The Babcock & Wilcox Company

Chapter 35
Sulfur Dioxide Control

Sulfur appears in the life cycle of most plants and Pure water has a pH of 7 and is defined as neutral,
animals. Most sulfur emitted to the atmosphere origi- while lower values are defined as acidic and higher
nates in the form of hydrogen sulfide from the decay values as alkaline. If rainwater contained no sulfuric
of organic matter. These emissions slowly oxidize to or nitric acid, its pH would be approximately 5.7 due
sulfur dioxide (SO2). Under atmospheric conditions, to absorption of carbon dioxide (CO2) from the atmo-
SO2 is a reactive, acrid gas that can be rapidly assimi- sphere. The contributions of man-made SO2 and ni-
lated back to the environment. However, the combus- trogen oxides (NOx) further reduce the pH of rainwa-
tion of fossil fuels, in which large quantities of SO2 are ter. No uniformly accepted definition exists as to what
emitted to relatively small portions of the atmosphere, pH constitutes acid rain. Some authorities believe that
can stress the ecosystem in the path of these emissions. a pH of about 4.6 is sufficient to cause sustained dam-
Man is responsible for the majority of the SO2 emit- age to lakes and forests in the northeastern portion of
ted to the atmosphere. Annual worldwide emissions North America and in the Black Forest region of Europe.
are approximately 160 million tons, nearly half of
which are from industrial sources. The two principal
industrial sources are fossil fuel combustion and met- SO2 emissions regulations
allurgical ore refining. Legislative action has been responsible for most in-
When gaseous SO2 combines with liquid (
) water, dustrial SO2 controls. Major landmark regulations in-
it forms a dilute aqueous solution of sulfurous acid clude the Clean Air Act Amendments of 1970, 1977 and
(H2SO3). Sulfurous acid can easily oxidize in the at- 1990 in the United States (U.S.), the Stationary Emis-
mosphere to form sulfuric acid (H2SO4). Dilute sulfu- sions Standards of 1970 in Japan, and the 1983 SO2
ric acid is a major constituent of acid rain. (Nitric acid Emissions Regulations of the Federal Republic of Ger-
is the other major acidic constituent of acid rain.) The many. Since the mid-1980s, SO2 emissions regulations
respective reactions are written: have been implemented in most other industrialized
nations and many developing nations.
SO2 (g) + H2O (
) → H2 SO3 (aq) (1)

O2 (g) + 2H2 SO3 (aq) → 2H2 SO4 (aq) (2) SO2 control
Most utilities have adopted one of two strategies for
SO2 can also oxidize in the atmosphere to produce gas- SO2 control, either switching to low sulfur coal or in-
eous sulfur trioxide (SO3). Sulfur trioxide reactions are stalling scrubbers.
written: A variety of SO2 control processes and technologies
are in use and others are in various stages of devel-
2SO2 (g) + O2 (g) → 2SO3 (g) (3) opment. Commercialized processes include wet, semi-
dry (slurry spray with drying) and completely dry pro-
SO3 (g) + H2O(g) → H2 SO4 (
) (4) cesses. The wet flue gas desulfurization (WFGD)
scrubber is the dominant worldwide technology for the
While Equations 1 and 2 describe the mechanism control of SO2 from utility power plants, with approxi-
by which SO2 is converted to sulfuric acid in acid rain, mately 85% of the installed capacity, although the dry
Equations 3 and 4 characterize dry deposition of acidi- flue gas desulfurization (DFGD) systems are also used
fied dust particles and aerosols. for selected lower sulfur applications.
The pH scale, a measure of the degree of acidity or Total annual SO2 emissions in the U.S., including
alkalinity, is the method used to quantify the acidity electric utility SO2 emissions, have declined since 1970
of acid rain. as various regulations have been adopted. During the

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 The Babcock & Wilcox Company

same period, electricity generation from coal has almost with forced oxidation. These absorber internals were
tripled (see Table 1).1,2 subject to severe scaling and plugging of internal com-
A significant portion of this emissions reduction has ponents, such as spray nozzles. With the development
been the result of switching to low sulfur coal, predomi- of forced oxidation, the scaling has effectively been
nantly from the western U.S. In 1970 virtually all of eliminated. This, along with improvements in acces-
the utility coal came from the eastern, higher sulfur sory equipment such as pumps, has eliminated the
coal fields, while by 2000 approximately half of the need for spare scrubber modules. Most wet scrubbers
coal came from western low sulfur sources. Slightly include a spare recirculation pump and spray header.
less than two-thirds of SO2 emission reductions have However, the pump and header reliability are such that
been attributed to fuel switching while over a third even spare pumps are not required in some designs.
has been through the installation of flue gas desulfu- Since the mid-1990s the use of a single absorber
rization systems, predominantly wet scrubbers. More module in WFGD systems has become an accepted
than 30% of the U.S. coal-fired capacity already has design. Single absorber modules have been supplied
FGD systems installed and operating. This may come to handle 1300 MW boilers. Some designs use a single
close to doubling over the next decade and a half as absorber to treat the flue gas from multiple boilers. The
existing regulations are implemented and proposed availability of most of these systems has been ap-
regulations are adopted. proaching 100%. In most cases, forced outages or load
reductions have been due to problems with support
systems such as reagent preparation, dewatering and
Wet scrubbers gypsum handling rather than the absorber module.
General arrangement and design Fig. 1 provides a
Reagents side view of a 660 MW modern coal-fired power sys-
Wet scrubbing processes are often categorized by tem showing the location of the SO2 scrubber absorber
reagent and other process parameters. The primary module. Absorber modules are located on either side
reagent used in wet scrubbers is limestone. However, of the stack though other arrangements are possible.
any alkaline reagent can be used, especially where The dust collector, in this case an ESP, is placed up-
site-specific economics provide an advantage. Other stream of the wet scrubber. In this arrangement, the
common reagents are lime (CaO), magnesium en- induced draft (ID) fan is between the dust collector
hanced lime (MgO and CaO), ammonia (NH3), and and the scrubber, permitting the fan to operate in a
sodium carbonate (Na2CO3). The first part of this particulate-free, dry flue gas. In cases of retrofit to
chapter concentrates on limestone-based wet scrub- existing units, it is sometimes necessary to add a
bing systems with forced oxidation to produce gyp- booster fan between the ID fan and the scrubber. In
sum. The next major section focuses on lime-based some systems, the booster fan is installed after the wet
semi-dry or dry systems. scrubber in what is referred to as the wet position. This
Reagent regeneration A number of the wet processes is not the preferred method as wet fans require more
are also classified as either non-regenerable or regen- maintenance and are more expensive.
erable systems. In non-regenerable systems, the re- The most common WFGD absorber module is the
agent in the scrubber is consumed to directly gener- spray tower design shown in Fig. 2. The flue gas en-
ate a byproduct containing the sulfur, such as gyp- ters the side of the spray tower at approximately its
sum. In regenerable systems, the spent reagent is midpoint and exits through a transition at the top. The
regenerated in a separate step to renew the reagent upper portion of the module (absorption zone) provides
material for further use and to produce a separate for the scrubbing of the flue gas to remove the SO2
byproduct, such as elemental sulfur. The dominant while the lower portion of the module serves as an
limestone and lime reagent systems used today are integral slurry reaction tank (also frequently referred
non-regenerable. In many cases the regenerable sys- to as the recirculation tank and oxidation zone) to com-
tems have been retrofitted with non-regenerable lime- plete the chemical reactions to produce gypsum. The
stone or lime reagent systems to reduce costs and im- self-supporting absorber towers typically range in di-
prove unit availability. ameter from 20 to 80 ft (6 to 24 m) and can reach 150
ft (46 m) in height. In some designs, the lower reac-
Absorber design tion tank is flared downward to provide a larger di-
Evolution The first WFGD scrubbers installed in
the U.S. were combined particulate collectors and SO2
absorbers. However, the energy requirements for the Table 1
venturi scrubbers used for particulate collection U.S. SO2 Emissions and Coal-Fired Power Generation
proved to be excessive. High efficiency dust collectors,
usually electrostatic precipitators (ESPs), replaced Coal Fired
venturi scrubbers, and separate, much lower pressure Total U.S. SO2 Utility SO2 Utility Generation
drop absorber towers were used to absorb the SO2. 106 t/yr 106 t/yr 1012 kWh
The WFGD systems installed in the 1970s and early 1970 31 17 0.7
1980s were typically sized with multiple modules with 1980 26 17 1.2
spare spray headers and sometimes spare scrubber 1990 23 16 1.6
(absorber) modules. Prior to about 1978, most of the 2000 16 11 2.0
lime and limestone WFGD systems were not designed

