Flue-Gas Desulfurization (Scrubbers)

(Nazaroff & Alvarez-Cohen, Section 7.C.2, much augmented)

(Mihelcic & Zimmerman, Section 12.8.2)
Packed-bed scrubbers, also called
wet scrubbers or absorbing towers,
(Gongyi Lianghui Environmental Protection Machinery Equipment Factory) are pieces of equipment installed in
power plants to remove selected
gases (and sometimes also
particulates) from combustion fumes
in order to meet emission standards.

The usual gas being removed is

SO2, and we address here the
design of a scrubber in this
particular application.

The key aspect of the process is

the dissolution of the gas from the
fumes into a liquid made of water
with suitable additives.
This process is called stripping.

The outflowing liquid is collected,

concentrated, and recycled.
Ultimately, the stripped gas ends up
as a solid residue.

Example of post-operation pollution control (effluent treatment)

1
As an aside:
Example of pre-operation pollution control (pollution prevention)

Some scrubbers are large and costly to build. They are also costly to operate.

2
 Air-Cure Pte Ltd., Singapore
Smaller scrubber

This type of scrubber is most commonly used for

the removal of noxious gases from airstreams.
It is designed for high-efficiency collection and
low-pressure drop. The vertical design has a
relatively small footprint making it ideal for
applications where floor space is at a premium.
(http://www.ceilcoteapc.com.sg/spt-hrp_scrubbers.htm)

Packed Tower Features:

- Capacity from 20 to 100,000 cfm
- High-efficiency packing for removal of
soluble/reactive gases and liquid droplets down
to 7 microns
- Lower portion of shell serving as integral sump
for recycle liquid
- Single spray nozzle liquid distributor for
minimum fouling

Applications:
- Scrubbing in semiconductor manufacturing
- Wastewater treatment odor control
- Acrylic acid scrubbing
- Foundry amine scrubbing
- NOx control

Inside look of a packed tower scrubber

In its essential aspect, a scrubber is a vertical tank

(tower) in which gas and liquid flow against each
other: The liquid solution flows downward while
the gas bubbles to the top, each moved under the
action of gravity.

To maximize contact between liquid and gas, the

tower is also packed with a large number of small
objects forcing the liquid to percolate slowly
through tortuous paths and the gas to rise in small
bubbles. As the liquid and gas compete for
space, very intimate contact takes place between
the two, and a very large contact area exists
through which the transfer of chemical species
can take place.

The counter flow with vapor moving upward and

liquid downward is very practical for two reasons:
(1) It happens naturally by gravity as the liquid
trickles down while the gas bubbles up through it,
and (2) the fumes encounter increasingly less
loaded liquid as they get progressively cleaner on
their way upward.

3
 How the equipment fits in the overall system

Once collected at the bottom,

the laden solution (a Calcium
solution in the case of SO2)
undergoes further reactions
until a more valuable substance
can be extracted, such as
calcium sulfite (CaSO3) or
calcium sulfate (CaSO4), which
can be turned into plaster
board.

The chemistry of desulfurization

The liquid used to wash the flue gas is a water-based calcium solution.
Limestone (CaCO3) is cheap and creates an alkaline environment in water:

CaCO3 + H2O Ca++ + HCO3 + OH

This alkalinity (presence of OH radicals) negates the acidity (presence of H+ protons)

formed by the SO2 in solution:

SO2 + H2O HSO3 + H+

The H+ protons combine with the OH radicals to form water:

H+ + OH H2O

while the radical HCO3 binds with H+ to create H2CO3 (carbonic acid), which creates an
equilibrium with water (H2O) and carbon dioxide (CO2):

HCO3 + H+ H2CO3 H2O + CO2

4
Chemistry of desulfurization (contd)

The net result is the transformation of CaCO3 to calcium ions (Ca++), the release of carbon
dioxide and production of HSO3 :

CaCO3 + 2 SO2 + H2O Ca++ + CO2 + 2 HSO3

The carbon dioxide bubbles up as a gas, while HSO3 remains in the water solution (if the
temperature is not too high see final note below).

In the effluent hold tank, at the foot of the tower where the liquid is collected before final
treatment, another load of limestone is added to the liquid, and a further reaction takes
place:

CaCO3 + 2 HSO3 + Ca++ 2 CaSO3 + CO2 + H2O

Calcium sulfite CaSO3 is a solid precipitate. It is important to have the precipitation occur
in the effluent hold tank rather than in the tower itself. Otherwise, the tower would become
clogged. This is why the temperature and pH inside the tower need to be controlled.

