ABSORPTION

FLUE GAS
DESULFURIZATION
 CREATED BY

 ZELİHA SALDIR
 ITIR SARI
 TUĞBA BEĞENDİ
 MUSTAFA ÖZGİRAY
 YAKUP TURGUT
 INTRODUCTION
 Absorption, or gas absorption, is a unit operation used
in the chemical industry to separate gases by washing
or scrubbing a gas mixture with a suitable liquid .
 The fundamental physical principles underlying the
process of gas absorption are the solubility of the
absorbed gas and the rate of mass transfer. One or more
of the constituents of the gas mixture dissolves or is
absorbed in the liquid and can thus be removed from
the mixture. In some systems, this gaseous constituent
forms a physical solution with the liquid or the solvent,
and in other cases , it reacts with the liquid chemically.
 The purpose of such scrubbing operations may be
any of the following : gas purification (eg , removal
of air pollutants from exhausts gases or contaminants
from gases that will be further processed) , product
recovery , or production of solutions of gases for
various purposes.
Gas absorption is usually carried out in vertical
counter current columns as shown in figure 1.The
solvent is fed at the top of the absorber , whereas
the gas mixture enters from the bottom .The
absorbed substence is washed out by the solvent
and leaves the absorber at the bottom as a liquid
solution . The solvent is often recovered in a
subsequent stripping or desorption operation . This
second step is essentially the reverse of absorption
and involves counter current contacting of the
liquid loaded with solute using and inert gas or
water vapor .
 The absorber may be a packed column , plate
column , spray column , venturi scrubbers ,
bubble column , falling films , wet scrubbers
,stirred tanks
PACKED COLUMN
The packed column is a shell either filled with
randomly packed elements or having a regular
solid structure designed to disperse the liquid and
bring it Dumped-type packing elements come in a
great variety of shapes and construction materials,
which are intended to create a large internal surface
but a small pressure drop. Structured ,or arranged
packings may be made of corrugated metal or
plastic sheets providing a large number of regularly
arranged channels ,but a variety of other
geometries exists.
Packing materials may be classified as follows,
 rock
 3-coke
 4-stonaware shapes
 4a-raching rings
 4b-berl saddle
 4c-sprial rings 1-wood slats
 2-broken
 4d-grid bloks
 5-miscalloneous material
Rashing rings are the most widely used form
of tower packing. They are cylindrical rings,
of the some length as the diameter of the
cylinder and with the walls as thin as the
material will permit. Rashing rings are almost
always dumped into the tower at random and
not stacked regularly. They offer the best
combination of low weight per unit
volume,free volume,free cross section and
total surface of any type of packing.
 A packed bed column contains a support plate, a
liquid distributor, and a mist eliminator.
Mist eliminators are used to condense any vaporized
scrubbing liquid. Support plates hold the packing in
place.

The advantages of packed columns include simple and,as

long as the tower diameter is not too large,usually
relatively cheaper construction. These columns are
preferred for corrosive gases becuase packing, but not
plates, can be made from ceramic or plastic materials.
Packed columns are also used in vacuum applications
because the pressure drop, especialli for regularly
structured packings, is usually less then through plate
columns.
 Usage examples
Packed columns are used mostly in air pollution
control..
The water soluble ethylene gas ishydrolyzed to ethylene
gylcol.
Packed columns are also used in the chemical
,petrochemical,food, pharmaceutical,paper, and
aerospace industries.
TRAY COLUMN
 Tray absorbers are used in applications where tall
columns are required, because tall, random-type
packed towers are subject to channeling and
maldistribution of the liquid streams. Plate towers can
be more easily cleaned. Plates are also preferred in
applications having large heat effects since cooling
coils are more easily installed in plate towers and
liquid can be withdrawn more easily from plates than
from packings for external cooling. Tray columns
have got some disadvantage. These are slow reaction
rate processes, higher pressure drops than packed
beds and plugging and fouling may be occur.
Tray absorbers are used in applications where
tall columns are required,because tall,random-
type packed towers are subject to channeling
and maldistribution of the liquid streams. Plate
towers can be more easily cleaned. Plates are
also pereffered in applications having large heat
effects since cooling coils are more easily
installed in plate towers and liquid can be
withdrawn more easily from plates than from
packings for external cooling.
 Usage Examples
 Tray columns are used in a refinery dehexanizer to
decrease the benzene content in the naptha feed to
the process. This results in lower automobile exhaust
emissions.
 STIRRED TANKS
 If the absorbtion process includes a slow liquid-
phase chemical reaction, or close control of the
process is needed, stirred tanks are used.the gas is
introduced directly into the liquid and mixed by the
stirred in a stirred tank.
 Usage examples