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Stack

Low NOX SCR

Burners
Furnace

Air Heater Absorber

Precipitator Induced
Draft
Pulverizers Fan
Forced
Draft
Fans

Fig. 1 Typical emission control components for a coal-fired utility boiler.

ameter tank for larger slurry inventory and longer faces can create growing deposits which can affect
retention time. Other key components shown include scrubber operation. Deposits are minimized by a com-
the slurry recirculation pumps, interspatial spray bination of features that effectively keep the slurry
headers and nozzles for slurry injection, moisture away from the wet-dry interface region.
separators to minimize moisture carryover, oxidizing The fluework from the exit of the wet scrubber to
air injection system, slurry reaction tank agitators to the stack is an important facet of the system design.
prevent settling, and the perforated tray to enhance The potential for severe corrosion and deposition in
SO2 removal performance. The following sections dis- these flues is well documented. This potential for se-
cuss the gas flow path, slurry flow path, and the ma- vere corrosion arises from many factors. The flue gas
terials used in the tower shell design to accommodate leaves the moisture separator saturated with water
the highly corrosive environment. vapor. Some carryover of slurry droplets smaller than
Gas flow path As noted above, the flue gas enters 20 microns is inevitable. These droplets will usually
the absorber at about the midpoint and turns and flows be slightly acidic and may contain high concentrations
up through an absorption tray, a spray zone, and of dissolved chlorides. The flue gases will contain some
moisture separators before exiting the absorber and residual SO2 and ample oxygen to oxidize the SO2 to
flowing to the stack. Because the flue gas enters the SO3. Because the flue gas is saturated with water
absorber from the side, gas flow non-uniformity in the vapor, surface condensation is inevitable. This con-
tower is a potential issue. This non-uniformity reduces densate can become severely acidic (pH less than 1)
overall SO 2 removal performance and aggravates leading to the formation and accumulation of acidic
moisture separator carryover. The absorber design deposits of sulfuric acid and calcium salts on the walls
depicted in Fig. 2 incorporates a perforated plate tray and floor of the flue.
that reduces flue gas flow maldistribution. The pres- Two approaches are used to minimize these effects:
sure drop across the tray is usually between 1 and 3 flue gas reheat and flue/stack lining. The former op-
in. wg (0.2 and 0.7 kPa). The tray provides intimate tion involves reheating the flue gas so that no drop-
gas/liquid contacting and increases the slurry resi- lets remain. Reheating the flue gas that is leaving the
dence time in the absorption zone. Some absorbers scrubber has been accomplished by various means:
have two trays providing multiple contact zones for 1. steam coil heaters,
SO2 removal. Absorber modules that do not use a tray 2. mixing with some hot flue gas which is bypassed
are referred to as open spray towers. Flue gas enters around the scrubber,
the scrubber module at a temperature of 250 to 350F 3. mixing with hot air, and
(121 to 177C) and is evaporatively cooled to its adia- 4. regenerative heat exchangers that transfer heat
batic saturation temperature by a slurry cascading from the hot flue gas inlet to the cooler flue gas
from the absorber tray. A wet-dry interface exists at outlet.
the scrubber inlet where the inlet fluework at the gas Several problems are associated with each of the
temperature of approximately 300F (149C) merges reheat methods, primarily corrosion and deposition.
with the scrubber shell which is at saturation tempera- As a result, operation without flue gas reheat, i.e.,
ture of around 125F (52C). Reagent slurry droplets with a wet stack, has become popular in the U.S. Under
impinging and drying out on the relatively hot sur- these conditions, the fluework from the scrubber to the

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 The Babcock & Wilcox Company

stack is made of high alloy materials or lined with is added to replenish the alkalinity required to remove
corrosion resistant materials, and the stack is lined SO2. Reaction products are pumped from the absorber
with acid resistant linings or is made of alloys. Mois- to the dewatering system. Spray nozzles are used in
ture collection devices are installed in the outlet flues and wet scrubbers to atomize the slurry into fine droplets
stack, and drains are provided to capture the moisture and provide contact surface area for the slurry and
carryover and condensate collected in these devices. The flue gas. The operating pressures typically vary be-
use of regenerative gas-gas heaters is prevalent inter- tween about 5 and 20 psi (34 and 138 kPa). Spray
nationally because of restrictions on stack plumes. nozzles without internal obstructions are favored to
Slurry flow path The bottom of the absorber is an minimize plugging by tramp debris. The arrangement
integral reaction or recirculation tank. Slurry-contain- of the spray headers and nozzles is designed to ensure
ing reaction products and unreacted fresh reagent are complete coverage of the absorber cross-section and pre-
pumped from the recirculation tank to the spray head- vent gas bypassing through areas of low slurry spray
ers and fall through the spray zone, tray and gas in- flux, which reduces overall SO2 removal efficiency.
let zone to the tank. The slurry is continuously recir- A portion of the slurry droplets is entrained by the
culated in this loop. Fresh reagent such as limestone gas and carried up to the moisture separators. The

Fig. 2 Wet flue gas desulfurization absorber module.

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moisture separators collect and coalesce these slurry are risks to using flake-glass linings and they require
droplets so that they will drain back down into the ab- the most maintenance. It is expected that these lin-
sorber. Otherwise, slurry droplet carryover would re- ings would require annual inspections and repair of
sult in the buildup of slurry in outlet flues, fallout in about 3% of the surface area. This is, therefore, not a
the area around the power plant, and excessive par- good selection for absorbers requiring two to three
ticulate emissions. The moisture separators in most wet years between outages. Flake-glass or epoxy resin lin-
scrubbers are of the chevron design (see Fig. 2). Chev- ing systems are frequently suggested for slurry tanks,
rons are closely spaced corrugated plates that collect process trenches and sumps. The lining in tanks and
slurry droplets by impaction. They efficiently collect sumps is less subject to problems because there is less
droplets larger than about 20 microns in diameter. erosion, no internals, a limited number of connections,
The recirculation tank size is set: 1) to meet the and no direct contact with the flue gas.
requirements of the recirculation pump suction head, Rubber linings have provided a range of operating
2) to allow time for the chemical reactions of sulfite issues in the U.S. because of the many failures in the
oxidation and limestone dissolution, and 3) to provide early use of scrubbers. The failures were due to in-
time and surface area for gypsum crystal growth de- correct rubber selection and poor application. The tech-
velopment. Some of these rate processes are described nology has advanced and rubber lining can provide
in more detail later. good corrosion and erosion resistance over the life of the
Materials of construction The slurry pH of the re- plant. With rubber linings, inspection intervals of 12 to
circulated slurry is typically between 5 and 6 in the 18 months are recommended. Typically, minimal repair
recirculation tank of a limestone system. The pH in is required in the first four years. After that it is expected
the spray zone and on the tray can be as low as 3.5 to that 3% surface repair will be required each year.
4. Chloride concentrations (controlled by blowdown) Tile-lined concrete is a good selection for absorber
are usually designed at 20,000 ppm by weight. How- modules. The tile provides excellent erosion resistance
ever, some systems run up to 50,000 ppm. Systems that in the impingement areas and under the agitators.
use seawater as makeup water can run as high as It also has high chloride resistance. The tile does re-
100,000 ppm. Alloy construction has been the most quire some grout repair. The recommended time be-
popular selection for absorber materials in the U.S. tween outages is 18 to 24 months.
(see Table 2). Rubber-lined, carbon steel scrubber mod- Alloy construction is frequently selected for the ab-
ules are popular in Europe. In addition, there are a sorber vessel. Areas of wear can be addressed with a
number of quality lining systems available. limited amount of erosion resistant coatings/linings.
The industry has used a number of different alloys The outage time required to inspect and repair ero-
for the absorber shell, tray and internal supports. sion barriers (linings) is reduced compared to coated
Rubber linings, flake-glass linings and ceramic tile or lined designs.
systems have also been used. The material selection
on any project is dependent on the process chemistry
and the cost-benefit analysis of the material from a Absorption of SO2
lifecycle perspective. There are a number of parameters that control the
Flake-glass lined carbon steel is the least expensive SO2 removal capability of a wet absorber as listed in
and provides the lowest installed capital cost, particu- Table 3. The effects of these parameters can be better
larly in areas with low field labor costs. However, there understood when the two primary functions of the

Table 2
Some Alloy Choices for Wet FGD Slurry Service

Alloy UNS Number Cr Wt % Mo Wt % Ni Wt % N Wt % Maximum Cl ppm

316L S31603 16.0 2.0 10.0 0 10,000

20 N08020 19.0 2.0 32.0 0 12,000
317L S31703 18.0 3.0 11.0 0 15,000
825 N08825 19.5 2.5 38.0 0 15,000
317LM S31725 18.0 4.0 13.5 0 18,000
317LMN S31726 17.0 4.0 13.5 0.1 20,000
904L N08904 19.0 4.0 23.0 0 20,000
2205 S32205 22.0 3.0 4.5 0.14 30,000
255 S32550 24.0 2.9 4.5 0.1 45,000
G N06007 21.0 5.5 36.0 0 50,000
254-SMO S31254 19.5 6.0 17.5 0.18 55,000
AL-6XN N08367 20.0 6.0 23.5 0.18 55,000
625 N06625 20.0 8.0 58.0 0 55,000
C-22 N06022 20.0 12.5 50.0 0 100,000
C-276 N10276 14.5 15.0 51.0 0 100,000

Note: Compositions are ASTM minimums.

