,
but it was related with the solubility of gypsum therefore
preventing measures were not possible. The leaching values of most
of the heavy metals from FGD-gypsums were far below the
non-hazardous limit. This was related with the protonation of
the gypsum surface induced by the addition of Al2(SO4)3 and the
formation of SO4-complexes. It is known when the pH of an aqueous
solution is lower than the point zero charge (pzc) value, acidic
waters donate H+ than OH, and therefore the adsorbent surface is
positively charged (repelling cations). The pzc analyses of the
FGD-gypsum indicated that the pH lower than 7.5 the FGD-gypsum
surface is positively charged. Therefore, the acidic conditions of the
aqueous phase of gypsum slurry (pH 4.6–5.14) from this power
plant caused by the addition of Al2(SO4)3 probably gave rise to the
protonation of the surface of FGD-gypsum and to the formation of
SO4-complexes, which probably contributed to the maintenance
of metals in solution [97].
Other approaches of FGD-gypsum studies are those related with
the retention and speciation of trace pollutants, especially of Se and
Hg, in FGD-gypsum. The retention of Se in FGD-gypsum has been
attributed to the similar structures of gypsum and calcium selenate
di-hydrate (CaSeO42H2O). These solid species are iso-morphous
and their lattice constant are very similar [97,98] showing that
SeO2 2
4 can substitute for SO4 in the gypsum structure [98–101].
Retention and speciation studies of Hg in FGD-gypsum point
out that the speciation of Hg in FGD-gypsum is highly dependent
on the operational conditions of the FGD system. Karies et al.
[102] indicated that most of Hg in FGD-gypsum during drying pro-
cess, wallboard manufacturing, and laboratory leaching conditions
correlated with the Fe content. Rallo et al. [103] and Córdoba et al.
[57] revealed that Hg appeared associated to S and Cl, respectively
in FGD-gypsum samples from different power plants. Sun et al.
[104] case study on the relationship between speciation and
release ability of Hg in FGD-gypsum revealed that the Hg concen-
tration of in FGD-gypsum was more likely to be related to S (IV), Fe,
and Se contents.
5. Fate of trace pollutants in FGD systems
A number of studies [50,105–110] have evaluated the partition-
ing behaviour and fate of trace elements from coal-combustion in
power plants under different operational conditions whereas stud-
ies on the partitioning, behaviour, and fate of trace elements in coal-
fired power plants equipped with FGD system are much more scarce
[6,111–113]. These studies and others (7–8; 60–61) have shown
that FGD chemistry allows also the capture of many pollutants other
than S, such as F, As, B, Cl, Se or Hg both in a gaseous form and/or as
PM. One of the most investigated trace elements is Hg.
Coal Hg is converted to gaseous Hg0 in the combustion flame
and is subsequently partially oxidised (35–95%) as the combustion
gases cool down [113]. Gaseous compounds of Hg2+ are generally
water-soluble and can absorb in the aqueous phase of the absor-
bent slurry of wet FGD systems. However, gaseous Hg0 is insoluble
in water and therefore does not absorb. It is speculated that some
of Hg2+ can be converted back to Hg0 and re-emitted [56,60,114].
Mercury leaves the power plants mainly in the fly ash and flue
gas; only a minor part is present in the FGD-gypsum, sludge of the
waste water treatment plant, and effluent [81]. However, accord-
ing to other works such as those presented by Álvarez-Ayuso
284 P. Córdoba / Fuel 144 (2015) 274–286

et al. [61] and Cheng et al. [114], the partitioning of Hg OUT-FGD demand in Asia Pacific region. The market comprises of key appli-
can vary greatly. These authors reported that 60% and 70% of Hg cation segments including new systems and replacement and
removed by the FGD was found in the FGD-gypsum, respectively, reagents market. The market for FGD equipment and components
and about 35% and 4%, respectively, was emitted into the atmo- has also increased significantly for replacing old FGD components.
sphere. This suggests that the partitioning of Hg OUT-FGD could Asia Pacific dominated the market in 2012 and accounted for over
depend on e.g. specific operational conditions of power plants. 55% of the global annual revenue [119]. Asia Pacific is confronted
According to Meij [50] the temperature of the electrostatic precip- with implementation of impending regulations continuously over
itator and the Cl content of the fuel have a large effect on Hg spe- the past couple of years; hence several manufacturers (especially
ciation, which in turn greatly affects the emissions. Gullit et al. coal fired industries) are opting for the retrofitted FGD systems
[116] reported that calcium compounds can promote the adsorp- [119].