 Stirred tanks can be used in

lime slurry
carbonation,paper stock
chlorication, regular oil
hydrogenation,fermentation
broth aeration,penicilin
production, citric acid
production,and aeration of
activated sludge.
 BUBBLE COLUMN
 Structured catalytic bubble columns are new, very
promising types of multiphase reactors. Their
configuration lies basically between slurry reactors
and trickle bed reactors. The solid phase, consisting
of catalyst particles, is enclosed in fixed wire gauze
wraps, which are mounted along the height of the
column. The gas phase is dispersed into the liquid
phase and it flows in the empty passages between
adjacent envelopes. The liquid phase may be operated
in a batch manner or it may also circulate in co-
current or counter-current manner to the gas flow.
The main advantages of this reactor type with respect
with the conventional slurry bubble column are:
1.no problems for separating catalyst from the
liquid;
2.improved conversion and selectivity due to
staging of the liquid phase;
3.no scale up problems because the hydrodynamics
is dictated by the size of the open channels of the
catalytic structure.
 Usage Examples
 Bubble columns can be used to
purify nitroglycerin with water,
in the chemical industry for
hydrogenation, oxidation,
chlorination, and alkylation,
and in the biotechnological
field for effluent treatmet,
single-cell protein productin,
animal cell culture, and
antibiotic fermentation. Bubble
columns can be used for
radioactive elements because
there are no moving parts.
Venturi Scrubbers
 Adjustable-throat venturi scrubber with
movable plate
Venturi scrubbers can be used for removing gaseous
pollutants; however, they are not used when removal
of gaseous pollutants is the only concern.
The high inlet gas velocities in a venturi scrubber
result in a very short contact time between the liquid
and gas phases. This short contact time limits gas
absorption. However, because venturis have a
relatively open design compared to other scrubbers,
they are very useful for simultaneous gaseous and
particulate pollutant removal, especially when:
 •Scaling could be a problem
•A high concentration of dust is in the inlet stream
•The dust is sticky or has a tendency to plug openings
•The gaseous contaminant is very soluble or
chemically reactive with the liquid

To maximize the absorption of gases, venturis are

designed to operate at a different set of conditions
from those used to collect particles. The gas velocities
are lower and the liquid-to-gas ratios are higher for
absorption.
For a given venturi design, if the gas velocity is
decreased, then the pressure drop (resistance to
flow) will also decrease and vice versa. Therefore,
by reducing pressure drop, the gas velocity is
decreased and the corresponding residence time is
increased. Liquid-to-gas ratios for these gas
absorption applications are approximately 2.7 to 5.3
l/m3 (20 to 40 gal/1000 ft3). The reduction in gas
velocity allows for a longer contact time between
phases and better absorption.
Increasing the liquid-to-gas ratio will increase the
potential solubility of the pollutant in the liquid.
Flooded elbow
 Venturi scrubbers can have the highest particle
collection efficiencies (especially for very small
particles) of any wet scrubbing system.
 They are the most widely used scrubbers because
their open construction enables them to remove most
particles without plugging or scaling. Venturis can
also be used to absorb pollutant gases; however, they
are not as efficient for this as are packed or plate
towers.
 Venturi scrubbers have been designed to
collect particles at very high collection
efficiencies, sometimes exceeding 99%. The
ability of venturis to handle large inlet
volumes at high temperatures makes them very
attractive to many industries; consequently,
they are used to reduce particulate emissions
in a number of industrial applications.
 This ability is particularly desirable for cement kiln
emission reduction and for control of emissions from
basic oxygen furnaces in the steel industry, where the
inlet gas enters the scrubber at temperatures greater
than 350 °C (660 °F).
 Venturis are also used to control fly ash and sulfur
dioxide emissions from industrial and utility boilers.
 Falling film
 With high efficiency in absorbing HCl
(hydrochloric) gas, H2S, HF, SO2, NH3 gas,
graphite falling film absorbers comprise of
absorption liquid distributor, cooling and
absorption section and Gas-Liquid separator.
 Absorption liquid distributor is for film
forming and flow into absorption tube in
cooling and absorption section.
 On request, cooling and absorption section
has two models basis of its heat transfer unit
-Shell and Tube and Block. Gas-Liquid
separator is to separate tail gas and product. 
 Its convincing advantages and
disadvantages is following: -
 Advanges  Disadvanges
 High efficiency of  Restricted by pressure
absorption drop  Film breakup
 Low outlet temperature  Flooding