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 The Babcock & Wilcox Company

absorber, physical and chemical, are considered. The

physical parameters set the gas/slurry contacting sur- Table 3
face created in the absorber and the chemical factors Effect of Various Design Parameters on SO2 Removal
control the rate that absorbed SO2 is removed from the
liquid phase of the slurry. When
The SO2 removal efficiency of a scrubber is deter- Parameter Type Parameter Increases
mined by the amount of SO2 that can be absorbed by
Inlet SO2 Chemical Removal decreases
a unit volume of slurry. Limestone based systems are L/G Physical Removal increases
reaction-rate limited. That is, the SO2 absorption is Tray ∆P Physical Removal increases
controlled by how fast the absorbed SO2 can be reacted Stoichiometry Chemical Removal increases
with limestone in the scrubber. The system must pro- pH Chemical Removal increases
vide sufficient alkalinity to react with the SO2. The al- Nozzle pressure Physical Removal increases
kalinity can be present as Ca and CO3 ions or as solid Cl-concentration Chemical Removal decreases
CaCO3. There are three primary methods of increas-
ing the alkalinity in the absorption zone.
The first method is to increase the liquid to gas ra-
tio (L/G) in the absorber. By increasing the flow of
slurry, more liquid contact is provided. The increased the magnesium will be a dissolved species. Organic acid
flow does not change the effective surface in terms of can be added to limestone systems to achieve the re-
area per unit volume of slurry. It does provide more moval of liquid based (dissolved species) systems.
total surface area and alkalinity to the absorption
zone. This does not increase the absorption per unit
volume of slurry. However, it increases the total vol-
Limestone forced oxidized (LSFO)
ume of slurry in the spray zone. process description
The second method is to increase the total and dis- Limestone based wet FGD systems are classified as
solved alkalinity per unit volume of slurry. This is ac- non-regenerable. This means that the reagent is con-
complished by increasing the limestone to SO2 ratio in sumed by the process and must therefore be continu-
the slurry and/or by increasing the absorber reaction ally replenished. A generic diagram of non-regenera-
tank solids residence time. Increasing the stoichiom- tive processes is shown in Fig. 3. Each consists of four
etry increases both the dissolved alkalinity and the process steps: reagent preparation, SO2 absorption,
solid phase alkalinity. Increasing the tank residence slurry dewatering, and final disposal. Within each of
time increases the dissolved alkalinity because there these process steps many variations exist. Essentially
is more time for limestone to dissolve. all wet FGD installations have some unique aspects.
The third method is to use one or more trays. A tray The following discussion will consider the limestone
is a much more efficient contact device than a slurry forced oxidized system, which is the most common sys-
spray. This is because a tray creates more surface area tem in use today. The LSFO system produces a gyp-
between the slurry and the gas. Therefore, the tray sum byproduct that is typically sold for use in the
generates more surface area per unit volume of slurry. manufacture of wallboard. It can also be sold to the
The tray also provides significant holdup time for the cement industry, used as fertilizer, or sent to a landfill.
slurry. This increases the limestone dissolution in the
absorption zone and increases the absorption per unit Reagent preparation
volume. The limestone dissolution on the tray can be as
much as 50% of the dissolution in the entire absorber. The primary advantages of limestone are its wide
The benefits of the absorber tray compared to an availability and cost effectiveness; roughly 5 to 6% of
open spray tower include: the earth’s crust consists of calcium and magnesium
carbonates and silicates. Limestone, consisting mostly
1. reduced liquid to gas ratios of calcium carbonate (CaCO3), is easily mined, trans-
2. increased absorption for the same L/G ported and stored. Its storage and conveying at the
3. more uniform gas distribution plant site are similar to coal handling. A typical analy-
4. fewer recirculation pumps sis of a limestone suitable for use in a wet scrubber is
5. fewer spray headers listed in Table 4.
6. reduced pump maintenance Limestone can be ground dry in an air-swept mill,
7. acts as a maintenance platform or wet in an overflow ball mill and can be ground
There are absorber designs based on reagents such onsite at the power plant, or offsite at a separate loca-
as sodium carbonate which are dissolved chemistry tion. In North America, most limestone wet FGD sys-
absorbers. In these designs, there is sufficient liquid tems feature onsite wet grinding for slurry prepara-
phase alkalinity available so that the SO2 removal be- tion. In most cases, the system of choice is a closed loop
comes gas phase limited. For these systems, the L/G ball mill circuit. A typical ball mill circuit is shown in
and tray pressure drop are much lower. Such systems Fig. 4. The energy required to achieve a given grind
can achieve removal efficiencies as high as 99% at low size is estimated by the Bond relationship:
tray pressure drops and an L/G of about 40 gpm/1000 10Wi 10Wi
acfm. Magnesium enhanced lime systems are solid W = − (5)
chemistry systems that run like liquid systems because DP DF

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Reagent

Table 4
Reagent Typical Limestone Composition
Preparation
Component %
CaCO3 93 − 97
Available CaCO3 92 − 96
Flue
MgCO3 0.5 − 2
Flue Gas to Stack
Gas In SO Total inerts 3 − 7
Wet
Scrubber SiO2 0.5 − 3
Return
Water Fe2O3 0.5 − 3
R2O3 (other metal oxides) 0.5 − 4
Spent Chloride Purge
Slurry

Slurry Sludge/Cake Sale or

Dewatering Disposal For systems making marketable gypsum, limestone
purity is a primary factor (see Table 4). The concen-
Fig. 3 Wet FGD system diagram. tration of inerts affects the gypsum purity, defined as
the percent pure gypsum (CaSO4 · 2H2O). In addition
there are limits to the amount of SiO2, Fe2O3 and total
metal oxides (R2O3) in the gypsum.
where Limestone can also be dry ground at a central loca-
tion and transported by truck to the FGD system. At
W = power, kWh/t of product the site, the pulverized limestone is pneumatically
Wi = Bond work index, kWh (micron)1/2/t conveyed to a storage bunker. It is then fed to water-
DP = diameter in microns for which 80% of prod- filled slurry preparation tanks. This system requires less
uct is finer space than onsite grinding facilities and reduces some
DF = diameter in microns for which 80% of feed is of the FGD operating burden. However, offsite grind-
finer ing is typically more expensive than onsite preparation.
The Bond work index for calcitic limestones ranges from
about 8 to 15 kWh (micron)1/2/t; 10 to 12 is typical.
For onsite grinding systems following Fig. 4, the
limestone is received with a maximum diameter of
about 0.75 in. (19 mm) or less and is fed through a
weigh belt feeder to the ball mill. Either fresh or re-
cycled water is added at the ball mill feed chute in pro-
portion to the feed rate of the limestone. The output
from the mill overflows to the mill product tank where
it is pumped to a set of hydroclones to separate the
fines from the coarse fraction. The coarse fraction (un-
derflow) is returned to the ball mill for further grind-
ing while the fine material is sent to the limestone feed
tank. The water balance is maintained to provide 25
to 35% suspended limestone solids in the feed tank.
The limestone grind is usually expressed as a per-
cent passing a certain sieve size. The typical grind is
90 to 95% passing 325 mesh (44 microns). Fine grind-
ing requires a larger ball mill system and higher op-
erating power consumption. Finer material provides
greater limestone utilization in a smaller reaction
tank and higher dissolution rate due to the higher sur-
face area of finer limestone particles. Stoichiometry, or
reagent ratio, is defined as the molar ratio of the reac-
tant, CaCO3 for limestone systems, to the SO2 removed.
The limestone grinding mill shown in Fig. 4 is a hori-
zontal ball mill. The mill consists of a cylindrical shell
containing steel balls ranging in size from 1 to 4 in.
(25 to 102 mm). The cylinder is rotated and the lime-
stone is ground by the tumbling of the balls and lime-
stone in the mill. Other types of wet mills include ver-
tical tower mills and attrition mills. Fig. 4 Limestone reagent preparation system.