tion of Hg2Cl2 on FA particles, thus increasing the removal in the The U.S. is estimated to dominate the FGD market in North
electrostatic precipitator, and decreasing the incoming proportion America due to the enactment of numerous regulations including
of Hg to FGD system. U.S. ARP (Acid Rain Program). Canada is estimated to be the second
Regarding the emission abatement capacity for Hg, measure- dominant region in North America.
ments in US showed that the combination of Selective Catalysis In Europe, the implementation of European Union National
Reduction (SCR), electrostatic precipitator, and wet FGD gave rise Emission Ceilings [120] helped in reducing the SO2 levels in the
to Hg removals of 84–89% [117]. In Japan, 33% Hg removal as atmosphere. In 2011, EU NEC revised the ceiling level for SO2 with
reported for electrostatic precipitator and 70% for the combination a view to reducing harmful emissions and assist in reducing global
of electrostatic precipitator and FGD [111]. These removals rates for warming.
Hg in the US and Japan were similar to the Dutch findings [53],
except for the electrostatic precipitator. In this work was also
7. Conclusions
reported that if a high dust SCR for NOx reduction is present, the
total removal of Hg can be up to 90%. SCR catalysis can act to oxidise
According to the literature, the wet limestone FGD system is the
a significant proportion of the Hg0 into Hg2+, thereby enhancing the
FGD process most widely used because of its high desulphurisation
capture of Hg in downstream wet FGD. Therefore the co-benefit of
performance and low operating cost. Among control parameters
increased Hg2+ through the SCR catalyst is very important to the
evaluated in this review, pH range > limestone reactivity and SO2
overall control of Hg emissions from coal-fired power plants [118].
concentration > efficiency of particulate control devices > water
The distribution of moderately and volatile elements such As,
re-circulation to the scrubber > entrainment of particles by the
Se, F, Cl, and B, has also been studied in FGD systems. Most of spec-
OUT-FGD gas, are the key factors that control the desulphurisation
ialised literature [1,5–8] reports that most of trace elements in FGD
efficiency and the abatement capacity for inorganic trace pollu-
systems are removed in the aqueous effluent (filtered water) and
tants in wet limestone FGD systems.
only a fraction of a few remain in the flue gases (such as B, Hg,
Wet limestone FGD systems are designed to operate at optimal
and Se). Álvarez-Ayuso [61] indicated that Cl (80%) remained in
pH range of 5.0–6.0. At lower pH values (4.0 > pH), the equilibrium
the effluent arising from the gypsum slurry filtration, whereas S,
pressure of SO2 increases and as a consequence the gas absorption
F, As, and Se were mostly partitioned in the FGD-gypsum with val-
rate decreases and approximates to zero, whereas pH values >6.3
ues comprised in the range 90–99%. The abatement for As, Cl, F, S,
may give rise to scrubber scale problems by precipitation of CaSO3.
and Se attained values from 96% to 100%; whereas an abatement
The dissolution state of CaSO3 is possible for pH values <6.3.
capacity about 60% was attained for Hg. This retention efficiency
Wet limestone FGD systems reach high retention efficiencies for
for Hg was consistent with data reported by Meij et al. [50], who
trace elements (>90%). Moderately and highly volatile elements
found, on average, Hg removal of 54.4 ± 24% when studying the
such as Cl and B are usually removed in the aqueous phase effluent,
behaviour of Hg in coal-combustion power plants in the Nether-
whereas S, F, As, and Se are retained in the FGD-gypsum; only a
lands. Cheng et al. [115] reported removal efficiencies by a wet
fraction of a few remain in the flue gases (such as B, Hg, and Se).