 No need after-cooling
 Low flow resistance
 Easy maintenance 
SPRAY COLUMN
Spray columns are differetal contactors. The
liquid stream enters the coloumn through
one or more spray nozzles at different
heights in the column. The droplets formed
provide a large surface area for exposure to
the gas stream,with smaller droplets
resulting in a greater Exchange area. The
liquid and gas streams can flow counter-
currently or in paralel. An optimum droplet
velocity is essential because low velocity
will lead to low contact or turbulence and
high velocity may cause flooding.
 A mist eliminator is used to
separate any liquid that is
entrained into the gaseous
phase. Spray columns are used
to absorb SO2 from coal-fired
boiler exhaust gases.
 WET SCRUBBER
 Wetted packed towers are the simplest and most
commonly used approaches to gas scrubbing.
The principle of this type of scrubber is to
remove contaminants from the gas stream by
passing the stream through a packed structure
which provides a large wetted surface area to
induce intimate contact between the gas and the
scrubbing liquor. the contaminant is absorbed
into or reacted with the scrubbing liquor.
 The packing of the tower is normally a proprietary
loose fill random packing designed to encourage
dispersion of the liquid flow without tracking, to
provide maximum contact area for the 'mass transfer'
interaction and to offer minimal back pressure to the
gas flow. The reactivity between the contaminant and
the scrubbing liquor influences the system designer's
determination of gas and liquor flow and the height
and diameter of the packed bed.

 A demister is fitted at the top of the tower to prevent

entrainment of droplets of the scrubbing liquor into
the extraction system or stack.
 Wetted packed towers can be designed for very high
efficiencies with relatively low capital and running
costs. The low pressure drop associated with packed
bed scrubbers permits the use of smaller more
economical fans. Although efficiency may be
affected, a packed tower will usually function when
gas or liquor flows vary from its original design
parameters.
 Usage examples
 Wet scrubbers are used by the food industry,such as in
cheese proessing for dust and ambient moisture
removal.
 FLUE GAS DESULFURIZATION
SYSTEM

Gas desulfurization can be accomplish by wet, dry,
or alkali scrubing.These methods are covered in this
section.
THE WET FLUE-GAS DESULFURİZATİON
SYSTEM
 The wet FDG system, also called a wet scrubber, is
cammonly based on low-cost lime-limestone in the
form of an aqeous slurry.this slurry, brought into
intimate contact with the flue gas by various
technique, absorbs the SO2 in it.
 The wet scrubbing process was orriginaly developed
in the 1930s by Imperial Chemical Industries (ICI) in
England.In the modern version of the process, the flue
gas is scrubbed with a slurry that contains lime (CaO)
and limestone (CaCO3) as well as the salts calcium
sulfite (CaSO3 .2H2O)and calcium sulfate (in hydrate
form, naturel gypsum, CaSO4 .2H2O).The SO2 in the
flue gas reacts with the slurry to form additional sulfite
and sulfate salts, which are recycled with the addition
of fresh lime or limestone. The chemical reaction
aren’t known with certainty but are thougth to be;
 CaO + H2O ----------- Ca(OH)2

