Reactive Absorption & Non-Equilibrium Absorption

CHE-396 Senior Design
Reactive Absorption and Estimation of Solvent Losses
Reactive Absorption & Nonequilibrium Absorption
Senior Design CHE 396
By Chemical Concepts
Clint McElroy
Jeromy Miceli
Mike Viirre
Chris Woltz
Prof. Andreas Linninger
Table of Content
Introduction____________________________________________________________1
Section I
Overview of Physical Absorption_____________________________________2
Isothermal Example Problem_________________________________________7
Heat Effects______________________________________________________9
Solvent Losses___________________________________________________11
Estimation of Solvent Losses________________________________________12
Example Problem: Absorption of Acetone with Acetic Acid_______________16
Design Decisions_________________________________________________18
Section II
Introduction to Reactive Absorption___________________________________19
Process Operation_________________________________________________21
The Rate Equation for Mass Transfer and Reaction_______________________22
References_______________________________________________________25
Introduction
Absorption is the unit operation where one or more components of a gas stream are
removed by being taken up (absorbed) in a nonvolatile liquid (solvent). Physical
absorption and reactive absorption are the both readily used in industry today. Physical
absorption, the most common of the two, can be modeled in a number of ways. The 1st
being the isothermal case, the 2nd being the non-isothermal case, and finally the 3rd being
the case of an non-isothermal absorber including solvent losses. Each of these cases,
including a detailed sample calculation of the isothermal case, will be looked at in greater
detail.
Reactive absorption involves a liquid phase reaction that effects the liquid mass transfer
coefficient of the solvent. There are several advantages and disadvantages when
considering a reactive absorption unit. These advantages and disadvantages along with a
brief introduction on mass transfer will be included following physical absorption.
Page 1
Overview of Physical Absorption
Absorber
Absorption is the unit operation where one or more components of a gas stream are
removed by being taken up (absorbed) in a liquid solvent. Absorption can be either
physical or chemical. In physical absorption the gas is removed because it has a greater
solubility in the solvent than in other gases. In other words, the gas solute has a greater
affinity to be in the liquid phase. In chemical absorption the solute reacts with the solvent
and remains in solution. The reaction can either be reversible or irreversible. Reversible
reactions are often favored because the solvent can be regenerated, unlike irreversible
reactions, where the resulting liquid must be disposed of. A simple absorption system is
shown below in Figure 1.
j
Stripper
Absorber
Figure 1: Absorption Process

A brief overview of physical absorption will now be given to introduce the basic
principles and assumptions used when considering such a process.
In three component systems it is often assumed that
1. Carrier gas is insoluble.
2. Solvent is nonvolatile.
3. The system is isothermal and isobaric.
The Gibbs phase rule yields three degrees of freedom for the following three component
vapor/liquid system. Setting the temperature and pressure as constant, one degree of
freedom remains. Equilibrium data is usually represented by plotting solute compositions
in the vapor versus solute compositions in the liquid phase or by using Henrys law.
pB = HBxB
(1)
Page 2
Henrys law relates the partial pressure of B in the vapor (pB) to the mole fraction of B in
the liquid (xB) by using Henrys constant (HB) for the particular system. Since partial
pressure is defined as
yB = pB / ptot
(2)
yB = (HB / ptot)xB
(3)
Henrys law becomes
Since H is roughly independent of the total pressure, as pressure is increased, the mole
fraction in the vapor phase decreases. In other words, at greater pressures the gas solute
is absorbed more into the liquid phase. Henrys law constants depend on temperature and
are only valid for low concentrations of B or very dilute solutes.
The derivation of the operating lines for absorption are accomplished by material
balances around the top of the column. Again, these calculations are developed assuming
isothermal/isobaric operation, negligible heat of absorption, insoluble carrier gas, and a
nonvolatile solvent. Figure 2 is a representation of an absorber where L and G are the
solvent and carrier gas flow rates, respectively.
V,y1
yj+1
L,x0
1
yj+1
xj
N
V,yN+1
L,xN
Figure 2: Absorber
For very dilute solutions (<1% solute), overall flow rates can be used, and mass or mole
fractions can be used for operating equations and equilibria. However, overall flow rates
Page 3
of gas and liquid in concentrated mixtures cannot be considered because a significant