FGD system over 90% of Cl, 77% of B, 76% of Hg, 30% of Se, and
The gradual increase of the concentration of inorganic trace pol-
5% of As. For B and Cl over 99% were discharged from the coal com-
lutants in FGD waters as a consequence of the continuous water re-
bustion process with the effluent. Approximately 90% of Hg, 30% of
circulation in the scrubber, accounts for the enrichment inorganic
Se, and 5% of As removed by the FGD was associated with FGD-
trace pollutants in the re-circulated waters. High levels of these
gypsum; and less than 5% of Se and 0.5% of B were emitted into
metals and other pollutants in filtered water increase the emission
the atmosphere. Córdoba et al. [43] also reported high retention
of metals by entraining and/or evaporation of droplets as PM from
capacity (92–100%) for gaseous Cl, F, and B, and relatively high effi-
gypsum slurry in the OUT-FGD. This in conjunction with the
ciencies for S (82–85%), Se (37–80%), and As (67–98%). The non-
entrainment of the unreacted limestone particles and of fly ash
retained FA by FGD and the particles and droplets from gypsum
particles accumulated in gypsum sludge by the OUT-FGD gas con-
slurry entrained in the OUT-FGD gas were found to be responsible
siderably reduce the abatement capacity of trace elements by wet
for the relatively lower retention efficiencies for Se and As com-
limestone FGDs.
pared with the other volatile elements.
As a result of the forthcoming implementation of oxy-fuel com-
According to these studies, it can be concluded that wet lime-
bustion at an industrial scale, the integration of oxy-fuel combus-
stone FGD systems reaches high retention efficiencies for trace ele-
tion in PCC–FGD processes reveals a number of uncertainties to be
ments (>90%). However, it is also important to note that the
investigated. The determination of the sources, pathways and
retention efficiency of FGD system for trace elements may be
especially the speciation and fate of trace pollutants during oxy-
reduced because of the emission of fly dust in evaporate droplets
PCC–FGD will be a priority to deal with.
saturated with gypsum [81].

References
6. State of the FGD market
[1] Soud HN. Developments in FGD. CCC/29, IEA Coal Research, London; 2000.
[2] United States Environmental Protection Agency (US EPA). Controlling SO2
The Chinese FGD market is expected to grow due to rising ther- emissions: a review of technologies. EPA/600/R-00/093; 2000.
mal power generation that is likely to fuel the FGD systems [3] Clarke L, Sloss L. Trace elements. EIACR/49.Ed, IEA coal research; 1992. p. 51.
 P. Córdoba / Fuel 144 (2015) 274–286
[4] Helle GN, Soren K, Jan EJ, Jorgen NJ, Jørn H, Folmer F, et al. Full-scale
measurements of SO2 gas phase concentrations and slurry compositions in a
wet flue gas desulphurisation spray absorber. Fuel 2004;83:1151–64.
[5] Clarke L. The fate of trace elements during combustion and gasification: an
overview. Fuel 1993;72(6):731–6.
[6] Aunela-Tapola L, Hatanpää E, Hoffren H, Laitinen T, Larjava K, Rasila P, et al. A
study of trace element behaviour in two modern coal-fired power plants: II.
Trace element balances in two plants equipped with semi-dry flue gas
desulphurization facilities. Fuel Proces Tech 1998;55(1):13–34.
[7] Heebink LV, Hassett DJ. Hg release from FGD. In: Proceeding of international
ash utilization symposium, CAER, University of Kentucky; 2003. p. 75.
[8] Schroeder K, Kairies C. Distribution of Hg in FGD by-products. In: Proceedings
of world of coal ash conference, CAER, University of Kentucky, April 11–1.
Paper 100; 2005.
[9] United States Environmental Protection Agency (US EPA). Flue gas
desulfurization system capabilities for coal-fired steam generators. Vol II
Technical Report. EPA-600/7-78-032b; March 1978.
[10] Reference document on best available techniques for large combustion plants
(BREFs); 2006.
[11] Babcock & Wilcox Power Generation Group (B&W). Steam-its generation and
use, 40th ed. Barbeton, Ohio: Babcock and Wilcox Company; 1991. p. 980.
[12] Polster M, Nolan PS, Batyko RJ. Babcock & Wilcox Technologies for power
plant stack emissions control. Paper N. BR-1571, U.S./Korea Electric Power
Technologies Seminar Mission, Seoul, Korea; October 1994.
[13] Lani BW, Babu M. Phase II: the age of high velocity scrubbing. EPRIDOE-EPA
combined utility air pollutant control symposium: the mega symposium: SO2
control technologies and continuous emission monitors, EPRI, Palo Alto, CA,
U.S. Department of Energy, Pittsburgh, PA,4 and U.S. Environmental
Protection Agency, Air Pollution Prevention and Control Division, Research
Triangle Park, NC. TR-108683-V2; 1997.
[14] Benson L, Garner J, Murphy JL, Thompson M, Weilert C. Henderson municipal
power & light a low-cost phase I clean air act retrofit. EPRI-DOEEPA combined
utility air pollutant control symposium: the mega symposium: SO2 control
technologies and continuous emission monitors, EPRI, Palo Alto, CA, U.S.
