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SO2 Absorption

06-311: Unit Operations Laboratory


Carnegie Mellon University

Group 8:
Marissa Arney
Stephen Cisar
Lakshmi Jayapalan
Michael Slowik
Table of Contents

Abstract… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … .1

Introduction… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … ...1

Equipment… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … .1

Part I. Rasching Rings


Procedure… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … .2
Theory… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … ..2
Results and Discussion… … … … … … … … … … … … … … … … … … … … … … … … … … 3

Part II. Activated Carbon


Procedure… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … .4
Theory… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … ..5
Results and Discussion… … … … … … … … … … … … … … … … … … … … … … … … … … 6

Future Experiments… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … ...7

References… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … .9

Nomenclature… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … ..10

Appendices
A: Equipment
B: Additional Theory for the Operating Line
C: Mass Transfer Coefficient Calculation
D: Activated Carbon Sample Calculation
E: Heat of Reaction Calculation
F: Void Fraction Calculations
G: Literature Value Mass Transfer Coefficient
Abstract

The purpose of this lab was to remove sulfur dioxide from air. We analyzed two methods of SO2
removal, the first of which was using an absorption column packed with 3/8 in. rasching rings.
The mass transfer coefficient of SO2 into the water was determined to be 17.028 mol/m3.s. This
value compared favorable to the literature value of 6.031 mol/m3.s for a similar SO2 absorption
system when considering different raschig rings and flowrates were used. The second method of
SO2 removal was the use of an absorption column packed with activated carbon. Activated
carbon serves as a catalyst to react the SO2 into H2SO4, therefore the SO2 is removed by both
absorption into the water and reaction. From the data collected it was determined that this
catalyst reaction was mass transfer limited because the overall reaction rate was not directly
dependant on the initial SO2 concentration. Using this knowledge to operate the column most
effectively it should be run at the highest possible vapor flowrate and highest initial SO2
concentration.

Introduction

Coal is burned all over the world to produce energy which is used to provide our modern society
with many of the amenities that we have grown accustomed to. One of the drawbacks however to
producing energy by combusting coal is that the process emits sulfur dioxide into the atmosphere.
This sulfur dioxide is a major pollutant that reacts with water droplets in the upper atmosphere to
produce acid rain. Acid rain has been the cause of many significant problems in the last fifty
years ranging from uninhabitable lakes and streams for fish in upstate New York to severe health
problems that caused deaths in Erie Pennsylvania. This has forced government officials to set
limitations on the amount of SO2 released into the atmosphere.

One method of removing the SO2 from the flue gas of coal to reach the government standards is
to use an absorption column. An absorption column is filled with a packing material in which a
liquid and gas stream come in contact with one another so that the undesired pollutant can be
removed. In the first part of the experiment rasching rings were used as the packing material and
the overall mass transfer coefficient was calculated. In the second part of the experiment the
packing material was activated carbon which required that the column be modeled both as an
absorption column and a plug flow reactor because a reaction was being catalyzed on the surface
of the packing material.

Equipment

To remove the SO2 from air, the SO2/air mixture was sent through an absorption column (Figure
A.1). The SO2/air mixture enters through the bottom, and travels up through the column,
contacting the liquid water running over the packing material. The liquid water scrubs the SO2
from the air, leaving the purified air to be removed off the top. The liquid water enters through
the top of the column and is evenly distributed across the entire cross sectional area.

Each column section is 11.5 in. high with a 4.0 in. inner diameter. The air, SO2, and water flow
rate could all be controlled through rotameters attached to the apparatus. A manometer was
hooked up across the top and bottom of the column to measure the pressure drop across the

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column. The air flowing out of the absorption column was sent through a SO2 detector, which
reported the concentration of SO2 remaining in the air in units of parts per million (ppm).

Part I. Rasching Rings

Procedure

The first part of this lab consisted of scrubbing SO2 out of air using an absorption column one
section high filled with 3/8 in. rasching rings. The column was run continuously with Air/SO2
mixture entering from the bottom, and pure water entering the top of the column at a set velocity.
Various flows of water, air, and SO2 were run through the column. The concentration of SO2 in
the air going into and out of the column for these varying amounts were measured to determine
the mass transfer coefficient of SO2 into the water.