amount of solute may be absorbed, which would change gas and liquid flow rates and
give a curved equilibrium line. For now, interest lies in simple ideal absorber design.
Mole ratios are used as a basis for calculating mass balances around portions of the
absorber. The mole ratios X and Y are defined in the following way.
moles B in the gas
Y= moles pure carrier gas C
and
moles B in liquid
X= moles pure solvent S
(4a)
These mole ratios are also related to mole fractions by

y
Y = 1
and
X=
x
1 x
(4b)
The mass balance around the top of the column and stage j gives
Yj+1G + X0L = XjL + Y1G
(5)
or
Moles B in/hr = moles B out/hr
Solving for Yj+1 we obtain the operating line for absorption
Yj1
L
L
X j (Y1 X 0 )
G
G
This is a straight line with slope L/G and intercept ( Y1
(6)
L
X 0 ) . Plotting Y vs X
G
equilibrium data and the operating line gives a McCabe-Thiele type of graph for an
absorber. The following steps are taken when developing a graphical solution for an
absorption problem:
1. Plot Y versus X equilibrium data (convert from fractions to ratios).
2. Values of X0, YN+1, Y1 and L/G are known. Point (X0,Y1) is on operating line, since it
represents passing streams.
3. Slope is L/G. Plot operating line.
4. Starting at stage 1, step off stages: equilibrium, operating, equilibrium, ect.
In designing an absorber, or in solving absorption problems, usually Y N+1, X0, and G are
known, and L is to be found for a given Y1. In other words, the solvent flow rate
necessary to achieve a desired absorption is to be calculated. Operating lines for four
different absorbent flow rates are shown in Figure (6.9 p284 Seader), where each
operating line passes through the terminal point, (Y 1, X0), at the top of the column, and
corresponds to a different liquid solvent rate and corresponding slope, L/G.
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To achieve the desired value of Y1, the solvent flow rate L must lie in the range of
(operating line 1) to Lmin (operating line 4). The value of the solute concentration in the
outlet liquid, XN depends on L by a material balance on the solute for the entire absorber.
From equation (5), for j=N,
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X 0 L YN 1G X N L Y1G
or
L
G (YN 1 Y1 )
(X N X 0 )
(7)
(8)
The value of Lmin corresponds to a value of XN (leaving the bottom of the tower) in
equilibrium with YN+1, the solute concentration in the feed gas. It takes an infinite
number of stages for this equilibrium to be achieved. An expression for L min can be
derived as follows.
For the solute at stage N, the equilibrium relationship can be expressed as
KN
y N 1 YN 1 /(1 YN 1 )
xN
X N /(1 X N )
(9)
Solving equation (9) for XN and substituting the result into equation (8) gives
L min
G (YN 1 Y1 )
{YN 1 /[YN 1 (K N 1) K N ]} X 0
(10)
For dilute-solute conditions, where Yy and Xx, equation (10) becomes
L min G (
y N 1 y1
)
y N 1
x0
KN
(11)
Furthermore, if the entering liquid contains no solute, that is, X00, equation (11)
becomes
L min GK N (
y N 1 y1
) =GKN(fraction of solute absorbed)
y N 1
(12)
This equation is reasonable because it would be expected that Lmin would increase with
increasing G, K-value, and fraction of solute absorbed.
A graphical derivation of Lmin is also possible. As stated before, the value of L min
corresponds to a value of XN in equilibrium with YN+1. Since this is an equilibrium stage
(at stage YN+1), as well as a point on the operating line, the operating line extends from
the point (Y1, X0) to the equilibrium curve at YN+1. The slope of this line, and hence L min,
can be determined from these two points.
The selection of the actual operating solvent flow rate is based on some multiple of L min,
typically from 1.1 to 2. A value of 1.5 is typically used. In Figure (6.9 p284 Seader),
operating lines 2 and 3 correspond to 2.0 and 1.5 times Lmin, respectively. As the
Page 6
operating line moves from 1 to 4, the number of required equilibrium stages, N, increases
from zero to infinity. Thus, a trade-off exists between L and N, and an optimal value of L
exists.
To illustrate this method a sample problem will now be discussed.
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Case Study:
Isothermal Example Problem
Absorption is to be used to recover acetone from a gas mixture. Readily available acetic
acid will be used as the solvent. The inlet gas contains 5 mole % acetone and 95 mole %
methane. Using a basis of calculation of 100 mol/s of gas feed and assuming isothermal
conditions at 1 atm, determine the number of equilibrium stages required to recover 90%
of the acetone. Equilibrium data for the acetone acetic acid system is readily available.
The equation for the operating line is
X 0 L YN 1G X N L Y1G
10% of acetone remains in exit gas steam