Department of Energy, Pittsburgh, PA, and U.S. EPA, Air Pollution Prevention
and Control Division, Research Triangle Park, NC. TR-108683-V2; 1997.
[15] Kamall R. Flue Gas Desulphurisation (FGD) technologies. Cleaner coal
technology programme, Department of Trade and Industry, 1 Victoria
Street, London SW1H 0ET; 2000.
[16] Zheng Y, Kiil S, Johnsson JE, Zhong Q. Use of spray dry absorption product in
wet flue gas desulphurization plants: pilot-scale experiments. Fuel
2002;81:1899–905.
[17] Centro de Investigaciones Energéticas y Medioambientales (CIEMAT). Flue
gas cleaning. Clean coal technologies handbook; 2000.
[18] Babu M, Forsythe RC, Runyon CV, Kanary DA, Pennline HW, Sarkus T,
Thompson JL. Results of 1.0 MMBtu/hour testing and plants for a 4 MW pilot
HALT program for SO2 control. Proceedings of the third annual pittsburgh
coal conference, Pittsburgh, PA; 1986.
[19] Frandsen JBW, Kiil S, Johnsson JE. Optimisation of a wet FGD pilot plant using
fine limestone and organic acids. Chem Eng Sci 2001;56:3275–87.
[20] Gutiérrez Ortiz FJ. A simple realistic modeling of full-scale wet limestone FGD
units. Chem Eng J 2010;165:426–39.
[21] Brown SR, DeVault RF, Williams PJ. Determination of wet FGD limestone
reactivity. Electric power. Babcock & Wilcox Power Generation Group, Inc.,
Barberton, Ohio, USA; 2010.
[22] Kikkawa H, Nakamoto T, Morishita M, Yamada K. New wet FGD process using
granular limestone. Ind Eng Chem Res 2002;41:3028–36.
[23] Sheng-yu L, Bin Qu, Jin G, Jian-ying L, Zhi-xiang Y, Cheng-hua X. New
limestone-gypsum flue gas desulfuization technology. In: Proceeding of:
energy and environment technology. ICEET ‘09. International conference on,
vol. 3; 2009.
[24] Kikkawa H, Kaku H, Nozawa S, Kohata K. New wet FGD process using granular
limestone. In: Proceedings of power gen Europe’ 97. Power Engineering
International: Tulsa; 1997. p. 585–601.
[25] Werner W, Gopendra KR. Kinetics of lime-limestone sulfation: review of lime
reactivity and sulfation kinetics in the dry limestone desulfurization
processes. High Temp–High Pressures 1981;13:333–45.
[26] Hartman M, Coughlin RW. Ind Eng Chem Process Des Dev 1974;13:248–53.
[27] Córdoba P, Ochoa-González R, Font O, Izquierdo M, Querol X, Leiva C, et al.
Partitioning of trace inorganic elements in a coal-fired power plant equipped
with a wet flue gas desulphurisation system. Fuel 2012;92:145–57.
[28] Kiil S, Nygaard H, Johnsson JE. Simulation studies of the influence of HCl
absorption on the performance of a wet flue gas desulphurisation pilot plant.
Chem Eng Sci 2002;57:347–435.
[29] Gutiérrez Ortiz FJ, Vidal F, Ollero P, Salvador L, Cortés V, Giménez A. Pilot
plant technical assessment of wet flue gas desulfurization using limestone.
Ind Eng Chem Res 2006;45:1466–77.
[30] Walsh M.A., Mengel M.L., Evans A, Gal, Cavallari G, Bienati M, Cavezzale P.
Parameters impacting limestone dissolutions in FGD systems. Marsulex
Environmental Technologies, Corp and Termokimik Corporation – Impianti e
Procedimenti Industriali SpA; 2006.
[31] Dou B, Pan W, Jin Q, Wang W, Li Y. Prediction of SO2 removal efficiency for
wet Flue Gas Desulfurization. Energy Convers Manage 2009;50:2457–553.
[32] Zhong Y, Gao X, Huo W, Luo Z, Ni M, Gen K. A model for performance
optimization of wet flue gas desulfurization systems of power plants. Fuel
Process Technol 2008;89:1025–32.