Ca(OH)2 + CO2 --------- CaCO3 +H2O

CaCO3 + CO2 + H2O------- Ca(HCO3)2

Ca(HCO3)2 + SO2 + H2O --------CaSO3 .2H2O + 2CO2

CaSO3 . 2H2O + 1/2O2 ------------ CaSO4 .2H2O

 One technique employs a spray tower downstream of the
particulate-removalsystem (electrostatic precipitator or fabric
fitler). The flue gas is drawn into the spray tower by the main
steam-generator induced-draft fan where it flows in
countercurrent fashion to the limestone-slurry spray. A mist
eliminator at the upper exit of the tower removes any spray
droplets entrained by the gas. The gas may have to be slightly
reheated before it enters the stack to inprove atmospheric
dispersion.
 The sprayed limestone slurry collects in the bottom of the
tower and is recirculated back to the spray nozzles by a pump.
A system of feed and bleed charges a fresh slurry, under pH
control , and discharges an equivalent amount from the
circulating slurry. The fresh slurry is prepared by mixing the
lime-limestone with water in a ‘slaker-grinder’ and stirred in a
slurry tank. The bled slurry is sent to a dewatering system,
which is in the form of thickeners and filters or centrifuges,
where water is removed from the calcium-sulfur salts. The
reclaimed water is used to help make fresh slurry.
 The wet scrubber has the advantages of high SO2
removal efficiencies, good reliability, and low flue-
gas energy requirements.In addition, it is capable of
removing from the flue gases residual particulates
that might have escaped the particulate-removal
system.
A main disadvantages is the build up of scale in the spray
tower and possibilitiy of plugging. The prevention of such
scale is essential to the reliable operation of the tower.
Scaling occurs because both calcium sulfite and calcium
sulfate have low water solubility, normally around 30
percent, and can therefore form supersaturated water
solutions. A minimum liquid-to-gas ratio must therefore be
used, its value depending upon the SO2 content of the flue
gas and the expected extent of sulfite oxidation. Precipitation
occurs at a finite rate, which necessitates holding the SO2-
absorbing liquar in a delay tank after each pass. An
insufficient delay time increases supersturation and promates
scalling. Another tecnique for controlling scale is the use of
seed crystals. These are calcium sulfite and sulfate
precipitate crystals, in a supersaturated solution, that are
maintained in the SO2-absorbing liquor. They provide sites
around which preferential precipitation takes place and
enhance the precipitation rate.
 Other disadvantages of the wet scrubers are the
reheating of the flue gas, a larger gas pressure drop
requiring higher fan power requirements than the dry
FGD system (below), and typicallyhigher capital and
operating costs.
 The waste material from wet scrubbers is a water-
logged sludge that poses difficult and costy disposal
problems.
 THE DRY FLUE-GAS
DESULFURİZATİON SYSTEM
 Like the wet scrubber, above, the dry FGD system, also called
a dry scrubber, utilizes an aqueous slıurry of lime, CaO, to
capture flue gas SO2 by forming calcium sulfites and sulfates
in spray absorbers. The slurry in the case, however, is
atomized, usually by a centrifugal atomizer, into a fine spray
that promotes the chemical absorption of SO2 and, because of
the small spray paticle size, is quickly dried bye the hot flue
gases themselves to a particulate suspension that is carried
along with the desulfurized gas stream. The reaction
particulates as well those carried by the flue gases (fly ash) are
then removed, mainly by a fabric fitler, before the gas is
drawn by the induced-draft fan to the stack.
 A major component of this system is the slurry-
generating system. A ‘slaker’ meters lime and water
into an agitated tank to prepare a slaked lime slurry
which, in turn, is diluted by additional water and
processed to remove inert impurities called grits,
which are disposed of. The lime slurry is pumped to
the spray absorber with the flow controlled by the
amount of SO2 in the flue gas.
 Particulates both coming in with the flue gas and
generated in the FGD are collected from the absorber
and fabric-filter hoppers and sent to a recycling silo
for disposal or for recycling of a portion of it with the
slurry (depending upon the extent of original
utilization of the reactant in the absorber). The
recycled slurry is enriched by an alkaline material,
such as CaO, MgO, K2O, or Na2O.
 The main advantages of the dry system are he
dry, powdery nature of the waste material, which
poses fewer and less costly disposal problems then
the wet waste from the wet FGD system (thought
these problems are still large), and the mechanical
simplicity of the system.
The main disadvantage is that the efficiency of
SO2 removal is lower than that of the wet scrubber.
1979 NSPS (New Source Performances Standards)
regulations, which specify only 70 percent SO2
removal in new plants, have encouraged the
developmed of the system, however.
Other disadvantages are the need for careful design
optimization of the spray absorber and the slaker, and
the storng dependence of collection efficiency on
absorber outlet temperature, which neccessitates
opereting as close as is safe to the saturation temperature
that corresponds to the partial presure of the water vapor
in the gas in order to avoid condensation (below the
coresponding dew point). This poses problems with
fitler-bag performance.
 SİNGLE ALKALİ SCRUBBİNG