(5 moles in)(.1 recovered) = .5 moles in exit gas stream
The mole ratios at the top of the operating line are
moles acetone (.1)(5)
X0=0 and
Y1=
=
=.00526
moles CH4
95
The known mole ratio at the bottom of the operating line is
YN+1=
.05
moles acetone
=.0526
1 .05
moles CH4
The equilibrium curve is generated from the vapor liquid equilibrium data given, by first
converting the mole fractions to mole ratios (y,x Y, X ), then plotting Y vs X. The
molar flow rate of the carrier gas G is given in the problem as
moles CH4
G = 95 second
(L/G)min is found as the slope of the operating line from point (Y 1,Xo) to the intersection
with the equilibrium curve at YN+1.
From graph, (L/G)min = 2.973 so, Lmin = (2.973)(95) = 282.4
moles acid
second
Lactual = 1.5 Lmin = 423.6 and (L/G)actual = 4.460

A solution for Lmin can also be found using the analytical method outined above.
Equation (10) gives the relationship between Lmin and KN. KN values can be found in the
literature, or from equation (9). The value for Y N+1 is known, and the XN stream is in
equilibrium with the YN+1 stream.
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y N 1
.05 (specified in problem)
3.24
xN
.0154 (from equilibrium data)
G (YN 1 Y1 )
95(.0526 .00526)
287.1
{YN 1 /[ YN 1 (K N 1) K N ]} X 0 {.0526 /[.0526(3.24 1) 3.24]} 0
KN=
L min
This value is very close to the one found using the graphical method.
Plot the operating line from (Y 1,Xo) with a slope of (L/G) min and step off stages to
determine the number of equilibrium stages needed. From the figure below it is seen that
about five equilibrium stages will be necessary to recover 90% of the acetone.
This is the theoretical number of stages required. The actual number of stages is found
from the relation Nactual = Ntheoretical / Eo where Eo is the stage efficiency. Therefore the
actual number of stages for a stage efficiency of 25% is
Nactual = 5/.25 = 20
So 20 equilibrium stages are needed to absorb 90% of the acetone from the inlet gas
stream.
Page 9
Heat Effects
One of the most important considerations when designing a gas-absorption column is to
determine whether or not to consider temperature effects. These temperature effects can
directly influence the solubility of the solute gas and are due to heat effects. Heat effects
to consider when designing a gas-absorber are:
1) The heat of solution of the solute that entails the heat of condensation, heats of
mixing, and heats of reaction.
2) The heat of vaporization or condensation of the solvent.
3) The exchange of sensible heat between the gas and liquid phases.
4) The loss of sensible heat from the fluids to internal or external cooling coils or to the
atmosphere via the tower walls.
There are various conditions that give rise to heat effects. The 1st being a considerable
heat of solution and the 2nd being a large amount of solute absorbed in the liquid phase.
The 2nd consideration can be achieved by high pressures in the absorber, low liquid flow
rate (L/G is small), and when the solute has a high solubility. When the solute is
absorbed rapidly, the equilibrium line tends to be curved upward towards the solute rich
end of the absorber. If the solvent is volatile and the rich gas is not saturated with respect
to the solvent, the solvent may evaporate near the bottom of the absorber and condense
near the top causing the operating line and the equilibrium lines to approach each other
somewhere in the column. This is known as a pinch point in the column. The pinch
point increases the height and the number of trays needed to absorb a certain amount of
solute in the solvent.
Operating variables such as pressure, temperature, L/G ratios also effect the performance
of a gas-liquid absorber. These will be discussed in more detail below.
Raising the operating pressure of the absorber tends to increase the separation efficiency
considerably. For example: the absorption of methanol from water-saturated air showed
that when the pressure was increased by a factor of two, the solvent was able to absorb
two times the concentration of methanol that could be tolerated in the feed gas while still
achieving the end concentration in the gas.
The temperature of the fresh solvent has little to no effect on the degree of absorption.
However, the temperature and humidity of the rich gas do effect the absorption process.
Cooling and consequent dehumidification of the feed gas to an absorption tower can be
very beneficial. High humidity or relative saturation with the solvent limits the capacity
of the gas phase to take up latent heat and does not favor absorption. If heat effects are
present, a dehumidification system may be beneficial and should be further investigated.
High liquid-to-gas ratios (L/G ratios) tend to result in less strongly developed temperature
profiles because of the high heat capacity of the liquid phase. As the L/G ratio increases,
the operating lines move farther away from the equilibrium line and more solute is
absorbed in each stage of the absorber. However, more heat is liberated in each stage and
Page 10
the temperature of each stage rises, shifting the equilibrium line upward. On the other
hand, as L/G decreases, the temperature maximum moves to the top of the tower and
inhibits the solvents ability to absorb the solute.
As discussed above, an absorber may form a pinch point when the solvent is volatile and
the solute is saturated with respect to the solvent. This in turn effects the number of trays
in the tower. Some solutions to reducing the number of plates are:
1)
2)
3)
4)
increasing the solvent flow rate