285
[33] Gage CL. Limestone dissolution in modelling of slurry scrubbing for flue gas
desulfurization. Ph.D. thesis. University of Texas, Austin; 1989.
[34] Argarwal RS, Rochelle GT. Chemistry of limestone slurry scrubbing. SO2
control symposium, vol. 3. U.S. Environ Prot Agency, Res Dev, EPA-600-R-95-
015, Boston; 1993. p. 78.
[35] Brogren C, Karlson HT. A model for prediction of limestone dissolution in wet
flue gas desulfurization applications. Ind Eng Chem Res 1997;36:3889–97.
[36] Eden D, Luckas M. A heat and mass transfer model for the simulation of the
wet limestone flue gas scrubbing process. Chem Eng Technol 1998;21:56–60.
[37] Lancia A, Musmarra D, Pepe F. Modeling of SO2 absorption into limestone
suspensions. Ind Eng Chem Res 1997;36:197–203.
[38] Gerbec M, Stergarsek A, Kocjancic R. Simulation model of wet flue gas
desulphurization plant. Comput Chem Eng 1995;19:283–6.
[39] Brogren C, Karlsson HT. Modelling the absorption of SO2 in a spray scrubber
using the penetration theory. Chem Eng Sci 1997;1:3085–99.
[40] Warych J, Szymanowski M. Model of the wet limestone flue gas
desulfurization process for cost optimization. Ind Eng Chem Res
2001;40:2597–605.
[41] Xiang GM. Studies of slurry jet flue gas desulfurization. Beijing: Tsinghua
University; 2002.
[42] Kiil S, Michelsen ML, Dam-Johansen K. Experimental investigation and
modelling of a wet flue gas desulphurisation pilot plant. Ind Eng Chem Res
1998;37:2792–806.
[43] Takeshita M, Soud, H. FGD performance and experience on coal-fired plants.
IEACR/58, London: IEA Coal Research; 1993.
[44] Zheng Y, Kiil S, Johnsson JE. Experimental investigation of a pilot-scale jet
bubbling reactor for wet flue gas desulphurisation. Chem Eng Sci
2003;58:4695–703.
[45] Davidson RM. Chlorine and other halogens in coal, IEAPER/28. London: IEA
Coal Research; 1996.
[46] Shao D, Hutchinson EJ, Cao H, Pan WP. Behaviour of chlorine during coal
pyrolysis. Energy Fuels 1994;8:399–401.
[47] Deacon H. U.S. Patent 165,802; 1875.
[48] Griffin RDA. Theory of dioxin formation in municipal solid waste combustion.
Chemosphere 1986;1:1987.
[49] Yoo KS, Kim KT. Effect of HCl on sulfation reaction of limestone slurry in a jet
bubbling reactor. Hwahak Konghak. J Korean Chem Eng 1998;36(5):
641–5.
[50] Meij R. The fate of mercury in coal-fired power plants and the influence of
wet flue-gas desulphurisation. Water Air Soil Pollut 1991;56:21–33.
[51] Meij R, Vredenbregt LHJ, TeWinkel BH. The fate of mercury in coal-fired
power plants. J Air Waste Manage Assoc 2002;52:912–7.
[52] Meij R, Te Winkel BH. Mercury emissions of coal-fired power stations, firing
bituminous coal, as a function of plant parameters, coal composition and co-
combustion. In: Proceedings of the international conference on air quality IV
(mercury, trace elements and Particulate Matter). Arlington, VA, USA; 22–24
September 2003.
[53] Meij R, te Winkel H. Mercury emissions from coal-fired power stations: the
current state of the art in the Netherlands. Sci Tot Environ 2006;368:393–6.
[54] Galbreath KC, Zygarlicke CJ. Mercury transformations in coal combustion flue
gas. Fuel Proc Technol 2000;65–66:289–310.
[55] Senior CL, Helble JJ, Sarofim AF. Emissions of mercury, trace elements, and
fine particles from stationary combustion sources. Fuel Process Technol
2000;65–66:263–88.
[56] Wo J, Zhang M, Cheng X, Zhong X, Jiang Xu, Xinhua Xu. Hg2+ reduction and
reemission from simulated wet flue gas desulphurization liquors. J Hazard
Mater 2009;172:1106–10.
[57] Córdoba P, Maroto-Valer M, Ayora C, Perry R, Rallo M, Font O, et al. Unusual
speciation and retention of Hg at a coal-fired power plant. Environ Sci
Technol 2012;46:7890–7.
