ABSORPTION

FLUE GAS
DESULFURIZATION

CREATED BY

ZELHA SALDIR
ITIR SARI
TUBA BEEND
MUSTAFA ZGRAY
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

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

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,fermen
tation 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 cocurrent 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-togas 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
High efficiency of
absorption drop
Low outlet
temperature
No need aftercooling
Low flow resistance

Easy maintenance

Disadvanges
Restricted by
pressure
Film breakup
Flooding

Spray columns
are differetal
SPRAY
COLUMN

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
DESULFURZATON 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 arent
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 induceddraft 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.

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 SO2absorbing liquor. They provide sites around

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

DESULFURZATON SYSTEM

Like the wet scrubber, above, the dry FGD

system, also called a dry scrubber, utilizes an
aqueous slurry 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.

SNGLE ALKAL SCRUBBNG

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 forcedcirculation 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 lowpressure 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 Dsposal
Manual, which incorporates the latest wastedisposal 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.