Additional remarks

To ensure proper functioning, it is important to dose correctly the amount of limestone in

the liquid fed at the top of the tower and to feed the remainder of the limestone to the
effluent hold tank directly. The amount of limestone in the liquid is determined using
stoichiometry (1 mole of CaCO3 for 2 moles of SO2, that is, 100 g of limestone per 128 g
of sulfur dioxide removed from the flue gas) and is easily controlled by monitoring the pH,
since it makes an alkaline solution.

The fact that some significant portion of the SO2 in the liquid turns into another chemical,
namely HSO3, makes more room for SO2 in the liquid and consequently promotes a
greater suction of SO2 from gas to liquid. When properly dosed, the limestone slurry is
able to hold 6 to 15 times more S than pure water. This is very beneficial.

5
The central piece of equipment consists of a
vertical tank, called tower, in which the fumes
(vapor) are fed at the bottom, move upward
through one or several layers of packed
objects and exit at the top. Simultaneously,
the cleaning liquid is poured from the top and
trickles downward through the packed layers.

The variable are defined as:

X = number of moles of SO2 in the liquid on

a per-mass basis (moles per kg of liquid)
X' = number of moles of HSO3 in the liquid on
a per-mass basis (moles per kg of liquid)
Y = number of moles of SO2 in the vapor (fumes)
on a per-mass basis (moles per kg of vapor)

L = mass flow of liquid trickling down

(kg of liquid per minute)
V = mass flow of vapor bubbling upward
(kg of vapor per minute)

H = height of the packed layers in the tower

(meters)

The entrance and exit values are noted as:

Yin = inlet value of Y (at bottom)

Yout = exit value of Y (at the top)
Xin, Xin' = inlet values of X and X' (at the top)
Xout, Xout' = exit values of X and X' (at the bottom).

Since the vapor consists in the fumes coming from the combustion chamber, its chemical
composition is known, and Yin is therefore given.

Regulatory standards impose a certain level of cleanliness in the fumes released to the
environment and therefore set the value of Yout. Alternatively, one may impose a certain
efficiency of removal (ex. = 95%).

The efficiency (sometimes called performance and denoted P) is defined as

Yout
1
Yin

Thus, Yout is often set by the value of Yin (fume composition) and (required efficiency):

Yout (1 )Yin

6
 To maximize the passage of SO2 from vapor to liquid, we inject a clean liquid
at the top and take Xin = Xin' = 0.

X in X in' 0

Finally, Xout and Xout' may be whatever we wish them to be. If at all possible,
however, we would want to maximize them in order to minimize the amount of
liquid being used (minimization of energy for pumping to the top of the tower
and minimization of volume to be treated downstream of the tower).

The removal of SO2 from the vapor and its dissolution into the liquid make the mass
flow of vapor (V) decrease upward and the mass flow of liquid (L) increase
downward, but these changes are negligible because the absolute mass of SO2
being transferred is rather modest; the fume remains mostly air and CO2, and the
slurry remains mostly water.

We can then safely assume that the mass flow rates L and V stay at constant values
throughout the tower:
L constant
V constant

Chemical equilibrium

Inside the liquid, a chemical equilibrium exists between the two forms of sulfur, SO2 and
HSO3. Assuming first-order chemical kinetics, we can then state that there exists a
proportionality between the two concentrations, namely:

X ' c X

The coefficient c may be called the conversion factor. Its value ranges from 5 to about
14. Thus, the total amount of S in the solution is

X X ' (1 c) X

which is 6 to 15 times what the amount would have been without the calcium additive.

7
 Equilibrium line

At the interface between gas

and liquid, SO2 is exchanged
between the two until equilibrium
is achieved.
Equilibrium obeys Henrys Law
of proportionality between gas
and liquid phases:

Y m X

At the temperature and pressure common in the operation of scrubbers,

SO2 equilibrium is achieved when the gas fraction is about 36 times the
liquid fraction. Therefore, a practical value is

m 36

The value of m varies with the nature of the gas being scrubbed and with temperature.
The value quoted here is strictly for SO2 at around 40oC.
Should another gas be stripped (ex. H2S), the m value may be very different.

Connection between the value of m and Henrys Law

Since the coefficient of proportionality m reflects a chemical equilibrium between

(essentially) air and (essentially) water, it can be none other than a disguised form of
the Henrys Law constant.