[58] Blythe G, De Berry D, Marsh B, Paradis J, Range J. Bench-scale evaluation of
the fate of mercury in wet FGD systems. EPRI, Palo Alto, CA; 2004. p. 94304–
1395.
[59] Currie J, et al. Bench-scale kinetics study of mercury reactions in FGD liquors.
In: Proceedings of the DOE NETL mercury control technology conference,
Pittsburgh, PA; 2006.
[60] Omine N, Romero CE, Kikkawa H, Wu S, Eswaran S. Study of elemental
mercury re-emission in simulated wet scrubber. Fuel 2012;91:93–101.
[61] Álvarez-Ayuso E, Querol X, Tomás A. Environmental impact of coal
combustion desulphurisation plant: abatement capacity of desulphurisation
process and environmental characterisation of combustion by-products.
Chemosphere 2006;665:2009–17.
[62] Font O, Querol X, Moreno T, Ballesteros JC, Giménez A. Effect of aluminium
sulphate addition on reducing the leachable potential of fluorine from FGD
gypsum. Proceedings: 2nd international conference on engineering for waste
valorisation. Patras. Greece, ISBN: 978-960-530-101-9; 2008. p. 150.
[63] Pauly H. Ralstonite from Ivigtut, South Greenland. Am Miner
1965;50:1851–64.
[64] Mori T, Matsuda S, Nakajima F, Nishimura T, Arika Y. Effect of Al3+ and F on
the desulfurization reaction in limestone slurry scrubbing process. Ind Eng
Chem Process Des Dev 1981;20:144.
[65] Maroney P, Davidson SA, Katzberger SM, Cichazowicz JE. Particulate control
integration with wet scrubber SO2 removal and waste generation. In:
Proceedings of the 6th symposium on the transfer and utilization of
particulate control technology. Electric Power Research Institute: Palo Alto,
CA; 1986. p. (17) 1–22.
286 P. Córdoba / Fuel 144 (2015) 274–286
[66] Farmer WR, Jarvis JB, Mosser R. Effects of aluminium/fluoride chemistry in
wet limestone flue gas desulfurization. Chem Eng Commun 1989;77:135.
[67] Ukawa N, Okino S, Iwaki T, Oshima M, Watanabe Y. The effects of fluoride
complexes in wet flue gas desulfurization. J Chem Eng Jpn 1992;25:146–52.
[68] Álvarez-Ayuso E, Querol X. Study of the use of coal fly ash as an additive to
minimise fluoride leaching from FGD gypsum for its disposal. Chemosphere
2008;71:140–6.
[69] Álvarez-Ayuso E, Querol X. Stabilization of FGD gypsum for its disposal in
landfills using amorphous aluminium oxide as fluoride retention.
Chemosphere 2007;69:295–302.
[70] Córdoba P, Ayora C, Moreno N, Font O, Izquierdo M, Querol X. Influence of an
aluminium additive in aqueous and solid speciation of elements in flue gas
desulphurisation system. Energy 2013;50:438–44.
[71] Rochelle GT, King CJ. The effect of additives on mass transfer in CaCO3 and
CaO slurry scrubbing of SO2 from waste gases. Ind Eng Chem Fundam
1977;16(1):67–75.
[72] Rochelle GT, Weems WT, Smith RJ, Hsiang MW. Buffer additives for lime/
limestone slurry scrubbing. ASC Symp Ser 1982;188:243–65.
[73] Chang JCS, Mobley JD. Testing and commercialization of byproduct dibasic
acids as bu4er additives for limestone 9ue gas desulfurization systems. J Air
Pollut Control Assoc 1983;33(10):955–62.
[74] Chi CT, Lester H. Utilization of adipic acid byproducts for energy recovery and
enhancement of flue gas desulfurization. Environ Prog 1989;4:223–6.
[75] Heidel B, Hilber M, Scheffknecht G. Impact of additives for enhanced sulfur
dioxide removal on re-emissions of mercury in wet flue gas desulfurization.
Appl Energy 2014;111:485–91.
[76] Córdoba P, Font O, Izquierdo M, Querol X, Tobías A, López-Antón MA, et al.
Enrichment of inorganic trace pollutants in re-circulated water streams from
a wet limestone flue gas desulphurisation system in two coal power plants.
Fuel Process Technol 2011;92:1764–75.