strategically placed coolers in the tower
dehumidifying the inlet gas
raising the operating pressure
The number of stages in an absorber is very important in terms of costing the absorber
and running the absorber. Decreasing the number of stages in turn decreases the cost of
the absorber. However, the above suggestions cost may outweigh the expense of the
trays.
Equipment considerations are also important when designing an absorber unit. If the
solute concentration in the feed gas is large and the heat of solution of the solute is large,
cooling coils should be considered. In most cases, heat liberation is largest towards the
bottom of the tower where more absorption takes place. In this situation, cooling coils
may only be needed at the bottom of the tower. Coggan & Bourne found that a 12-plate
tower with two strategically placed interstage coolers tripled the amount of ammonia feed
concentration for given off-gas specifications. More separation was possible in this unit
than with a simple column of 100 stages with no coolers.
There are a variety of ways in which a designer would go about approaching heat effects.
Depending on the job in consideration, a designer may:
1) add internal or external heat-transfer surface to remove heat from the absorber
2) treat the process as isothermal, where the temperature of the liquid is the same
everywhere in the absorber and the feed gas is sufficiently dilute
3) employ the classical adiabatic model, which assumes the heat of solution only shows
up as sensible heat in the liquid phase and the solvent vaporization is negligible
4) use semi-theoretical shortcut methods derived from rigorous calculations
5) employ rigorous design procedures requiring the use of a computer
For preliminary screening, the simpler cases may be sufficient (such as the above
example), but for a final absorber design, one should consider the rigorous approach.
Next we will discuss the more rigorous design procedure in the form of the matrix
method. This method will take into account all of the above heat effects including
solvent losses.
Page 11
Solvent losses
In the example we made many assumptions. Many are valid, such as the column
operating at constant pressure. However, there are many assumptions that are not
completely accurate and could harm the validity of our work. One of these assumptions
is that the solvent will not interact with the gas stream and be taken away by this stream.
If the solvent is water this is not really important, but if the solvent is anything other than
water, we want to account for possible solvent losses. The reason for this could be
economic (recovery of a valuable product or reactant) or environmental (removal of a
harmful impurity).
A good approximation to these losses can be found in Douglas (Douglas, 79). At lower
pressures we can assume that the fugacities of all species can be neglected. This means
that we can simplify our equilibrium relations to simply
PtyS = SPSxS
With a good recovery of solute we can assume that the only liquid in the top of the
column is that of the solvent
xS 1
If the solvent chosen has many of the same properties as the solute then the activity of the
solvent will be almost unity
S = 1
Going back to the first equation we obtain
yS = PS/PT
Hence, a quick estimate of solvent losses can be had by
mS
yS
G ySG
1 yS
While this provides a fairly simple model at which to obtain the value of solvent losses it
is not a satisfactory solution for real world conditions. What if we dont recover at or
above 99%? What if we dont operate the column isothermally? If we are truly
interested in what is happening inside the column, we need a more rigorous method to
explain the absorber. This method, known as the matrix method (Wankat), utilizes a
multivariate Newtonian convergence to attain the flows and temperatures of every stage
in the column. The basis of this method is described below:
Page 12
Estimation of Solvent Losses