Theory

Rasching rings, like most packing materials, are inert materials that serve to increase the
interfacial area between the air and water, therefore increasing the amount of SO2 absorbed.
Every packing material has a different mass transfer coefficient, which is dependent on the
amount of contact between the liquid and vapor phases.

The overall mass transfer coefficients are calculated for rasching rings by manipulating the design
equation, (1), for a differential slice of the absorber (Prieve).

yb
V dy
zT =
K y aS ∫y −
ya
y*
(1)

zT is the height of the absorber column, V is the molar flowrate of the vapor, Ky is the overall mass
transfer coefficient, a is the interfacial area, S is the cross-sectional area of the column, and the
integral term is the height of a “transfer unit”. A transfer unit is a slice of the absorber across
which the mole fraction of the gas, y, undergoes a change equal to the average driving force,
(y-y*)avg.

To determine the height of the transfer unit the operating and equilibrium lines are plotted on
mole fraction coordinates as in Figure 1 (see Appendix B for more information on the operating
line).

yb
Operating

ya Equilibrium
yb*

xa xb xb*
-2-
Figure 1. Height of a Transfer Unit
The equilibrium curve and operating line are plotted on mole fraction coordinates. Both lines are
straight when assuming that there is only one transferable component, and the streams are
sufficiently dilute as in this case. Equation (2) is used in conjunction with this graph to determine
the height of a transfer unit

If there is only one transferable component and the streams are sufficiently dilute then
both the operating and equilibrium lines will be straight. When this is true then the
integral in equation (1) can be written as

yb − y a
yb
dy
∫y −
ya
=
y * ( y b − y b *) − ( y a − y a *)
(2)

 yb − yb * 
Ln
 y − y * 
 a a 

where yb-yb* and ya-ya* are the driving forces at the top and bottom of the column for mass
transfer of the SO2 between the two phases. yb* is found by dropping a line parallel to the y axis
from the point (xb,yb) to the equilibrium curve as can be seen in Figure 1. The value of ya* can be
found in the same manner.

Results and Discussion

Experimental data and results for the 3/8 in. rasching ring trials are given in Table 1. A mass
transfer coefficient of 17.028 mol/m3⋅s was obtained from our experimental data.

Table 1- Mass Transfer Coefficients Data & Results


The data and results for Kya in an absorption column packed with 3/8 in. rasching rings used to remove SO2
from an inlet vapor feed stream are given below. A range of values was reported for the outlet SO2
concentration because the detector did not stabilize to one value. The final Kya was determined by
averaging the four values at each end of the range for both experiments.

Air In SO2 In Total inlet Water inlet SO2 outlet


Experiment Flowrate Flowrate Flowrate, G Flowrate, L Concentr. Ky a
# (L/min) (L/min) (L/min) (gal/min) (ppm) (mol/m3⋅s)
1 7.16 0.87 8.03 1.8 65 - 85 15.644 - 15.077
2 9.46 1.57 11.03 2.4 150 - 200 19.112 - 18.309
Average 17.028

In 1949 Whitney and Vivian performed several SO2 absorption experiments, similar to the one in
this lab, in an attempt to come up with a generalized empirical correlation for the overall mass
transfer coefficient using rasching rings. Using this correlation (Appendix G) with our vapor and
liquid flowrates Kya was determined to be 6.031 mol/m3.s. This value is approximately one third
of our value for one of two reasons. In their experiment they used 1.0 in. rasching rings which
yield a smaller interfacial area for mass transfer when compared to the 3/8 in. rings that were used
in this experiment. A smaller interfacial area gives a smaller liquid/vapor phase interface
resulting in less mass transfer, which can be seen in a lower Kya.