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Slurry dewatering and disposal Secondary dewatering of the gypsum is typically ac-
complished using either horizontal belt or drum vacuum
The disposal of reaction products from limestone wet filters. Horizontal belt filters are typically used for wall-
scrubbers includes ponding, landfilling, and the pro- board grade gypsum production because the final cake
duction of high grade gypsum for wallboard, cement must contain no more than 10% moisture. Drum filters
and fertilizer. In the production of high grade gypsum, are prevalent when higher moisture fractions are accept-
the spent slurry consisting of the reaction products, able (20%), such as for the cement industry and fertil-
inerts from the limestone, excess reagent, and flyash izer. However, with recent design improvements, some
is dewatered in two stages (primary and secondary drum filters can achieve 10% cake moisture. Centrifuges
dewatering). In addition, a purge stream is used to have also been used in secondary dewatering.
remove chlorides and fine particles from the WFGD The production of wallboard grade gypsum requires
system. A typical system is shown in Fig. 5. that the slurry on the vacuum filter be washed with
Hydroclones are used for primary dewatering of fresh water to remove total dissolved solids (TDS) and
gypsum. Multiple hydroclones are mounted in a clus- –
specific ions such as chloride, Cl . The actual specifi-
ter and fed by slurry pumped from the absorber reac- cations will vary based on the wallboard manufac-
tion tank to a radial distributor and then to the indi- turer’s requirements.
vidual hydroclones. The hydroclone classifies the sol-
ids in the feed slurry by particle size. A dilute slurry Purge system
of fine particles leaves through the hydroclone over-
flow and a concentrated slurry of coarse particles is The hydroclone overflow contains a higher percent-
discharged from the hydroclone underflow. Typically age of fine particles of inerts and flyash than the
a feed slurry containing 15 to 20% suspended solids slurry fed to the hydroclones. This stream is the source
will produce an overflow stream containing 3 to 4% for the purge stream. The purge stream flow rate can
suspended solids and an underflow stream contain- be set by the amount needed to purge dissolved solids
ing 50 to 55% suspended solids from the primary cy- from the system or by the need to remove impurities
clone. Most of the hydroclone overflow is returned to and fines. Typically, the raw purge stream is sent to a
the absorber. Recycling of this finer fraction of the second set of (purge) hydroclones to further concen-
solids allows for crystal growth of the gypsum and trate fines in the overflow and reduce the final purge
better utilization of unreacted limestone. A portion of stream total suspended solids (TSS) to about 1.5%. The
the overflow is sent to a purge system for removal of underflow is returned to the absorber. Concentrating
fine particles and chlorides. the fines in the overflow helps reduce the amount of
pure gypsum in the final purge stream.
The purge stream flow is usually set to control chlo-
ride concentration, typically to a design concentration
Final Purge to of 20,000 ppm or less.
Waste Water
To Absorber Raw Purge Treatment The final purge stream is typically ponded or sent
Purge to a waste water treatment system for removal of other
Hydroclone chemical species and suspended solids. The treated
water can then be returned to a river or other body of
water. The solids removed in the treatment system are
Absorber
Blowdown
concentrated or sent to a landfill.
Primary
Hydroclone WFGD system water balance
To Absorber
The wet FGD system loses water to evaporation when
the incoming gas is quenched. There is also some loss to
the gypsum cake. In addition, there is a loss of water in
the purge stream. Within the system, water is used for
preparing the limestone slurry, washing the moisture
separators, cake wash, and as seal water for the vacuum
Gypsum filter seal pumps. Reclaim water (filtrate) from the
vacuum filters is collected and used for limestone prepa-
Table ration and level control in the absorber reaction tank.
Vacuum Filter Cake wash water and vacuum pump seal water
To Atmosphere must be fresh water from a well, river or lake. For all
other uses including moisture separator wash water,
Filtrate
the requirements are less stringent. Sources for the
Return
Filtrate
remaining water can be cooling tower blowdown, sec-
Pump
Pump Vacuum
Receiver
ondary sewage treatment plant effluent, and seawa-
Tank ter, among others.
Filtrate
Water Process flow diagram and mass balance
To Absorber Tank
and Mill A typical limestone based wet scrubbing process us-
ing in-situ forced oxidation is shown in Fig. 6. In this
Fig. 5 Slurry dewatering system. example, the reagent preparation system includes a

35-8 Steam 41 / Sulfur Dioxide Control

 The Babcock & Wilcox Company

closed circuit ball mill system using water that is recycled A summary of the major power requirements for
from the slurry dewatering system. The feed slurry is this limestone to gypsum process is shown in Table 6.
pumped to the absorber reaction tank as required to The operating power requirement for the example
control the pH in the tank or to achieve the desired SO2 displayed in this table is 1.9% of gross unit output. This
removal efficiency or emission concentration. The use of percentage will vary with coal sulfur content and the
pH control can result in excessive limestone consump- required removal efficiency. Higher overall sulfur re-
tion at low boiler loads or when firing lower than design moval or high sulfur loading requires higher L/G, more
sulfur coals without operator intervention. Excess lime- pressure drop, more oxidation air, etc.
stone can adversely affect gypsum purity. By contrast,
limestone consumption can be minimized by controlling Wet scrubber chemistry
to a removal efficiency or SO2 emission set point.
Air is also pumped to this reaction tank and distrib- SO2 absorption in a wet scrubber and its subsequent
uted by a sparge grid or agitator. Oxidation air can reaction with alkaline earth materials such as lime-
also be introduced into the tank by air lances and dis- stone is an elementary acid-base reaction which takes
persed with specially designed agitators. The oxygen place in an aqueous environment. However, the
in the air reacts with sulfite present in the slurry to chemical processes involved are complex. SO2 is a rela-
produce gypsum (CaSO4 · 2H2O). tively insoluble gas in water. Calcium carbonate
The slurry is pumped from the reaction tank to the (CaCO3) also has a low solubility in water. The princi-
spray headers shown in Fig. 2. The slurry is sprayed pal reaction products are calcium sulfite hemi-hydrate
countercurrently into the flue gas where it absorbs the (CaSO 3 · ½ H 2 O) and calcium sulfate dihydrate
SO2. From there, the slurry falls to the sieve tray where (CaSO4 · 2H2O), or gypsum. These two salts also have
additional SO2 is absorbed into the froth created by low solubility in water.
the interaction of the flue gas and slurry on the tray. In a limestone system with forced oxidation, the fol-
The slurry then drains to the reaction tank. lowing reaction model can be used to describe the pro-
The reaction products, primarily gypsum, are con- cess using the chemical species in Table 7.
tinuously withdrawn from the wet scrubber. This In the gas/liquid contact zone:
spent slurry is pumped via gypsum blowdown pumps
to the dewatering system. The spent slurry typically SO2 ( g )  SO2 ( aq )
contains about 15 to 20% suspended solids. A Dissolving gaseous SO2 (6)
hydroclone is used to concentrate the slurry. The un-
derflow from the hydroclone is concentrated to 50%
solids. The overflow containing 4% suspended solids
is sent back to the absorber and to the purge stream. SO2 ( aq ) + H2O  HSO−3 + H+
The underflow from the hydroclone is directed to a (7)
Hydrolysis of SO2
vacuum filter where the filtered solids are washed with
fresh water and dewatered to form a filter cake con-
taining about 10% free moisture. The cake is then sent
CaCO3 ( s ) + H+  Ca ++ + HCO−3
by truck to a wallboard manufacturer. A mass balance (8)
for this example is presented in Table 5. Dissolution of limestone

Limestone Recycle Water

ID Fan Absorber Tower Stack
Limestone Flue Gas from Flue Gas to Stack
Day Bin Dust Collector
Moisture Separators
Hydroclone
Wash Water
Absorber Spray
Headers Chloride
Feed Slurry Trays
Purge
Hydroclone Storage Tank
Hydroclone To
Absorber
Fresh Water for
Filter Cake Wash
Limestone Gypsum
Feed Slurry to Wallboard
Manufacturer

Weigh Oxidation
Feeder Air
Mixers Table
Vacuum
Filter
Absorber Absorber
Ball Mill Reaction Recirculation Recycle Water
Tank Pump
Mill Product
Tank

Fig. 6 Wet scrubber FGD system flow diagram (see Table 5 for mass balance).