For more concentrated solutions, absorbers and strippers are usually not isothermal, total
flow rates are not constant, and solutes may not be independent. For this reason, a much
better approximation of the actual operation of the absorber is a stage by stage calculation
of the absorber using a matrix method as described by Wankat (Wankat, 497). We first
start with mass balances from the bottom of the absorber and number going upward
according to the following diagram:
Calculating Solvent Losses Assuming Non-Isothermal Conditions and NonConstant Flow Rates
The General method of solving the absorber stage by stage is to first set up the mass
balances. The mass balance for stage 1 is:
B11 C1 2 D1
(15-45)
where
VK
B1 1 1 1 , C1 1 , D1 F1 z 1 V0 y 0
(15-46)
L1
and the component flow rates are 1 L1 x 1 and 2 L 2 x 2 . These equations are
repeated for each component.
For stage N the mass balance is
A N N B N N D N
(15-47)
where
V K
V K
A N N 1 N 1 , B N 1 N N
(15-48)
L N 1
LN
D N FN z N L N 1 x N 1
To solve the mass balances, a different matrix for each component must be made and
solved independently. The general solution for each of the matrices is:
Page 13

B1
A
2
C1
B2
C2
A N 1
B N 1
C N 1
AN
BN
1 D 1
D
2
2

N 1 D N 1
N D N
(8-23)
For a general stage j within the absorber, the mass balance for any component is:
Vj L j L j x j V j1 y j1 L j1 x j1 Fj z j
()
The unknown vapor compositions, yj and yj-1 can be replaced using the equilibrium
expressions:
y j K j x j and y j1 K j1 x j1
E j
T j1
E j
T j
V j1
Lj
h j
T j
E j
T j1
H j1
V j1 C PV , j1 A j
T j1
Vj
H j
T j
L j1
L j c PL , j Vj C PV , j B j
h j1
T j1
L j1c PL , j1 C j
(15-55a)
(15-55b)
(15-55c)
where we have identified the terms A, B and C for the tridiagonal matrix. The total
stream heat capacities can be determined from individual component heat capacities. For
ideal mixtures this is
C
c PL , j c PL ,i x i , C PV, j C PV ,i y i
(15-56)
i 1
j
i 1
j
For the next trial we hope to have (Ej)k+1 = 0. If we define
E j k D j
(15-57)
then the equations for the Tj can be written as

C1
0

B1
A
T1 D1
B
C
1
2
2
T D
2
2
0
A3
B3
C3
T3 D 2

(15-58)

A N 1 B N 1 C N 1
TN 1 D N 1
AN
BN

TN D N
This matrix can be inverted using a computer algorithm. The result will be all of the Tj
values. The check for convergence is by defining a T. This T can typically be defined
as approximately 10-2 to 10-3. The check is:
T j T
(15-59)
Page 14
If for all stages the convergence of Tj is achieved then the problem is solved. If (15-59)
is not satisfied, determine new temperatures using (15-54).
T j1 TJ 1 k 1 (T j1 ) k
(15-54)
This method can best be visualized in the form of a flow diagram as below (Wankat):
The major drawback to this method is the fact that the n n coefficient matrix depends
upon the number of stages. Of course, the number of stages is usually the thing you are
looking for in order to obtain a desired composition. Therefore, you must guess the
Page 15
number of stages and calculate the flows and compositions based on this number. If the
number you chose was not sufficient you must chose a higher one and repeat the process.
This tedious method obviously lends itself better to computer calculations than hand
calculations. Below is one iteration of the procedure using acetic acid as the solvent,
methane as a carrier gas and acetone as the solvent.
Page 16
Case Study:
Example Problem: Absorption of Acetone with Acetic Acid
An absorber with 3 equilibrium stages is operating at 1 atm of pressure. The feed is 100
mol/hr of a 95 mol% methane, 5 mol% acetone mixture which enters at 56C. The
solvent is pure acetic acid at 100 mol/hr and 30C. Find the outlet compositions
assuming an insulated column.
Solution: As a first guess lets assume the entire column is at the highest possible
temperature of 56C. We will also make some initial guesses about the liquid and vapor
flow rates:
L4=100
L3=101
L2=102
L1=103
V3=95 (mole/hr)
V2=97
V1=98
V0=100
Let's first find the K values for the individual components:

KAcetone(56) = 0.1106 , KAcid(56)= 0.9967 , KMethane(56)=200
We can now construct the mass matrices for the individual components:
M Acetone
1.105
.106
1.968
M Acid .948
M Methane
1.105
.105
1
1.958
.948
195.17
194.17
1
1.104
D Acetone
0
1
1.957
1
195.17
194.15
5
0
0
0
0
100
D Acid
1
195.16
D Methane
95
0
0
The inverse of the M matrix multiplied by the D matrix yields the solution matrix to l .
Where, as mentioned before 1 L1 x 1 . Once the l matrix is determined we can solve for
the new L values and check to see how closely they agree with the old L values. If they
are not within some value that can be chosen to be approximately 10-3 or so. Let's
proceed:
Page 17
L New
100
100
99.7
compared to our initial guesses of L Old 101 .
98.9
102
97.5
103
For these values , where
L j,old L j, New
L J ,old
, is higher than the allowable limits so we
must use our new approximation of L at every stage to get new component balance
matrices for the components. This was done three more times and the following flow
rates were obtained:
100
99.3
L
99.0
98.6
101.7
101.1
V
100.8
100
Now that the mass balance has been solved we must now solve the energy equations to
obtain the new temperature at each stage. This involves a new single tridiagonal matrix
whose coefficients depend upon the specific heats of liquid and gas at each stage. These
values are found from equations 15-56 and the cp functions are given in literature.
With these values the energy matrix can be formulated:
B1
A
2
0
C1
B2
A3
0
C 2
B 2
T1 D 1
T D
21
2
T3 D 3
The following values for delta T were obtained:

30
35.8
Temperatur e Pr ofile
52.7
56
These T values are not within the T value so we must take these new estimates of the
temperature and calculate new K values for all of the components on all of the stages.
Then we must perform new mass balances on each component as shown above. Once the
new mass balance is obtained we get a new temperature and see if this temperature is
Page 18
within T of the old temperature. Once this is done the column has been solved. This
procedure needed five more iterations to obtain the following results:
Amount of Acetone recovered in Solvent: 3.7 mol/h (74%)
Amount of Acetic Acid lost in gas stream: 7.9 mol/h (7.9%)
The following temperature profile was obtained:
Stage
V3
V2
V1
V0
Temperature
30
40.2
48.3
56
Temperature Profile of Acetone Absorption Process

60
50
Temperature, C
40
30
20
10
0
0
0.5
1.5
2.5
3.5
Stage (0 is the bottom of column)
Design Decisions
This clearly shows that temperature changes within the column are certainly not
negligible. These figures also give conclusive proof that solvent losses are an extremely
important aspect when designing a column. In our case we were operating in a fairly
narrow temperature range so the most important factor for this column is the pressure of
the structure.
When two atmospheres of pressure were used in this same 3-stage column it was possible
to recover 84% of the acetone and lose only 3.4% of the acid. One solution would be to
install a compressor to achieve these higher purity levels, however the pressure is but one
of the design variables. While it would be great to operate at 10 atm and require only on
Page 19
theoretical stage, this is not practical. The best combination of variables, unfortunately,
must be found by trial and error. Hold the pressure constant and perturb the number of
stages or the flow rate. Do you get the desired recovery? What is the highest recovery
for the lowest price?
This can be a time consuming process, but overall, the probable design result would be to
keep the costly solvent flow rate lower by increasing the number of stages and hope that
this will be sufficient without adding a compressor. The above example was carried out
with three stages simply to show how the computation could be carried out by hand.
However, a much better separation would be achieved with 10 or 15 stages.
Page 20
Introduction to Reactive Absorption