[77] Ochoa-Gonzalez R, Diaz-Somoano M, Martinez-Tarrazona MR. Control of Hg0
re-emission from gypsum slurries by means of additives in typical wet
scrubber conditions. Fuel 2013;105:112–8.
[78] Meij R. Composition and particle size of and exposure to coal fly ash. J Aerosol
Sci 2000;31:676–7.
[79] Meij R, te Winkel H. The emissions and environmental impact of PM10 and
trace elements from a modern coal-fired power plant equipped with ESP and
wet FGD. Fuel Pro Technol 2004;85:641–56.
[80] Meij R, te Winkel H. The emissions of heavy metals and persistent organic
pollutants from modern coal-fired power stations. Atmos Environ
2007;40:9262–72.
[81] Meij R. Trace element behaviour in coal-fired power plants. Fuel Process
Technol 1994;39:199–217.
[82] ABETRAP European project. Research funding of coal and steel (RFCS), RFCR-
CT-2006-00006.
[83] Hrastel I, Gerbec M, Stergarsek A. Technology optimization of wet flue gas
desulphurization process. Chem Eng Technol 2007;30:220–33.
[84] Kong H. Experimental and theoretical study on limestone wet flue gas
desulfurization. Hangzhou: Zhejiang University; 2001.
[85] Gao H, Li C, Zenga G, Zhanga W, Shia L, Li S, et al. Flue gas desulphurization
based on limestone–gypsum with a novel wet-type PCF device. Sep Purif
Technol 2011;76:253–60.
[86] Eurogypsum. FGD gypsum quality criteria and analysis methods. Brussels,
Association of European Gypsum Industries; 2012.
[87] European Coal Combustion Products Association (ECOBA). <http://
www.ecoba.com/index.html> [accessed 2012].
[88] Solem-Tishmack JK, McCarthy GJ, Docktor B, Eylands KE, Thompson JS,
Hassett DJ. High-calcium coal combustion by-products: engineering
properties, ettringite formation, and potential application in solidification
and stabilization of selenium and boron. Cem Concr Res 1995;25:658–70.
[89] Stehouwer RC, Sutton P, Dick WA. Minespoil amendment with dry flue gas
desulfurization by-products: plant growth. J Environ Qual 1995;24:861–9.
[90] Payette RM, Wolfe WE, Beeghly J. Use of clean coal combustion by-products
in highway repairs. Fuel 1997;76:749–53.
[91] Chen LM, Dick WA, Nelson S. Flue gas desulfurization products as sulphur
sources for alfalfa and soybean. Agron J 2005;97:265–71.
[92] Chou MIM, Bruinius JA, Bening V, Chou SFJ, Carty RH. Producing ammonium
sulfate from flue gas desulfurization by-products. Energy Source
2005;27:1061–71.
[93] Leiva C, García Arenas C, Vilches LF, Vale J, Gimenez A, Ballesteros JC, et al. Use
of FGD-gypsum in fire resistant panels. Waste Manage 2010;30:1123–9.
[94] Lee M, Jang YN, Ryu K, Kim W, Bang J. Mineral carbonation of flue gas
desulfurization gypsum for CO2 sequestration. Energy 2012;47:370–7.
[95] Council decision 2003/33/EC of 19 December 2002 establishing criteria and
procedures for the acceptance of waste at landfills pursuant to Article 16 of
and Annex II to Directive 1999/31/EC.
[96] EN-12457-4 characterization of waste-leaching-compliance test for leaching
of granular waste materials and sludges – Part 4: one stage batch test at a
liquid to solid ratio of 10 l/kg for materials with particle size below 10 mm
(without or with size reduction).
[97] Cordoba P. Partitioning and speciation of trace elements at two coal-fired
power plants equipped with a wet limestone Flue Gas Desulphurisation
(FGD) system. PhD dissertation, Institute of Environmental Assessment and
Water Research (IDÆA-CSIC); 2013.
[98] Pedersen BF, Semmingsen D. Neutron-diffraction refinement of the structure
of gypsum CaSO4.2H2O. Acta Crystallogr 1982;38:1074–7.
[99] Kruger RR, Abriel W. Growth and structure refinement of CaSeO4H2O. Acta
Crystallogr 1991;47:1958–9.
[100] Freyer D, Voigt W. Crystallization and phase stability of CaSO4 and
CaSO4-based salts. Monatsh Chem 2003;134:693–719.