Steam 41 / Sulfur Dioxide Control 35-9

 The Babcock & Wilcox Company

Table 5
Mass Balance for the Limestone Forced Oxidation System Shown in Fig. 6

Gas side Inlet Exit

Stream designation A B
Flow rate, ACFM 1,710,000 1,462,000
Total mass flow rate, lb/h 5,521,000 5,924,175 500 MW boiler burning coal with 4.1% sulfur
Mass flow rate of H2O, lb/h 240,000 550,000 Limestone stoichiometry = 1.03
Mass flow rate of SO2, lb/h 34,900 698 SO2 efficiency = 98%
Mass flow rate of HCl, lb/h 458 5
Static pressure, in. wg 12 1
Temperature, F 300 129

Feed To Hydroclone Hydroclone Filter Wash Filter Recycle Hydroclone Chloride

Liquid side Slurry Hydroclone Overflow Underflow Water Cake Water Underflow Purge

Stream designation 1 2 3 4 5 6 7 8 9

Flow rate, GPM 330 961 648 271 53 22 71 11 41

Total flow rate,
lb/h 204,225 573,964 354,000 197,435 26,500 107,493 390,338 6,296 20,500
Flow rate of sus.
solids, lb/h 61,268 114,793 15,000 98,718 0 96,743 0 944 0
% suspended solids 30 20 4.3 50 0 90 0 15 0
Chloride conc.,
ppm in liquid 8,000 20,000 20,000 20,000 50 1,000 8,000 20,000 20,000
pH 7.8 5.5 5.5 5.5 7 7 6 5.5 5.5
Temperature, F 100 129 129 129 120 120 120 129 129

HCO−3 + H+  CO2 ( aq ) + H2O or

(9) kg a
Acid-base neutralization dy
Ng = ∫ y− y* = ∫ G
dV (16b)
CO2 ( aq )  CO2 ( g ) where
CO2 stripping (10)
G =
molar gas flow rate, moles/s
In the reaction tank: y =
mole fraction of SO2 in flue gas
kg =
gas film mass transfer coefficient, moles/m2 s
CaCO3 ( s ) + H+  Ca ++ + HCO−3 a interfacial surface area, m2/m3
=
(11) y* =
equilibrium SO2 concentration at the gas/liq-
Dissolution of limestone uid interface
V = volume of the gas/liquid regime, m3
HCO−3 + H+  CO2 ( aq ) + H2O Ng = number of gas phase transfer units, dimen-
(12) sionless
Acid-base neutralization
Although kg can be approximated, the interfacial
CO2 ( aq )  CO2 ( g ) surface area can not. The gas phase mass transfer rate
CO2 stripping (13) must be determined experimentally. This involves op-
erating the scrubber under conditions in which y* → 0.
Equation 16 can then be integrated to:
O2 ( g ) + 2HSO−3 → 2SO4= + 2H+
(14) N g = −
n (1 − E ) = kg a V / G (17)
Sulfite oxidation
where
Ca ++ + SO4= + 2H2O  CaSO4 ⋅ 2H2O
(15) Ng = overall number of gas phase transfer units,
Precipitation of gypsum
dimensionless
Reaction 6 expresses the mass transfer rate of SO2 E = overall SO2 fractional efficiency
from the gas phase to the liquid or aqueous phase. Its Many factors determine the number of gas phase
mass transfer rate can be expressed by: transfer units (Ng). These include the slurry spray rate,
the droplet size and spatial distributions, the gas phase
d(Gy ) residence time (height of spray zone), the liquid residence
= kg a ( y − y*) (16a)
dV time, wall effects, and the gas flow distribution.

35-10 Steam 41 / Sulfur Dioxide Control

 The Babcock & Wilcox Company

In a limestone based wet scrubber, the rate-limit- stone is added directly to the reaction tank. The pH of
ing reactions in the gas/liquid contact zone are believed the slurry returning from the gas/liquid contact zone
to be Reaction 8. The reaction rate for limestone dis- to the reaction tank can be as low as 3.5. The pH in
solution can be expressed by: the reaction tank is usually 5.2 to 6.2. Therefore, the
overall reaction in the reaction tank is:
d [CaCO3 ]
dt
( )
= kc H+  − H+  Spc [CaCO3 ] (18)
eq CaCO3 ( s ) + H+ + HSO−3 + 1
2 O2 + H2O →
(19)
CaSO4 ⋅ 2H2O ( s ) + CO2 ( g )
where
[CaCO3] = calcium carbonate concentration in the The rate of gypsum crystallization in the reaction
slurry, moles/l tank can be expressed by:
kc = reaction rate constant
[H+] = hydrogen ion concentration, moles/l d [CaSO4 ⋅ 2H2O]
[H+]eq = equilibrium (H+) at the limestone sur-
face, moles/l dt (20)
Spc = specific surface area of limestone in = k ( R − 1) Spg [CaSO4 ⋅ 2H2O]
slurry
The reaction tank permits Reactions 12 through 16 where
to approach completion. In a limestone scrubber, lime- k = crystallization rate constant
R = ACa ++ ASO= / K Sp
4
ACa++ = activity of Ca++ ion
Table 6 ASO= = activity of SO 4= ion
4
Typical Power Requirements for Limestone Ksp = solubility product of gypsum
Scrubber with Forced Oxidation Spg = specific surface area of gypsum
Absorber System Avg. Power (kW) R is a measure of the level of supersaturation. If R
is greater than 1, the solution is supersaturated with
Oxidation air blower 1300 gypsum. If R is less than 1, the solution is subsaturated
Absorber recirc. pumps 3250
in gypsum.
Absorber recirc. tank agitators 250
Moisture separator wash water pump 50
The reaction tank serves a second important func-
Misc. pumps and agitators 50 tion in lime/limestone scrubber systems. The tank is
Subtotal 4900 sized to provide sufficient time for the dissolved gyp-
sum to crystallize and precipitate. Typically, the reac-
Dewatering Area Avg. Power (kW) tion tank is designed for three to five minutes of resi-
Vacuum pump for filter 330
dence time based upon the recirculation rate. An ad-
Reclaim water pump 50 ditional consideration in sizing the reaction tank is to
Filter drive 15 provide sufficient solids retention time, based on gyp-
Misc. pumps and agitators 30 sum produced, to allow the crystals to grow to a suit-
Subtotal 425 able particle size.

Reagent Preparation Avg. Power (kW)

Ball mill 1200
Mill product tank pump 30
Limestone feed tank agitator 80 Table 7
Misc. pumps and agitators 30 Chemical Species Found in Scrubber Reaction Model
Subtotal 1340
SO2 sulfur dioxide
Other Systems Avg. Power (kW) H2 O water
−
HSO3 bisulfite ion
General-instrument air 80 H+ hydrogen ion
Booster fan power 2830 CaCO3 calcium carbonate (main limestone
Subtotal 2910 constituent)
Ca++ calcium ion
Total 9575 CO2 carbon dioxide
−
HCO3 bicarbonate ion
Notes: CaSO3 1/2 H2O calcium sulfite hemihydrate
•

500 MW boiler burning coal with 4.1% sulfur CaSO4 2 H2O• calcium sulfate dihydrate (gypsum)
Heating valule of coal = 10,950 Btu/lb ( ) denotes liquid phase
Absorber L/G = 130 gal/1000 ACF (g) denotes gaseous phase
Total pressure drop = 12 in. wg (aq) denotes dissolved specie in water
Parasitic power = 9575 kW/500 MW (s) denotes solid phase
= 1.9%