Mass transfer in absorbers is explained using the two-film theory. The boundary between
the gas phase and the liquid phase is presumed to consist of a gas film adjacent to a liquid
film. Flow in both of these films is assumed to be laminar or stagnant. The main-body gas
phase and liquid phase are assumed to be completely mixed in turbulent flow so that no
concentration gradient exists in the main body of either phase. The solute concentration
in the gas film at the interface is assumed to be in equilibrium with the solute
concentration in the liquid film at the interface. There is a solute concentration gradient
across both the gas film and the liquid film.
The rate of mass transfer from the main-body gas phase through the gas film is
given by:
N kG ( p p )
Where kG is the gas phase mass transfer coefficient and p and p are the pressures in the
bulk gas and gas film respectively.
Similarly, the solute transferred per unit time through the liquid film to the mainbody liquid phase is given by:
N kL ( x x )
Where (x x ) represents the concentration driving force for mass transfer from the
liquid film to the bulk liquid phase, and kL is the liquid phase mass transfer coefficient.
Mass transfer theory considers that the gas-film and liquid-film resistances are in
series. Overall mass transfer coefficients for both phases are defined as :
1
1
m
KG
kG kL
m= slope of equilibrium curve
1
1
1
KL
mkG kL
The overall transfer coefficient depends partly on the nature of the gas film and partly on
the nature of the liquid film.
In reactive absorption, a fluid-fluid reaction takes place between a gas phase and a liquid
phase. At the same time, mass transfer from the gas to the liquid phase is also occurring.
To be able to completely understand reactive absorption, one must first gain some
understanding of the kinetics of fluid-fluid reactions. A detailed discussion into the theory
of such is well beyond the scope of this paper. Literature on this subject can be found in
most books on chemical reaction kinetics such as (Levenspiel,1999 ).
Absorption occurs through mass transfer. Therefore any factors that have any effect on
the overall mass transfer coefficient will affect the rate of absorption. Many times the
presence of a chemical reaction can influence the mass transfer rate. One must consider
the impacts of chemical equilibrium and reaction kinetics on the absorption rate in
Page 21
addition to accounting for the effects of gas solubility, diffusivity, and system
hydrodynamics.
There is no sharp dividing line between pure physical absorption and absorption
controlled by the rate of a chemical reaction. Most cases fall in an intermediate range in
which the rate of absorption is limited both by the resistance to diffusion and by the finite
velocity of the reaction.
Consider an absorber with a reaction occurring in the liquid phase. Since the reaction is in
the liquid phase, the gas-phase rate coefficient K G is not affected. If the reaction is
extremely fast and irreversible, the rate of absorption may be governed completely by the
resistance to diffusion in the gas phase. Therefore the absorption rate can be estimated by
knowing the gas-phase rate coefficient KG. The liquid-phase rate coefficient KL is
strongly affected by fast chemical reactions and generally increased with increasing
reaction rate.
The highest possible absorption rates will occur under conditions in which the liquidphase resistance is negligible and the equilibrium back pressure of the gas over the
solvent is zero. This condition can be attained if KL is very large. Frequently, even though
reaction consumes the solute as it is dissolving, thereby enhancing both the mass-transfer
coefficient and the driving force for absorption, the reaction rate is slow enough that the
liquid-phase resistance must be taken into account. This may be due to an insufficient
supply of a second reagent or to an inherently slow chemical reaction. What this all boils
down to is that the liquid-phase rate coefficient K L in the presence of a chemical reaction
normally is larger than the value found when only physical absorption occurs. To account
for the effects of chemical reaction, the liquid enhancement factor, E is introduced.
E
( rate of take up of solute when reaction occurs)