Henrys Law states: PSO2 H [ SO2 ] with H = 0.81 atm/M at 25oC

= 1.05 atm/M at 40oC

In fumes (~ air): In liquid (~ water):

moles of SO2 moles of SO2
Y X
grams of air grams of water
moles of SO2 moles of air moles of SO2 liters of water

moles of air grams of air liters of water grams of water
PSO2 1 1
[ SO2 ]
Pair 28.95 grams / mole of air 997 grams / L of water
PSO2 1 [ SO2 ]
Equilibrium: Y mX m
Pair 28.95 g / mol 997 g / L
997 g / L PSO2 1 997 mol / L H
m 27.9 at 25oC and 1 atm
28.95 g / mol [ SO2 ] Pair 28.95 Pair
36.1 at 40oC and 1 atm

8
 Gas-liquid transfer

The actual flow in the tower is not at

equilibrium and a one-way exchange
takes place.

It can be assumed that away from

equilibrium, the transfer rate is
proportional to the difference Y - mX,
such that when Y - mX is positive, there
is an excess in the vapor phase and the
transfer is from vapor to liquid (toward
decreasing Y and increasing X), while
when Y - mX is negative, the transfer
goes in the opposite direction. The
transfer rate is furthermore proportional
to the area of contact between gas and
liquid. We model this as:

transfer rate K Ac (Y mX )

where K is a rate of transfer (mass per time and per area)

and Ac is the area of contact between gas and liquid.

Mass balance from top downward

An important relation is obtained when we perform a mass balance for a section of the
tower, from an arbitrary level to the top.

At the arbitrary level, the variables are Y,

X and X' , while at the top they are Yout,
Xin and Xin'.

Since the amount of entering sulfur is

equal to that going out during steady
operation, the sum of the influxes, VY from
below and L(Xin +Xin') from the top, must
be equal to the sum of the effluxes, VYout
from the top and L(X + X') from below:

V Y L ( X in X in' ) V Yout L ( X X ' )

Since Xin = 0 and X' = cX, a division by V yields:

L
Y Yout (1 c) X
V

9
 L
Y Yout (1 c) X
V

Operating line

On the X-Y plot, the previous

relation corresponds to a straight
line starting at (X = 0, Y = Yout),
corresponding to the top of the
tower, and slanting upward with
slope (1+c)L/V. This line is
called the operating line.

At the top of the graph, where Y

reaches its maximum value Yin,
which corresponds to the bottom
of the tower, one obtains the
value of Xout .

Since the amount of liquid used (L) is free to be chosen, we can consider a series of
different operating lines, one for every slope (1+c) L/V considered. In order to stay on
the upper side of the equilibrium curve, however, there exits a minimum acceptable
slope, and there is therefore a minimum value of the liquid mass flow, Lmin, that must be
used.

Minimum liquid needed

The maximum possible value of Xout is

1
X out.max Yin
m

which occurs when the liquid flowrate L is at its minimum allowed value

m Yout m
Lmin 1 V V
1 c Yin 1 c

In practice, for a reason that will be become clear later in the analysis, one must
stay clear from the minimum value and adopt for L a value that is a multiple of the
minimum, namely:

1 . 5 L min L 3 . 0 L min

safety limit wasteful beyond this

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Separate mass balances

The operating line sets one relationship

between the two variables, X and Y.

A separate mass balance must be performed

for each independently in other to determine
X and Y as functions of position inside the
tower.

To do this, we now consider a thin slice of the

packing inside the tower, from the level z to
the level z + dz, counting z downward from
the top (z = 0 where Y = Yout and X = Xin = 0).

The steady-state budgets express that the rate at which the amount in each phase
(gas or liquid) enters the slice is equal to the rate at which it exits plus or minus the
amount exchanged with the other phase:

V (Y dY ) V Y K dA c (Y mX )
L (1 c ) X K dA c (Y mX ) L (1 c ) ( X dX )

where dAc is the contact surface area between liquid and gas within the small volume.

Contact area Differential equations

If we define a as the surface area made available by the packed objects per volume of
packing (in ft2 per ft3), then dAc is equal to a times the volume of the slice.

If A=d 2/4 is the cross-sectional area of the tower of inner diameter d, this volume is Adz,
and the contact area in that volume is
dAc a A dz

The previous budget equations become:

V dY K a A (Y mX ) dz

(1 c ) L dX K a A (Y mX ) dz

Or, in the form of differential equations:

dY KaA
(Y mX )
dz V
dX KaA
(Y mX )
dz (1 c ) L

11
Types of packing elements

Variations of
Tellerette type

These elements are designed to create tortuous flow paths

in order to maximize contact between gas and liquid.