-3-
Another reason for the discrepancy in Kya is that our value was calculated from vapor flowrates
that were outside the flow regime used by Whitney and Vivian for their experiments. Their
generalized correlation was obtained for experiments conducted between 16.7 < G < 388 L/min.
Extreme caution always needs to be taken when extrapolating outside the data set because there is
no way to tell if Kya behaves in the same manner for velocities outside the tested region. This
generic caveat is particularly important here because Kya is dependent on the Reynolds number
which will change significantly outside the tested region.

In order to calculate the mass transfer coefficient, we made a few assumptions. First, we assumed
that air and SO2 behaved as ideal gases because the experiments were carried out at 298 K and 1
atm. All the streams entering the absorption column were assumed to be dilute so that the
operating line would be linear on mole fraction coordinates. This is justified because the inlet
and outlet streams are all around 10 mole% or less. According to Geankoplis (p. 619) for
preliminary engineering design calculations this is usually accurate. We also assumed there was
only one transferable component in the system even though the incoming air was not completely
saturated. This is because even though the vapor stream will absorb air the change will be
insignificant.

While recording the values for parts per million of SO2 exiting the column in the gas stream, we
noticed continual fluctuations in the reading. Instead of writing down a single value, we recorded
the range of values as can be seen from table 1. This seemingly large relative error did not have a
significant effect on the final mass transfer coefficient because a fluctuation in parts per million at
the outlet stream is insignificant compared to the inlet vapor flowrates which contains more than
105 ppm SO2.

The Kya value of 17.028 mol/m3.s was reported as the mass transfer coefficient by averaging the
four values from the range in table 1 the two experiments were conducted at different volumetric
flowrates. The reason for this is that according to Whitney and Vivian, the mass transfer
coefficient is proportional to L to a power of 0.82 and G to a power of 0.7. This relationship
causes the small difference in flowrates between experiments 1 and 2 to have a minimal effect on
the mass transfer coefficient.

Part II. Activated Carbon

Procedure

When the activated carbon was used for the packing material the SO2/air mixture was run through
three column sections with a water flow rate of zero. Instead of having a continuous flow of
water, the activated carbon was just wetted by allowing water to pass through the packing
material initially, and then allowing it to drain off. Between experiments water was used to rinse
and regenerate the packing material to remove all of the SO2. Having a water flow rate of zero
was necessary because the carbon particles were tightly packed within the column, which
inhibited a large amount of fluid flow. Therefore, for each experiment if the column wasn’t
operated in a batch process then the column would start flooding immediately.

In order to calculate how much SO2 was being removed from the air the breakthrough time of the
SO2 was measured. The breakthrough time, tb, is the length of time required for the packing
material to become ineffective at removing SO2. This was measured by using a stopwatch from

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the time the SO2/air mixture was introduced to the packing until the detector was pegged at 250
ppm.

The dry and wetted void fractions of the activated carbon were also measured by putting a given
amount of activated carbon in a beaker and weighing the system. Water was then added to the
beaker until it just filled all the voids within the activated carbon. It was then weighed. The water
within the beaker was then drained through a mesh screen, and the beaker was again weighed.

Theory

The raschig rings were inert materials whose sole function, like other inert packing materials, was
to increase the interfacial area between the gas and water, therefore increasing the amount of SO2
absorbed in the water. On the other hand, activated carbon serves as a catalyst to react the SO2
and form H2SO4 as in reaction (1).

activated
SO2 ( g ) + H 2 O( l ) + 1 / 2 O2  carbon
 → H 2 SO4 (l ) Reaction (1)

Since a reaction is occurring within the absorption column, the column also needs to be modeled
as a plug flow reactor (PFR) to accurately interpret the data.

The amount of SO2 removed by the column is dependant upon the kinetics of reaction (1).
Normally for a non-catalyzed reaction, (2), the kinetics can be described by equation (3)

A+B→ C Reaction (2)

− rA = k (T ) ⋅c A
n
(3)

where -rA is the rate of disappearance of component A in moles per volume per time, k(T) is the
reaction rate constant, cA is the concentration of reactant A, and n is the order of the reaction. If
the conversion with respect A is defined as in (4) then equation (3) can be rewritten as a function
of conversion and initial concentration as in (5).

moles A reacted
XA = (4)
moles A fed to reactor

− rA = k (T ) ⋅c AO (1 − X A ) (5)

Notice that in both equations (3) and (5) the reaction constant k is a

function of temperature. The dependance of k on T is very significant and can be seen from the
Arrehnius equation (6)

− E 
k (T ) = A exp  (6)
 RT 

where A is a pre-exponential constant, E is the activation energy, R is the gas constant, and T is
the temperature of the system.