Steam 41 / Sulfur Dioxide Control 35-11

 The Babcock & Wilcox Company

Performance enhancing additives soluble, the sulfite ion is the primary reactant in the
The steady-state hydrogen ion concentration of the gas/liquid interface as follows:
slurry in the gas/liquid contact zone is determined by SO3= + H+  HSO−3 (23)
the balance between the rate of H+ generation in Re-
action 7 and the rate of H+ consumption by Reactions Sodium carbonate can also be added to the lime/lime-
8 and 9. As the hydrogen ion concentration increases, stone system for a similar benefit.
i.e., as the pH drops, the equilibrium SO2 vapor pres- The total concentration of dissolved alkaline species
–
sure increases and SO2 removal efficiency is reduced. such as CO3=, HCO3− , SO3= and OH in the slurry is re-
This equilibrium relationship can be expressed by: ferred to as dissolved alkalinity. If the dissolved al-
kalinity is sufficiently high, the scrubber may become
C ′ × 103 H+  gas-phase diffusion controlled. This is illustrated in
y* = Fig. 7.3 Under these conditions the rate of SO2 absorp-
(
k1 k2 + H+  ) (21) tion is dependent only upon the amount of interfacial
surface area, i.e., the spray droplet surface area plus
where the tray froth surface area.
k1 = the equilibrium constant for Reaction 7,
moles/l atm Dry scrubbers
k2 = the equilibrium constant for Reaction 8, Dry scrubbing is more correctly referred to as spray
moles/l dryer absorption (SDA) to reflect the primary reaction
C′ = total concentration of dissolved SO2, milli- mechanisms involved in the process: drying alkaline
moles/l reagent slurry atomized into fine drops in the hot flue
= [SO2]aq + [ HSO3− ] gas stream and absorption of SO2 and other acid gases
[H+] = steady-state hydrogen ion concentration from the gas stream. The process is also called semi-
y* = SO2 vapor pressure expressed as ppm (as- dry scrubbing to distinguish it from injection of a dry
suming barometric pressure = 1 atm) solid reagent into the flue gas.
At 122F (50C): Dry scrubbing is the principal alternative to wet
scrubbing for SO2 control on utility boilers. Since the
k1 = 0.4643 moles/l atm initial installation in 1980, more than 13,000 MW of
k2 = 7.162 × 10-3 moles/l dry scrubbers have been installed at U.S. electric utili-
ties. The allowable SO2 emission permit limits have
As the SO2 vapor pressure rises, the rate of SO2 ab-
steadily decreased over time to levels requiring 90 to
sorption diminishes and approaches zero as y* → y.
95% removal, and the technology has proven to oper-
(See Equation 16.) If a simple means existed to reduce
ate reliably at these levels. The application of dry
the hydrogen ion concentration in the gas/liquid con-
scrubbers to large electric utility boilers is generally
tact zone, then the SO2 vapor pressure could be con-
limited to those burning low sulfur coals. This is due
trolled and the SO2 absorption rate would be maxi-
primarily to the higher unit reagent costs for dry
mized. A buffer is a chemical specie which performs
scrubbing. However, for smaller utility and industrial
this function. A class of weak organic acids has been
boiler applications, the simplicity and lower capital
found suitable for use in limestone scrubbers to con-
costs of dry scrubbing make it an attractive alterna-
trol pH and improve overall SO2 removal. These buff-
tive for higher sulfur coals. Spray dryer systems are
ers can be described by:
also considered maximum achievable control technol-
H+ + A−  AH (22) ogy (MACT) for combined HCl and SO2 control on
waste-to-energy units. In the U.S. utility market, dry
where AH is the generalized acid group. When the pH scrubbers have mainly been applied to units west of
falls in the gas/liquid contact zone, Reaction 22 is the Mississippi River, burning low sulfur fuels, with
driven to the right. Some organic acids which buffer generating capacities of 90 to 900 MW. However, of
in this range include adipic, formic and succinic acid. the more than 50 current U.S. utility and large coal-
Because these are water soluble, the pH buffering is fired industrial cogeneration installations, over 40%
nearly instantaneous compared to the lime or lime- of the installations are located in the east.
stone dissolution. Because the SO2 vapor pressure, i.e., The advantages of dry scrubbing over wet scrub-
the equilibrium SO2 concentration of the gas/liquid bing include:
interface, is proportional to the hydrogen ion concen-
tration, buffers minimize the rise in SO2 vapor pres- 1. less costly construction materials (carbon steel),
sure. The buffer concentration required to achieve a 2. fewer process unit operations,
given absorption depends upon SO2 concentration, L/G 3. simplicity of control and operation,
ratio (the ratio of slurry flow to gas flow), and contact 4. lower water consumption,
time. Typically, the concentration of these additives 5. lower auxiliary power consumption,
which is required to achieve adequate control ranges 6. use of available alkalinity in the flyash for SO2 ab-
from 3 to 30 millimoles/l. sorption,
A second additive used in wet FGD systems is mag- 7. integral SO3 emissions control, and
nesium oxide, which reacts with SO2 to form magne- 8. production of dry solid byproducts without the
sium sulfite. Because magnesium sulfite is highly need for dewatering.

35-12 Steam 41 / Sulfur Dioxide Control

 The Babcock & Wilcox Company

as a second stage SO2 removal reactor that can con-

tribute a significant fraction of the overall perfor-
mance. Operating data from an SDA/baghouse sys-
tem achieving 90% overall SO2 emissions reduction has
shown that the SDA accounted for 79% of the total
and the remaining 21% was obtained across the
baghouse. The particulate filter cake on the bags was
actually removing 63% of the SO2 entering the baghouse.
For large utility applications, the flue gases are in-
troduced to the spray chamber through a compound
gas disperser (upper and lower) as shown in Fig. 9 for
a vertical flow design. For lower gas flow applications,
all of the gas flow enters through the roof gas disperser.
The gas disperser is designed to assure good mixing
of the flue gases with the reagent spray, and to make
use of the full volume of the spray chamber. The ver-
tical gas flow configuration dominates utility boiler
SDA applications although there are a few horizon-
Fig. 7 Influence of dissolved alkalinity on SO2 performance (1 mil-
tal flow units in operation. The SDA chamber is sized
liequivalent = 50 ppm CaCO3). to provide sufficient gas-phase residence time for dry-
ing of the reagent slurry to produce free-flowing sol-
ids in the particulate collector. The required residence
System design time depends on the inlet flue gas temperature, feed
Fig. 8 depicts the equipment orientation for a typi- slurry solids loading, degree of atomization, and exit
cal utility SDA installation coupled with a baghouse gas temperature. In general, for atomization systems
(BH). Unlike a wet scrubber installation, the SDA is producing a Sauter mean drop diameter of 50 to 60
positioned before the dust collector. Flue gases leav- microns, 10 to 12 seconds is sufficient. This residence
ing the air heater at a temperature of 250 to 350F (121 time is calculated based on the spray chamber volume
to 177C) enter the spray chamber where the reagent and the outlet flue gas temperature and pressure. Field
slurry is sprayed into the gas stream, cooling the gas studies have shown that the flue gas temperature is
to 150 to 170F (66 to 77C). An electrostatic precipita- within ±10 to 20F (6 to 11C) of the SDA outlet tempera-
tor (ESP) or fabric filter (baghouse) may be used to ture throughout the entire spray chamber.
collect the reagent, flyash and reaction products. The reagent slurry is introduced to the reaction
Baghouses are the dominant selection for U.S. SDA chamber as a fine mist of droplets using a single,
installations (over 90%) and provide for lower reagent high-capacity rotary atomizer or multiple dual-fluid
consumption to achieve similar overall system SO2 (high pressure air/slurry) atomizers. A rotary atom-
emissions reductions. Both reverse-air and pulse-jet izer assembly for a large utility application is shown
baghouse designs are in use (see Chapter 33). The in Fig. 10. The assembly shown includes the 900 hp
baghouse is an integral part of the process and acts drive motor, a speed-increasing gearbox, the atomizer

Steam Generator

Selective Catalytic Spray Dryer Absorber

Reduction (SCR) System (Scrubber)

Air Heater
Fabric Filter
(Baghouse)

Fig. 8 Utility spray dryer absorption (SDA) system.

Steam 41 / Sulfur Dioxide Control 35-13

 The Babcock & Wilcox Company

wheel, and associated hardware. Rotary atomization (+100 micron) drops from primary atomization or the
far dominates (90+%) the utility and large industrial coalescence of sprays from multiple atomizers is a key
installed technology base. This is primarily because criteria for successful operation.
the rotary design provides higher slurry flow capac- Fig. 12 shows a compact selective catalytic reduc-
ity per atomizer and better performance with higher tion/SDA/BH installation for a 550 MW power plant.
solids slurries. Both systems have proven reliable and At this site, the two SDA chambers, each with a single
capable of consistently achieving low SO2 emissions. Key rotary atomizer, treat approximately 1,800,000 ACFM
performance requirements for SDA atomizers include: (850 m3/s) of flue gases from a pulverized coal-fired
boiler burning Powder River Basin coal to reduce SO2
1. ability to handle variable slurry flow rates,
emissions by 94%.
2. rapid response to flow rate changes,
3. uniform spray coverage of the SDA chamber, Process description
4. low susceptibility to pluggage and build-up, and
The quantity of water in the reagent slurry intro-
5. ease of removal for servicing.
duced into the SDA is controlled so that it almost com-
For rotary atomizers, the spray droplet size distri- pletely evaporates in suspension, leaving the solids
bution is a function of the speed of rotation, wheel di- exiting the spray chamber with a free moisture con-
ameter and wheel design as well as, to a lesser extent, tent of 1 to 2%. SO2 absorption takes place primarily
reagent slurry feed properties including the flow rate, while the water is evaporating and the flue gas is adia-
viscosity, density, and surface tension.4 Increasing the batically cooled by the spray. The difference between
wheel speed reduces the droplet size at the cost of the temperature of flue gas leaving the dry scrubber
higher power consumption. Note that for a rotary unit, and the adiabatic saturation temperature is known as
atomization quality is not sensitive to the diameter of the approach temperature. Flue gas saturation tem-
the exit nozzles and so does not degrade as the nozzles
wear from erosion by the reagent slurry. In addition
to the slurry properties, key design criteria for dual-
fluid nozzle atomizers include the nozzle exit orifice
dimensions and orientation, air pressure, and air-to-
slurry ratio. Water spray from a typical dual-fluid
atomizer with multiple exit orifices is shown in Fig.
11. For this system, minimizing formation of large

Inlet Flue
Gas (Upper)

Rotary
Atomizer

Central
Gas
Disperser
To
Particulate
Collection

Inlet Flue
Gas (Lower)

Fig. 9 Spray dryer absorber cutaway. Fig. 10 Rotary atomizer assembly.