[101] Fernández-González A, Andara A, Alía JM, Prieto M. Miscibility in the
CaSO42H2O–CaSeO42H2O system: implications for the crystallisation and
dehydration behaviour. Chem Geol 2006;225:256–65.
[102] Kairies CL, Schroeder KT, Cardone CR. Mercury in gypsum produced from flue
gas desulfurization. Fuel 2006;85:2530–6.
[103] Rallo M, López-Antón MA, Meij R, Perry R, Maroto-Valer MM. Mercury
speciation in gypsums produced from flue gas desulfurization by
temperature programmed decomposition. Fuel 2010;89:2157–9.
[104] Sun M, Hou J, Cheng G, Ali Baig S, Tan L, Xu X. The relationship between
speciation and release ability of mercury in flue gas desulfurization (FGD)
gypsum. Fuel 2014;125:66–72.
[105] Querol X, Crehuet R, Alastuey A, López-Soler A, Fernández-Turiel JL, Plana F,
et al. Geoquímica y mineralogía aplicadas a estudios de impacto
ambiental derivado de la combustión del carbón. Acta Geologica Hispanica
1996;30(1–3):145–53.
[106] Martínez-Tarazona RM, Spears A. The fate of trace elements and bulk
minerals in pulverized coal combustion in a power station. Fuel Proc Tec
1996;41:79–92.
[107] Yan R, Lu XH, Zeng HC. Trace elements in Chinese coals and their partitioning
during coal combustion. Comb Sci Technol 1999;145:57–81.
[108] Vassilev SV, Eskenazy GM, Vassileva CG. Behaviour of elements and minerals
during preparation and combustion of the Pernik coal, Bulgaria. Fuel Process
Technol 2001;72:103–29.
[109] Pires M, Querol X. Characterization of Candiota (South Brazil) coal and
combustion by-product. In J Coal Geol 2004;60:57–72.
[110] Li Z, Clemens AH, Moore TA, Gong D, Weaver SD, Eby N. Partitioning
behaviour of trace elements in a stoker-fired combustion unit: an example
using bituminous coals from the Greymouth coalfield (Cretaceous), New
Zealand. Int J Coal Geol 2005;63:98–116.
[111] Yokoyama T. Trace element emissions from coal-fired power plants in Japan.
Legislation, emissions, environmental control technologies. Proceedings of
CEM 99, international conference on emissions monitoring, held at the
University of Warwick, Coventry, UK, September 6–8, 1999. The paper was
presented at the Trace Elements Workshop organised by IEA on 9 September;
1999.
[112] Sandelin K, Backman R. Evinron Sci Technol 2001;35:826.
[113] Pavlish JH, Sondreal EA, Mann MD, Olson ES, Galbreath KC, Laudal DL, et al.
Status review of mercury control options for coal-fired power plants. Fuel
Proc Technol 2003;82(2–3):89–165.
[114] Stergaršek A, Horvat M, Frkal P, Stergaršek J. Removal of Hg0 from flue gases
in wet FGD by catalytic oxidation with air – an experimental study. Fuel
2010;89:3167–77.
[115] Cheng C, Hack P, Chu P, Chang Y, Lin T, Ko C, et al. Partitioning of mercury,
arsenic, selenium, boron, and chloride in a full-scale coal combustion process
equipped with selective catalytic reduction, electrostatic precipitation, and
flue gas desulfurization systems. Energy Fuels 2009;23:4805–16.
[116] Gullit BK, Ghorishi B, Huggins FE. Mercury chloride capture by alkaline
sorbents. In the Proceedings of the air and waste management association
93rd annual meeting in Salt Lake City, UT on June 18–22. Paper 259;
1999.
[117] Withum JA, Tseng SC, Locke JE. Mercury sampling at power plants with SCR-
FGD combinations. Presented at the MEC2 workshop mercury emissions
from coal in Ottawa, Canada, May 24–25; 2005.
[118] Gretta WJ, Morita I, Moffett JW. Mercury oxidation across SCR catalyst
at LG&E’s trimble county unit 1. Hitachi Power Systems America Ltd.;
2006.
[119] Flue gas desulfurization (FGD) systems market analysis to 2020 – global
market size, equipment market share, competitive landscape, regulations
and pricing analysis. <http://www.researchandmarkets.com/reports/
1445349/flue_gas_desulfurization_fgd_systems_market> [accessed April
2014].
[120] http://ec.europa.eu/environment/air/pollutants/ceilings.htm.