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The reaction catalyzed by the activated carbon is much more complicated than reaction (2)
because there are at least three steps taking place for the reaction to occur. Even though the exact
rate expressions for each mechanism are unknown, most catalytic data can be adequately modeled
by relatively simple nth order rate expressions like equation (3) or by simplified expressions like
equation (7).

k (T ) ⋅C A
− rA = (7)
1 + k1 (T ) ⋅C A

Up to this point it has been assumed that the kinetics are the slowest step in the catalytic reaction
with activated carbon. This may not be the case though because the reactants must diffuse onto
the surface of the catalyst before the reaction can occur. Since the overall reaction rate is now
dependent on both mass transfer and kinetics two rate constants kc and kr (for mass transfer and
kinetics respectively) are needed. The overall rate constant koverall is approximated by

1 1 1
= + (5)
koverall kr kc

There are two main scenarios that occur in catalytic reactions. The first scenario is where kr is
much greater than kc. In this case there is slow mass transfer but the reaction occurs very fast.
Here koverall is approximately equal to kc. The reaction will occur almost instantly after the
molecule reaches the catalyst. This is referred to as a diffusion controlled reaction. The second
case is where kc is much greater than kr. This is where the diffusion occurs very quickly but the
reaction is slow. Here koverall is approximately equal to kr. The diffusion to the catalyst will occur
almost instantaneously but the reaction will be limited by the reaction kinetics.

Results and Discussion

Results for the activated carbon experiments run at ambient conditions are given in Table 2. The
wetted and dry void fractions of the activated carbon were also determined experimentally to be
0.43 and 0.62 respectively. The total amount of water held within the column by the carbon was
calculated to be 1295ml.

Table 2- SO2 Catalyzed Reaction Rate Data


The results for SO2 removal by activated carbon in the absorption column are shown below. Experiments
1-3 and 4-5 were all conducted at constant air flow rates with varying amounts of SO2. Note that the units
for the reaction rate are not specified because it is a relative rate. For more details on this see Appendix D.

Experi- Air Flow SO2 flow Total Gas Initial Mass of SO2 Reaction
ment # Rate Rate Flowrate tb (min) Concentration removed before Rate
(ml/min) (ml/min) (ml/min) Of SO2 (mol/L) tb (gm)
1 8307 1929 10236 4.28 7.83x10-3 22.1 5.16
2 8307 1102.4 9409 4.17 4.87x10-3 12.3 2.94
3 8307 551.2 8858 6.29 2.59x10-3 9.5 1.50
---
4 3454 826.8 4281 20.37 8.03x10-3 44.8 2.19
5 3454 1929 5383 18.30 1.50x10-2 93.9 5.13

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For all the experiments conducted with the activated carbon it is believed that absorption,
adsorption, and reaction (1) all played a role in removing SO2 from the inlet stream. The
evidence that the reaction occurred was the column became very hot when the SO2 was fed to the
column indicating an exothermic reaction was taking place. This agrees with the calculated heat
of reaction which is negative (Appendix E). Also, the pH of the water within the column was
determined to be between 1-2, compared to pH of 7 at the inlet, after each experiment indicating
that sulfuric acid from reaction (1) lowered the pH.

Initially when the inlet flow rate of SO2 was decreased we thought that tb would increase. This
hypothesis was based on the fact that adsorption into the pores of the activated carbon was the
primary mechanism of SO2 removal, and that as the flow rate of SO2 decreased it would take
longer for all the pores to become saturated. This hypothesis is for the most part consistent with
the results in table 2. One discrepancy however lies in experiment 2 where tb decreases when the
SO2 flowrate is reduced. One reason for this could be that all the pores within the catalyst were
not regenerated between runs because not enough water was flushed through the packing. If this
was the case then tb is a slight function of the volumetric flowrate used during the rinsing process.