(rate of take up of solute for straight mass transfer)
kL
1
kLo
Process Operation
Pressure Constraints
Reactive absorption is best run at high pressures. The high pressure will force more gas
into the liquid phase and consequently a better reaction conversion will be attained.
However, to operate at high pressures requires the use of a compressor, which is usually
the most expensive unit in a plant design.
Temperature Considerations
In physical absorption it is best to operate at low temperatures to promote the gas to go to
the liquid phase and to avoid solvent losses to the vapor phase. In reactive absorption one
would want to operate at low enough temperatures to allow for absorption of the gas to
the liquid, but if the kinetics governing the reaction are not favorable at this temperature
Page 22
we have to weigh the possibilities of operating at a higher. The burden is on the engineer
to choose a solvent that reacts with the solute at low enough temperatures.
Finding a Suitable Flowrate
Flooding issues, like those in physical absorption dominate this topic. We obviously
want to operate below the flooding velocity of the gas. However, in chemical absorption
if the is essentially irreversible and the equilibrium partial pressure of the solute is zero,
then the countercurrent and co-current absorber require the same number of stages
(McCabe, 730). This is advantageous because co-current operation eliminates the
flooding concerns. We can have very high flow rates for both the gas and solvent streams
and still attain very good separations.
Applicability and Limitations
Reactive absorption is typically used when physical absorption is not able to attain the
proper separation desired. Here are some pros and cons with reactive absorption:
Advantages of using reactive absorption
1)
2)
3)
a reaction in the liquid phase reduces the equilibrium partial pressure of the solute
over the solution, which greatly increases the driving force for mass transfer
Absorption plus reaction increases the mass transfer coefficient by introducing a
greater effective interfacial area since absorption can now take place in the nearly
stagnant regions as well as in the liquid holdup
Chemical absorption usually has a much more favorable equilibrium relationship
than physical absorption (solubility of most gases is very low)
Disadvantages of using reactive absorption

1)
2)
3)
4)
the Murphee plate efficiency is often quite low (10% is not unusual)
the suitable solvent stream may not be available in the current process or the
solvent stream may be very expensive
heat of reaction introduces non-isothermal conditions which may require cooling
coils (increase in capital costs)
additional costly separation unit may be required
The Rate Equation for Mass Transfer and Reaction

The basic reaction in reactive absorption is:
Page 23

Solute (gas liquid) + solvent ( )
product (s or
or g)
Here we have three factors to consider: what happens in the gas film, in the liquid film,
and in the main body of the liquid as shown in the figure below:
From a discussion on the kinetic theory of fluid-fluid reactions with simultaneous mass
transfer ( Levenspiel, 1999 ) , it turns out that there are eight basic cases for which
reactive absorption can occur.
Case A:
Case B:
Case C:
Case D:
Case E and F:
Case G:
Case H:
Instantaneous reaction with low concentration of solute

Instantaneous reaction with high concentration of solute
Fast reaction in liquid film, with low concentration of solute
Fast reaction in liquid film, with high concentration of solute
Intermediate rate with reaction in the film and in the main body of
the liquid
Slow reaction in the main body but with film resistance
Slow reaction, no mass transfer resistance
These eight cases can best be visualized by the diagram below:
Page 24
The general rate equation for fluid-fluid reaction with simultaneous chemical reaction is:
1
1
H
A
HA
-rA=
kGa kLaE kCBf 1

gas film liquid film
resistance resistance
bulk liquid
resistance
where:
Page 25
a = interfacial area
H = Henrys constant
CB = solute concentration
E = liquid enhancement factor
The liquid enhancement factor E is extremely important when dealing with reactive
absorption systems. It is introduced into the rate expression to adjust the liquid mass
transfer coefficient and takes into account reaction conditions.
Page 26
References
1. Douglas, J.M., "Conceptual Design of Chemical Engineering," McGraw-Hill, New
York, 1988.
2. King, C.J., "Separation Processes," McGraw-Hill, New York, 1971.
3. Perry, R.H. and Green, "Perry's Chemical Engineer's Handbook," New York, 1997.
4. Reid, R.C., Prausnitz, J.M. and B.E. Poling, "Properties of gases and liquids,"
McGraw-Hill, New York, 1987.
5. Seader, J.D., and Henley, E.J., "Separation Process Principles," John Wiley & Sons,
New York, 1998.
6. Strigle, R.F., "Packed Tower Design and Applications," Gulf Publishing, Houston,
1994.
7. Wankat, P.C. "Equilibrium Staged Separations," Prentice Hall, Englewood Cliffs,
New Jersey, 1998
Page 27

Reactive Absorption & Non-Equilibrium Absorption

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CHE-396 Senior Design

Reactive Absorption and Estimation of Solvent Losses