35-14 Steam 41 / Sulfur Dioxide Control

 The Babcock & Wilcox Company

peratures are typically in the range of 115 to 125F (46

to 52C) for low moisture bituminous coals and 125 to
135F (52 to 57C) for high moisture subbituminous
coals. The stoichiometry is the molar ratio of the re-
agent consumed to either the inlet SO2 or the quan-
tity of SO2 removed in the process. Both definitions are
in common use. Reagent stoichiometry and approach
temperature are the two primary variables that con-
trol the scrubber’s SO2 removal efficiency. The optimal
conditions for SO2 absorption must be balanced with
practical drying considerations. The approach tem-
perature selected must be consistent with the atom-
izer feed slurry solids loading for efficient drying of
the reagent solids. The spraydown, or difference be-
tween the inlet and outlet flue gas temperatures, and
the solids loading of the atomizer feed slurry, determine
how much reagent may be introduced to the process.
The predominant reagent used in dry scrubbers is
lime slurry produced by slaking a high-calcium pebble
lime. The slaking process can use a ball mill or a simple
detention slaker. SDA systems that use only lime slurry
as the reagent are known as single pass systems.
Some of the lime remains unreacted following an ini-
tial pass through the spray chamber and is potentially
available for further SO2 collection. Solids collected
in the ESP or baghouse may be mixed with water and
reinjected in the spray chamber. This solids recycle sys-
tem is used at most utility SDA installations to make
use of the available alkalinity inherent in the flyash
and to minimize reagent use. Some of the recycled Fig. 11 Dual-fluid atomizer.

Fig. 12 B&W’s SDAs and fabric filter baghouse provide an integrated SO2 and particulate removal process.

Steam 41 / Sulfur Dioxide Control 35-15

 The Babcock & Wilcox Company

solids form an inert core supporting the finer lime sol- Head Tank
ids on the surface, thereby exposing more lime sur-
face area for SO2 absorption. The flyash may be re-
moved from the flue gas before the SDA by a pre-col- Flue
Gas
lector. This is common practice in Europe where mar- Inlet
keting of the flyash from coal-fired utility boilers is a ESP
Spray
well-established industry practice. Even with flyash Dryer Baghouse
Stack
pre-collection, a recycle system results in more efficient Absorber

lime utilization. Ash

The process is controlled by monitoring the flue gas Market
Disposal
temperature at the SDA outlet to control the amount Optional Flyash
Pre-Collection
of water or recycle slurry added to the atomizer feed.
SO2 emissions at the stack are compared to a desired
operating set point and the lime slurry flow to the at- Lime Recycle
omizers is adjusted to reduce the outlet SO2 as neces- Solids
sary. For a rotary atomizer, the atomizer spindle, which Process
connects the motor to the atomizer wheel, is monitored Water Water
continuously for vibrations to provide an early indica-
tion of unbalance or pluggage of the wheel.
Process flow diagram and mass balance Lime Feed
Recycle
Feed
A typical SDA process flow diagram is shown in Fig.
13. The flue gases, with or without pre-collection of Optional Solids Recycle
the flyash, enter the spray dryer absorber where the Fig. 13 Dry scrubber FGD system flow diagram (see Table 8 for
gas stream is cooled by the reagent slurry spray. The mass balance).
mixture then passes on to the baghouse for removal
of particulate before entering the ID fan and passing duce relatively insoluble products. The reaction path
up the stack. Pebble lime (CaO) is mixed with water can be described as follows:
at a controlled rate to maintain a high slaking tem-
perature that helps generate fine hydrated lime SO2 ( g )  SO2 ( aq )
(Ca(OH)2) particles with high surface area in the hy- (24)
drated lime slurry (18 to 25% solids). A portion of the Dissolving gaseous SO2
flyash, unreacted lime and reaction products collected
in the baghouse is mixed with water and returned to Ca(OH)2 ( s ) → Ca ++ + 2OH−
(25)
the process as a high solids (35 to 45% typical) slurry. Dissolution of lime
The remaining solids are directed to a storage silo for
byproduct utilization or disposal. The fresh lime and
recycle slurries are combined just prior to the SO2 ( aq ) + H2O  HSO−3 + H+
atomizer(s) to enable fast response to changes in gas (26)
Hydrolysis of SO2
flow, inlet SO2 concentrations, and SO2 emissions as
well as to minimize the potential for scaling. SO2 ( aq ) + OH−  HSO−3 (27)
Process mass balances for recycle and single pass
SDA system designs for a typical application are pre- OH− + H+  H2O (28)
sented in Table 8 while the power requirements are
provided in Table 9. In this example, use of the recycle
system reduces lime consumption by 3141 lb/h (1424.7 HSO−3 + OH−  SO3= + H2O
(29)
kg/h), or 42% over that expected with single-pass op- Neutralization
eration. The stoichiometry for the single pass system
is 1.78 on an inlet SO2 basis compared to 1.04 for the Ca ++ + SO3= + 1
2 H2O → CaSO3 ⋅ 1 2 H2O ( s )
recycle system. Note the difference in acceptable ap- (30)
Precipitation
proach temperatures for long-term operation of the two
systems. The 7% solids feed slurry with the single pass These reactions generally describe activity that
system requires operation at a 45F (25C) approach tem- takes place as heat transfer from the flue gas to the
perature or above for adequate drying while a 30F (17C) slurry droplet is evaporating water from the droplet.
approach is used with the recycle system. The rate-determining reaction may vary at different
stages of the drying and absorption process. The high
Dry scrubber chemistry pH in the droplet environment (10 to 12.5) helps main-
The mechanism of SO2 absorption in an SDA is simi- tain a low concentration of acid in the liquid phase
lar to that attained by wet scrubbing when viewed on that enhances SO2 absorption from the gas stream.
the level of what takes place in the individual slurry Rapid SO2 absorption occurs when liquid water is
droplets. Most of the reactions take place in the aque- present. The drying rate can be slowed down to pro-
ous phase; the SO2 and the alkaline constituents dis- long this period of efficient SO2 removal by adding deli-
solve into the liquid phase where ionic reactions pro- quescent salts to the reagent feed slurry. Salts such

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 The Babcock & Wilcox Company

Table 8
Mass Balance for Process Flowsheet Shown in Fig. 13

Recycle System Design

Flue gas stream SDA Inlet BH Inlet ID Fan Inlet
Stream designation A B C
500 MW boiler burning 0.44% sulfur coal
Flow rate, ACFM 1,729,848 1,571,675 1,609,250 with high calcium flyash
Flow rate, lb/h 5,244,973 5,454,664 5,508,400 Available flyash alkalinity = 0.40
SO2, ppmv 380 89 21 milliequivalents/gram
SO2, lb/h 4,381 1,086 263 Flue gas saturation temperature = 133F
Particulate, lb/h 26,835 148,511 76 SO2 emissions reduction = 94%
Temperature, F 275 163 159 SO2 emissions rate = 0.05 lb/106 Btu
Pressure, in. wg −16.0 −19.5 −27.0 Particulate emissions rate = 0.015 lb/106 Btu

Pebble Slaking Lime Recycle Process Recycle Atomizer Byproduct

Solids/slurry streams Lime Water Slurry Solids Water Slurry Feed Solids
Stream designation 1 2 3 4 5 6 7 8
Total flow rate, GPM 48 50 269 363 413
Total flow rate, lb/h 4,394 24,069 28,463 114,384 134,747 249,132 277,594 34,861
Solids flow, lb/h 4,394 0 5,693 112,096 0 112,096 117,789 34,167
Flyash, lb/h 24,273
Byproducts, lb/h 9,894
Water flow, lb/h 24,069 22,770 2,288 134,747 137,036 159,805 694
Solids loading, wt. % 100 0 20 98 0 45 42 98

Single Pass System Design

Flue gas stream SDA Inlet BH Inlet ID Fan Inlet
Stream designation A B C

Flow rate, ACFM 1,729,848 1,594,410 1,632,843

Flow rate, lb/h 5,244,973 5,424,712 5,478,350
SO2, ppmv 380 73 21
SO2, lb/h 4,381 880 263
Particulate, lb/h 26,835 40,936 76
Temperature, F 275 177 173
Pressure, in. wg −16.0 −19.5 −27.0

Pebble Slaking Lime Recycle Process Recycle Atomizer Byproduct

Solids/slurry streams Lime Water Slurry Solids Water* Slurry Feed Solids
Stream designation 1 2 3 4 5 6 7 8
Total flow rate, GPM 83 86 183 0 269
Total flow rate, lb/h 7,535 41,278 48,813 0 91,254 0 140,067 41,467
Solids flow, lb/h 7,535 0 9,763 0 0 0 9,763 40,638
Flyash, lb/h 26,787
Byproducts, lb/h 13,851
Water flow, lb/h 41,278 39,050 0 91,254 0 130,304 829
Solids loading, wt. % 100 0 20 0 0 7 98