Fp
a

12
 Since the operating line sets a relationship between Y and X, we can replace Y in
terms of X in the second equation to obtain a single equation for the variable X:

dX KaA KaA [(1 c ) L mV ]
Yout X
dz (1 c ) L (1 c ) LV

Integration from the top (where X = 0 at z = 0) downward (z > 0) yields:

V (e z 1)
X ( z) Yout
(1 c) L mV

where the coefficient in the exponent is defined as

KaA [(1 c ) L mV ]
0
(1 c) LV

The accompanying solution for Y is:

(1 c ) Le z mV
Y ( z) Yout
(1 c ) L mV

From this, we can determine the values at the bottom.

If H is the height of the packed layer inside the tower where the gas-to-liquid
exchange takes place, the bottom values are obtained for z = H:

V (e H 1)
X out Yout
(1 c ) L mV

Since the Yin value is known, the last equation sets a constraint on the dimensions
of the tower:

(1 c ) Le H mV
Yin Yout
(1 c ) L mV

1 m V Yin m V
H ln 1
1 c L out
Y 1 c L

13
 More practical notation

Define
mV 1 Lmin
1) the auxiliary parameter
(1 c ) L L

1
ln
1
2) the number N (not necessarily an integer)
1

V
3) the so-called height of a transfer unit HTU
KaA

With this, the expression for the height H of the tower becomes

H N HTU

A couple of remarks

Because a greater gas velocity promotes better contact, the density of contact area a is
somewhat dependent on the gas velocity v, and it is often impractical to try to estimate
HTU from its separate ingredients.
In many applications, therefore, the value of HTU is often determined experimentally.

Note that, in any event, the value of HTU does not depend on the overall dimensions of
the tower and absolute flow rates, but only on local variables, such as K, a and v.

We can also see now why the liquid flow rate L may not be taken at its minimum
value Lmin.

If it were (L = Lmin), the number of steps would be infinite and the required tower
height would be infinity! (N as max = mV/(1+c)Lmin = 1/).

This is why the actual liquid flow rate needs to be greater than the minimum value.

14
Watch out for flooding!

To reduce the diameter of the tower and therefore the cost, one wishes to pass the
required liquid and gas flows through the narrowest possible section, that is, at the
highest possible speeds.

There is, however, a limit on the gas velocity. If the gas velocity exceeds a certain
threshold, it literally blows the liquid away from the packing material and prevents it
from trickling downward. The result is an accumulation of liquid above the packed
layers and flooding in the upper section of the tower.

To determine the safest possible gas speed, the procedure is to calculate the
flooding speed and then take a fraction of the latter.

Variables used in connection

with this graph:

Fp = packing factor
(see earlier slide)
x = liquid density
(in lbm/ft3)
y = gas density
(in lbm/ft3)
x = 0.80 cp, liquid viscosity
gc = 32.17 ft.lbm/s2.lbf
gravitational constant

Gx = L/A = liquid mass flux

(in lbm/ft2.s)
Gy = V/A = gas mass flux
(in lbm/ft2.s)

15
The flooding speed is determined from the top curve of the graph shown on the
previous slide.

The abscissa is first calculated using the already known gas and liquid mass fluxes
(noting that Gx/Gy is equal to L/V) and the densities of both liquid (x) and gas (y).

From the abscissa, one goes up the graph to the top, dashed curve - labeled
"Flooding line" - and across to determine the corresponding ordinate.

In the expression forming the ordinate, all factors should be known except the gas
mass flux Gy. Thus, reading the graph provides a value for Gy. The flooding gas
velocity can then be obtained by eliminating mass with the density: vflooding = Gy/y.

The recommended operational speed is half of the flooding speed, thus:

Gy
v 0 .5 v flooding 0 .5
y

Once the gas speed is set, the cross-sectional area A of the tower is determined in
order to have the correct total gas flow rate (using V = yv A), and the required inner
diameter of the tower d is calculated (using A = d 2/4). Thus,

4V
d
y v

To facilitate the calculations, here are flooding values tabulated in metric units:

Gx y Fp G y2 Gx y Fp G y2
Gy x y ( x y ) y Gy x y ( x y ) y

0.010 0.718 0.40 0.161

0.015 0.682 0.50 0.131
0.02 0.642 0.60 0.113
0.03 0.617 0.80 0.0871
0.04 0.599 1.0 0.0663
0.05 0.581 1.5 0.0474
0.06 0.526 2.0 0.0306
0.08 0.461 3.0 0.0183
0.10 0.437 4.0 0.0131
0.15 0.355 5.0 0.00886
0.20 0.275 6.0 0.00703
0.30 0.197 8.0 0.00458
10.0 0.00306

Here, x and y are in kg/m3 while Gx and Gy are in kg/m2.s .