To understand the large fluctuations in the mass of the SO2 removed before tb the system needs to
be analyzed from a reaction catalysis point of view. Initially it was assumed that reaction (1) was
rate limiting and that the rate expression could be modeled by a simple nth order rate expression
like (3). This would mean that as the concentration of the incoming SO2 increases, the reaction
rate would increase. Experiments 1-3 support this theory. Experiments 4 and 5 however do not
follow the nth order rate expression because the rate is actually lower for higher concentrations.
Therefore, either the reaction can’t be modeled using (3) or the reaction must be dependent on
another phenomena is which is more important in this situation.

If reaction (1) is mass diffusion limited then from equation (5) the overall rate is dependent on kc
and not kr. The rate of mass transfer, kc, is a function of the overall mass transfer coefficient, Kya
because the SO2 needs to diffuse from the gas phase into the liquid phase, and then to the surface
of the particle. In experiments 1-3 as the total gas flowrate is decreased the rate decreases. This
is expected from a diffusion limited reaction because as the total flowrate decreases the velocity
decreases which decreases convective diffusion and decreases the overall mass transfer
coefficient. When Kya decreases there will be a smaller driving force for diffusion in the liquid
phase for resulting in less molecules of SO2 that reach the catalyst surface that are able to engage
in a reaction. Therefore, decreasing the total gas flowrate will decrease the reaction rate.

Experiment 4 and 5 independently support the mass transfer limited theory because as the total
flowrate increases then the reaction rate increases. We might expect that the rates for experiment
4 and 5 would be the lowest rates of all the experiment since their total flowrates are the lowest.
The reason this is not the case is that the overall mass transfer coefficient is also dependent on the
concentration in the gas phase as can be seen from equation (1). Therefore, the higher the initial
concentration of SO2 the larger the overall mass transfer coefficient. It is thus very hard to
compare all of the rates because there are competing affects at work; large flowrates in
Experiment 1-3 and large concentration in Experiment 4-5. The obvious choice therefore in
designing an absorption column like this is to run it at the highest concentration and flowrate as
possible to be most effective.

Future Experiments

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Several things could be improved in this lab if using activated carbon in the future. Most
importantly due to the production of sulfuric acid, proper meshes that prevent activated carbon
from falling through the redistribution holes need to be obtained to place in the column. The
current mesh material being used is corroded by the sulfuric acid, making removal of the
activated carbon from the column difficult. Dissolved meshes also cause activated carbon
granules to fall to the bottom of the column or get stuck in the redistribution holes, and remaining
mesh threads to be mixed in the activated carbon. Mesh material could also be placed on the top
of the column to prevent activated carbon granules from floating up into the top of the column if
flooding occurs.

Also, developing a way to collect all of the water used to rinse the column could be very
beneficial, this way accurate determinations of the actual amount of H2SO4 in the water could be
determined so that a complete mass balance on the system could be calculated. Also, if the acidic
water is produced on a wider scale, it will need to be collected and treated (why don’t we put the
pH PID control people on it) rather than sent down the drain.

Another experiment could be conducted using plain carbon as the packing material, which is the
same size as the activated carbon currently being used. This would provide a source of
comparison so that it could be determined exactly how effective the catalyst is in removing SO2
from the inlet gas, when compared to an identical but inert packing material.

In this lab due to such tight packing of the activated carbon and low void fraction it was
impossible to run the absorption column continuously. Rather we had to operate as a batch
absorption, rinsing the carbon with water and then running the gas through the column with the
water off and repeating the process. One way to operate the column continuously is to mix the
activated carbon with rasching rings in the column. This will create more voids in the column for
the air and water to pass through, therefore preventing flooding. If this mixing technique is used
the amount of activated carbon in the mixture will have to be accurately measured, and the
amount of SO2 absorption will have to be considered. Other techniques of increasing void
fraction while still using activated carbon would be to use bigger activated carbon particles so the
packing won’t be so tight, or to make activated carbon into rasching rings or another packing
material shape.