*Process water addition to lime slurry for atomizer feed to achieve desired SDA outlet temperature.

as calcium chloride also increase the equilibrium mois- performance. SO2 absorption continues at a slower rate
ture content of the end product. However, since the by reaction with the solids in the downstream particu-
use of these additives alters the drying performance late collector.
of the system, the operating conditions must be ad- An SDA/baghouse combination also provides effi-
justed (generally increasing the approach tempera- cient control of HCl, HF and SO3 emissions by the sum-
ture) to provide for good long-term operability of the mary reactions of:
SDA and the ash handling system. Ammonia injection
upstream of a dry scrubber also increases SO2 removal Ca(OH)2 + 2HC1 → CaC12 + 2H2O (31)

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 The Babcock & Wilcox Company

Sulfuric acid condenses on metal surfaces beginning

Table 9 in the temperature range of 200 to 300F (93 to 149C)
Typical Power Requirements for 500 MW and results in corrosion of metal surfaces in flues, air
SDA/Baghouse System in Table 8 heaters, dry ESPs and fans. Acid dew point curves are
Recycle System Single Pass
presented in Fig. 14. In addition, in units with wet
Design System Design scrubbers, any significant residual sulfuric acid mist
can cause visible plume or opacity problems (blue
Atomizers and plume), visible several miles from the power plant. Wet
accessories, kW 1190 640 scrubbers are not effective in removing acid mists
Reagent preparation, kW 230 125 because the rapid flue gas quenching in the scrubber
Baghouse accessories, kW 445 445 produces submicron aerosol mists which are not eas-
ID fan power 6780 6880 ily collected (20 to 30%). Dry scrubbers in combina-
Total 8645 8090
% of net 500 MW output 1.73 1.62
tion with downstream baghouses are effective in re-
moving H 2 SO 4 (> 95% typical). Finally, in units
equipped with SCR systems, excess ammonia (NH3)
leaving the SCR can react with SO3 to form sticky,
Ca(OH)2 + 2HF → CaF2 + 2H2O (32) acidic particles of ammonium bisulfate (NH4HSO4)
which can foul air heaters.
Ca(OH)2 + SO3 → CaSO4 + H2O (33)
Control methods
Proper accounting of the reagent consumption must Sorbent injection The injection of wet or dry alkali
include these side reactions, in addition to the SO2 re- compounds (usually calcium or magnesium oxide com-
moved in the process. pounds), typically in the furnace, after the SCR, or
The SDA process can make use of a variety of wa- upstream of the particulate collection device has been
ter sources for preparation of the reagent slurry and shown to be an effective means of controlling SO3/
cooling of the flue gas. River water, well water, cool- H2SO4. Sorbent injection has the advantage of low
ing tower blowdown, municipal waste water treatment capital cost, but has very high reagent cost due to the
effluent, and seawater have all been used successfully high stoichiometric ratio (4 to 8) that is needed to
in SDA applications. In general, lime slaking requires achieve 80 to 90% SO3/H2SO4 control. Dry ESP per-
good quality water with limitations on the sulfite, formance may be adversely affected by removing the
sulfate and TDS concentrations being the primary con- SO3 from the flue gas (see Chapter 33).
cerns for producing good quality fresh reagent slurry. Humidification Cooling the flue gas by humidifica-
Preparation of the recycle solids slurry and humidifi- tion upstream of an existing dry ESP will allow the
cation of the flue gas to the desired operating tempera- dry ESP to collect some sulfuric acid. It is possible to
ture can be achieved with lower quality water sources. operate a dry ESP at 20F (11C) below the acid dew
Selection of the process operating conditions must also point without encountering excessive corrosion. 20 to
consider the chloride content of the water sources to 40% sulfuric acid removal can be achieved in some in-
avoid problems with drying the reagent slurry and stances. This is possible because the acid is absorbed
potential corrosion. on the flyash rather than on the metal surfaces of the
dry ESP. Careful attention must be paid to thermal
insulation integrity and in-leakage of seal air streams.
Sulfur trioxide (SO3) Ammonia injection Ammonia injection upstream of
the dry ESP has been used to control acid mist. How-
SO3 and acid mist formation ever, there can be problems with ash handling, since
Sulfur trioxide (SO3) is formed directly in the com- the ash tends to be more cohesive. It is also possible
bustion of sulfur-containing fuels, and indirectly by that excess ammonia will react with the SO3 to form
the conversion of small quantities of flue gas SO2 to
SO3 in the presence of iron, some ash constituents such
320
as vanadium, and some selective catalytic reduction (160)
(SCR) catalysts. Under normal operating conditions 300
15% H O
in coal-fired boilers without SCR systems, 0.75% of the (149)
SO2 typically is converted to SO3. High vanadium con- 280
Dew Point, F(C)

taining ashes can increase this range to 2%. Conver- (138)

10% H O 5% H O
sion of SO2 to SO3 by SCR catalysts is dependent upon 260
SO2 concentration, gas temperature, and catalyst for- (127)
mulation with a typical range of an additional 0.7 to 240
1.5%. Catalysts have been formulated with relatively (116)
low SO2 to SO3 oxidation potential. 220
As the flue gas temperature falls below 1000F (104)
(538C), SO3 begins to react with water in the flue gas 200
(93) 0
to form sulfuric acid vapor, H2SO4. By the time the flue 5 10 15 20 25 30 35 40 45 50
gas exits the air heater, virtually all of the SO3 has H SO Concentration, ppm Wet Volume
reacted to form H2SO4. Fig. 14 Dew point versus concentration.

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submicron aerosols that are difficult to collect. Capi- Purge Air / Heater
Supply Skid
tal costs are low, but reagent costs are high.
Final Moisture
Wet precipitator To achieve very high removals of Separator
acid mist, a wet ESP can be used. For a utility boiler,
the wet ESP would be used downstream of the wet
FGD system. Purge Air
Piping
Either a stand-alone arrangement or an integrated Casing
close-coupled wet ESP can be used to control SO3; how- High Voltage
Support Insulator
ever, the standalone arrangement is typically more Partition
Wall
costly than the integrated design and consumes con- High Voltage
siderable additional space. Fig. 15 shows the inte- Wash Transformer-
Piping Rectifier Set
grated design.
The submicron nature of the acid mist can only be Collecting
treated in a multi-field unit. Acid mist removal effi- Field
ciencies of 80 to 90% can be achieved. For example, if (1 of 3
Shown) Discharge Electrode
the inlet is 34 ppmdv, less than 5 ppmdv at the stack Collecting Electrode
Liquid
can be achieved. Wet ESP can also remove 80 to 90% Collection
of any solid particulate that is present, such as re- Gutters
sidual flyash from the dry ESP and the small amounts
of gypsum that result from the wet FGD moisture
separator wash system. Even if a wet ESP is not in-
cluded in a wet FGD project today, careful thought
should be given to future needs. The addition of a wet
ESP to an existing wet FGD system may not be pos-
sible if provisions are not made before the initial wet
FGD system installation.

Fig. 15 Integrated wet ESP and wet FGD system.

References
1. “United States (U.S.) Environmental Protection Agency 3. Plummer, L.N., Wigley, T.M.L., and Parkhurst, D.L.,
(EPA), National Emissions Inventory Criteria Pollutant “The Kinetics of Calcite Dissolution in CO2-Water Systems
Data: Current Emissions Trends Summary 1970-2002,” at 5C to 60C and 0.0 to 1.0 atm CO2,” American Journal
www.epa.gov/ttn/chief/trends/index.html, accessed August of Science, Vol. 278, pp. 179-216, 1978.
28, 2003. 4 Master, K., Spray Drying in Practice, SprayDryConsult
2. Annual Energy Review 2002, U.S. Department of En- International, Denmark, 2002.
ergy, Energy Information Agency, Washington, D.C., No-
vember, 2003.

Bibliography
Hardman, R., Stacy, R., and Dismukes, E., “Estimating Lesley, S., “Trends in Emissions Standards,” CCC/77 Re-
Sulfuric Acid Aerosol Emissions from Coal-Fired Power port, IEA Clean Coal Centre, International Energy Agency,
Plants,” Taken from the Conference on Formation, Dis- London, England, United Kingdom, November, 2003.
tribution, Impact and Fate of Sulfur Trioxide in Utility
Flue Gas Streams, United States Department of Energy-
FETC, March, 1998.

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 The Babcock & Wilcox Company

Wet flue gas desulfurization module at a utility installation.

35-20 Steam 41 / Sulfur Dioxide Control