The packing factor Fp is dimensionless.

16
 A Final Note

The fumes exiting the furnace are hot and need to be cooled significantly before
entering the scrubber. This is necessary to reduce the volatility of HSO3 (into
which SO2 turns once in the liquid phase) and therefore to promote its retention into
the liquid used for the scrubbing.

Reheating the cleaned fumes is necessary afterwards for more efficient release
through the smokestack to the atmosphere.

Recapitulation of the design procedure

Establish the expected performance P = = 1 - Yout/Yin.

From Yin, Yout and the equilibrium line, determine Lmin, paying attention to the factor
(1+c) in order to take into account the chemical changes of SO2.

From Lmin, set the L value using the rule 1.5 Lmin L 3.0 Lmin.

Determine the value of the parameter = mV/(1+c)L.

Calculate the number N of stages, using its expression in terms of and .

Select or estimate a value for the height of a transfer unit (HTU).

Determine the tower height H = N x HTU.

Determine the flooding gas mass flux Gy from the flooding curve.

Set the gas velocity at half flooding value: v = 0.5 Gy/y.

Determine the tower cross-sectional area A and then its diameter d.

Estimate the amount of limestone needed.

17
An example

Given:

Flue gas flow of 10,000 ft3/min at T = 49oC and p = 1 atm

Incoming SO2 concentration is 0.30%
Assume an empirical multiplier value c = 6
Criterion for liquid flow is L = 1.8 Lmin
Packing with 1.5-in Berl saddles
HTU = 14 ft

Objective:

Remove 95% of the SO2

Question:

What should be the dimensions (height and inner diameter) of the tower?

Solution:

Start by finding Yin and Yout:

0.30% of moles of SO2 per mole of air Yin = 3 x 10-3 moles SO2/mole air

Since 1 mole of air weighs 28.8 g = 28.8 x 10-3 kg

Yin = 3 x 10-3 /28.8 x 10-3 = 0.104 moles SO2/kg air

95% reduction required Yout = 5% of Yin Yout = 5.21 x 10-3 moles SO2/kg air

Next put the gas flow rate in the required units (volume per time mass per time)

At 49oC = 322.15 K and 1 atm, volume of one mole of air is RT/p = 0.0264 m3,
corresponding to a density of 0.0288 kg / 0.0264 m3 = 1.09 kg/m3

The gas flow rate is 10,000 ft3/min = 283.3 m3/min V = 308.7 kg/min

Now, we can determine the minimum amount of liquid required:

m Yout
Lmin 1 V
36
0.95 (308.7 kg / min) 1508 kg / min
1 c Yin 1 6

18
From this follows the actual liquid flowrate to be used:

L 1 . 8 L min 2714 kg/min

Next we determine the parameter

mV 36 308 . 7 kg/min
0 . 585
(1 c ) L (1 6 ) 2714 kg/min

from which follows the number of HTUs needed

1
ln
1
N 5.26
1

Since we are given the height of the HTU, we immediately get the height of the tower:

HTU 14 ft H N HTU 5 . 26 14 ft 73 . 7 ft 22 . 5 m

The diameter of the tower is obtained by keeping a safety margin from flooding.
So, we calculate the quantities needed to use the flooding curve.

Gx L 2714
8 .794
G y V 308 .7
Gx y
y 1.09 kg/m 3 0.0679 lbm/ft 3 0.290
Gy x y
x 1000 kg/m 3 62.32 lbm/ft 3

G y2 Fp x0.1
0.060
gc ( x y ) y

19
Berl saddles 1.5-in size Fp = 65

G y2 (65)(0.80) 0.1
0.060
(32.17)(62.32 0.0679)(0.0679)

G y2 0.128 G y 0.358 lbm/ft 2 s = 1.752 kg/m 2 s

For effective operation, operate at 50% of flooding velocity:

1
Gy = 1.752 kg/m 2 s = 0.876 kg/m 2 s
2

From this follows the gas velocity

Gy 0.876 kg/m 2 .s
vy 0.804 m/s 48.24 m/ min
y 1.09 kg/m 3

Finally, determine the necessary cross-sectional area and inner diameter:

V 308.7 kg/ min

A 5.873 m 2
y v y (1.09kg/m 3 )(48.24 m/ min)

4A
A d2 d 2.73 m
4

Done !!!
We were able to get rid of 95% of the SO2!

20