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References

Blanco, J., Dahl, K., and Housing, C., Sulfur Dioxide Absorption. Unit Operations
Laboratory (06-311) Fall 1997.

Capaldo, K., Corbett, J., Kasibhatla, P., Fischbeck, P., and Pandis, S., Effects of Ship
Emissions on Sulfur Cycling and Radiative Climate Forcing over the Ocean.
Nature. Vol 400. 743-746. August 1999.

Fogler, H. Scott, Elements of Chemical Reaction Engineering. Second Edition, Prentice


Hall Inc., Upper Saddle River, New Jersey, 1992.

Geankopolis, Christie J., Transport Processes and Unit Operations. Third Edition,
Prentice Hall, Inc., Englewood Cliffs, New Jersey, 1993.

Pandis, Spyros. Chemical Reaction Engineering (06-301) class notes fall 1999.

Perry, Chemical Engineers’Handbook. Sixth Edition, McGraw-Hill Book Company,


New York, 1984.

Prieve, Dennis. Unit Operation of Chemical Engineering (06-202) class notes spring
1999.

Whitney, R. and Vivian, J., Absorption of Sulfur Dioxide in Water. Chemical Engineering
Progress. Vol 45. No 5. 323-337. May 1949.

This is excellent work -- I don't know what happened on your other two reports (one B level and
one C+ level), but this is very good. The writing, the analysis, and your conclusions. Clearly,
you got your act together. My rec = solid A on this report. MC

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Nomenclature

Uppercase

A pre-exponential constant
CA concentration of chemical A
E activation energy
G total vapor flowrate into the column
Ky overall mass transfer coefficient
L liquid flowrate into column
R gas constant
S cross-sectional area of the column
T temperature
V molar flowrate of the vapor
XA conversion of A

Lowercase

a interfacial area
k reaction rate constant
kc mass transfer rate constant
koverall overall rate constant
kr kinetics rate constant
rA reaction rate with respect to chemical A
tb break-through time
y mole fraction of gas in the vapor phase
zT height of the absorber column

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Appendix A: Equipment

Figure A.1: Absorption column

Figure A.2: Rasching Ring


Appendix B: Additional Theory for the Operating Line

To determine the operating line, the first step is to write a mass balance around the top piece of
the column which yields equation (B.1) where x and y are the mole fraction

L V y − La x a 
y= ⋅x +  a a  (B.1)
V  V 
of the transferable component in the liquid and vapor respectively, L is the total molar flow rate
of the liquid, and V is the total molar flow rate of the vapor. Equation (B.1) is called the
operating line. This line is usually slightly curved because the slope L/V changes along the
length of the column as the transferable component is absorbed.
A simplification to equation (B.1) can be made when only one component is transferred
between the phases. For example, in this lab if the evaporation of water into the air and the
dissolution of the air into the water can be neglected then the molar flow rates of the air and water
are constant along the length of the column. Therefore, L’(and similarly V’) can be defined by

(1 − x) ⋅L ≡ L′
(1 − y ) ⋅V ≡ V ′

These can be solved for L and V and plugged into equation (B.1) to yield

L′ xa V′y L′x V′ya


+ = + (B.2)
1 − xa 1 − y 1 − x 1 − ya

Now, define the mole ratio as

x
X ≡
1− x

for both the liquid and vapor phase. Equation (B.2) can then be rewritten in terms of mole ratios
to give

L′  L′ 
Y = ⋅X + Y a − ⋅X a  (B.3)
V′  V′ 

which is a straight line on mole ratio coordinates because the slope L’/V’is constant.
Additionally, if the liquid and vapor flowrates are extremely dilute with respect to the transferable
component then the mole ratio is approximately equal to the mole fraction. The mole ratios in
equation (B.3) can be replaced by mole fractions and will yield a linear plot as shown in Figure
(1). Since L ′≈L for dilute solutions equation (B.3) becomes

L  L 
y= ⋅x +  y a − ⋅x a  (B.4)
V  V 