 Clear water solutions of either sodium (usually in

the form of sodium hydroxide, NaoH, or sodium
sulfite, Na2So3) or ammonia (NH3) are excellent
absorbers or SO2. The advantages of alkali
scrubbing is tahat it avoids the scaling and plugging
problems of slurry scrubbing by using alkaline
earth. Ammonia scrubbing has the advantage that
the scrubber product, ammonium sulfate, can be
sold as a fertilizer, but the disadvantage that the
process produces troublesome fumes.
 A well-developed sodium scrubber is the Welman-
Lord SO2 recovery process, which has found use in
powerplants, refineries, sulferic acid plants, and other
industrial installations in the USA and Japan. The
process utilizes a water solution of sodium sulfite
(Na2SO3) for scrubbing and generates a
concentrated SO2 (about 90%), in effect removing
the SO2 gas from other flue gases.
 The flue gas from fossil powerplants (or nonferrous
smelters) is first pretreated by cooling and removal
of particulate matter, such as by electrostatic
precipitators, prior to being sent to the absorber. In
the absorber the water solition of sodium sulfite
absorbs the SO2 in the pretreated flue gas to produce
sodium bisulfite NaHSO3 according to
 SO2 + Na2SO3 + H2O ----------- 2NaHSO3
 The desulfurized gas is reheated before going to the
stack in order to improve atmospheric dispersion.
 The sodium bisulfite is sent to a forced-circulation
evaporator-crystallizer via a surge tank. The
evaporator-crystallizer is the herth of the system. The
surge tank allows steady flow rates into it despite gas
flow and concentration fluctuations. Through the
application of low-pressure steam, such as from a
turbine exhaust, the sulfite is regenerated in the form
of a slurry according to
 2NaHSO3 ----------- NaSO3 + SO2 + H2O
 The product SO2 may be utilized to produce
liquid SO2 or sulfuric acid, on
 site or in a satellite plant, or to produce
elemental sulfur. A well-known process for
doing this is called the Claus process, which is
based on the addition of H2S according to
 SO2 + 2 H2S ----------- 3S + 2 H2O
 NO REMOVAL
 A process for the removal of NO, also by the addition
of H2S, is proposed. It is given by
 NO + H2S ----------- S +1/2N2 + H2O
 The combined removal of SO2 and NO is under
study. In both reactions, the H2S must be completely
consumed as it is a pollutant itself.
 In 1977 the system was estimated to add an additional
$120/kW, or some 12 to 15 percent to the base capital
cost of a powerplant. It was said operating costs
would increase by about $60/MBtu.
 Most scrubbers in use by 1981 have been of the wet
type. There is not sufficient experience with the dry
type to establish which of the two may be selected by
utilities in the future. Presently all scrubber systems
are large and occupy a sizable area of a powerplant,
have capital costs that run in the tens of millions of
dollars for 500-to 1000-MW plants, and consume a
sizable fraction of the gross electrical output of these
plants. They also require a lot of maintenance , which
results in the doubling of operation and maintenance
personel and causes, consequently, larger operation
and maintenance costs. In addition, they generate
huge amounts of waste that has to be disposed of.
 There are two types of disposal of FGD wastes: wet
disposal, called ponding, and dry disposal in
landfills, which are getting scarce. In general utilities
are not always eager to build these disposal systems.
Nevertheless, some 19000 MW of FGD and sludge
disposal systems were in operation, and 26000 MW
were under construction or planned, in 1981. The
Electric Power Research Institute (EPRI) has
published the FGD Sludge Dİsposal Manual, which
incorporates the latest waste-disposal technology and
regulations and describes how to design an
environmentally acceptable waste-disposal system
and the options available for processing and disposal
of the wastes.