CHG 3111

Unit Operation

Chapter 10
Gas-Liquid Separation and Operations
4.1 Mass Transfer
CHG 3111/B. Kruczek
Approach
2
Mass Transfer Thermodynamics
(Equilibrium)
Mass and Energy
Balances
Size of
Equilibrium
Stage
Number of
Equilibrium
Stages
Operating
Conditions
Complete
Design
CHG 3111/B. Kruczek
3
Introduction
Separation by Phase Contact
Many chemical processes and biological substances occur as mixtures of different
components in the gas, liquid or solid phase.
To separate or remove one or more of the components from its original mixture, it
must be contacted with another phase.
The two phase pair can be gas-liquid, liquid-liquid or liquid-solid.
When different phases are brought into contact, a solute or solutes can diffuse from
on phase to the other.
The phases are then separated by physical methods, where one phase is enriched
while the other is depleted in one or more components.
Contact
Phase 2
Phase 1
Separation
Phase 1
Phase 2
The separation processes are classified depending on the nature of Phases 1 and 2:
Gas/Liquid: absorption and stripping; Vapor/Liquid: distillation; Liquid/Liquid: liquid extraction;
Liquid/Solid: leaching, crystallization, adsorption, ion exchange; Gas/Solid: adsorption
Other separation processes include:, membrane processes, filtration, settling and
sedimentation, centrifugal processes
CHG 3111/B. Kruczek
4
Introduction
Processing Methods:
Batch vs. continuous





Concurrent vs. countercurrent





Multi-stage process
V
2

L
0

V
1

L
1

time
V
2

L
1

V
1

L
0

V
1

L
1

V
2

L
0

Batch
process
Continuous
process
V
2

L
1

V
1

L
0

L and V are [kg or moles] in batch processes and [kg/s or moles/s] in continuous processes.
The two phases having the same subscript (e.g. L
1
, V
1
) are in equilibrium
Multi-stage processing is possible only in case of countercurrent operation. Why?
NB: Design of stage processes requires equilibrium relations between the phases in contact
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5
Equilibrium Relations Between Phases
Phase Rule and Equilibrium:
Phase rule determination of the degrees of freedom:

F = C P + 2


Example: CO
2
-air-water system has 2 phases and 3 components
F = C P + 2 = 3 -2 + 2 = 3; therefore, 3 variables need to be specified (e.g.: T, P, y
CO2
)
Where: P = number of phases at equilibrium
C = number of total components in the two phases
F = number of variants or degrees of freedom of the system
Gas-liquid equilibrium
For a specific system, equilibrium data is determined experimentally, but some
generalizations are applicable.
For a system involving ideal gas and liquid phases, Raoults law applies:

A A A A A s
y P p x p = =
For ideal liquid solutions the activity coefficient is equal to unity
Where: y
A
and x
A
are the mole fractions of A bulk gas and bulk liquid
phases, p
A
and p
As
are the partial and vapor pressures of A,
respectively, and
A
is the activity coefficient of A in liquid solution
CHG 3111/B. Kruczek
6
Equilibrium Relations Between Phases
Phase Rule and Equilibrium:
Gas-liquid equilibrium
Henrys law is applicable for dilute phases (x
A
< 0.1)
o r '
A A A A A
y P p H x y H x = = =
For x
A
> 0.1, p
A
is no longer directly proportional to x
A

Where: H and H are the Henrys law constants in appropriate units
CHG 3111/B. Kruczek
Absorption and Stripping
7
Mass Transfer Considerations
1. Mass transfer between phases
2. Single point analysis film and overall mass transfer
coefficients
3. Introduction to equipment
4. Equilibrium stage and Height of Transfer Unit
5. Operation and design of packed towers
CHG 3111/B. Kruczek
8
Mass Transfer Between Phases
Gas-Liquid Interface
Description of the system

V
V
L
L
Liquid (L) and gas (V) phases, both containing solute A, are brought in contact; we shell
first consider a single point anywhere within the system
Liquid is assumed to be non-volatile, while the bulk gas phase is assumed to be insoluble
in the liquid so that only solute A is being transported.
Bulk liquid and bulk gas phases are not in equilibrium, but equilibrium at the interface is
established instantaneously
Gas-phase
A in gas G
Liquid-phase
A in liquid L
y
Ai

x
Ai

y
AG

x
AL

Interface
N
A

Film
where: y
AG
and x
AL
are the
mole fractions of A bulk
gas and liquid phases,
and y
Ai
and x
Ai
are the
corresponding mole
fractions at the interface
( )
a n d f o r d i l u t e s o l u t i o n s '
A i A i A A
y f x y H x = =
CHG 3111/B. Kruczek
9
(A) (B)
N
A

Diffusion equation in a single phase (Ficks law):
N
A
= -cD
AB
(dy
A
/dz) + y
A
(N
A
+ N
B
)
Equimolar counterdiffusion Diffusion of (A) through non-diffusing (B)
N
A
= -N
B
N
B
= 0
(A) diffusing from the gas to liquid and
(B) in equimolar counter diffusion from
liquid to gas
(A) diffusing through a stagnant gas and then
through a stagnant liquid
Ammonia (B) Water (A):
Both ammonia and water are soluble in
each other and diffusion occurs by both
A and B

Air (B) Water (A):
water vaporizes to air, but air is insoluble in water.
Air (B) & Ammonia (A) Water (C):
Ammonia diffuses through B in the gas phase (air is
insoluble in water) and then through a non-diffusing
liquid (water does not vaporizes)
N
A
= k'
x
(x
Ai
x
AL
) = k'
y
(y
AG
y
Ai
) N
A
= k
x
(x
Ai
x
AL
) = k
y
(y
AG
y
Ai
)
Film Mass-Transfer Coefficients
(A) (B)
N
A

N
B

Mass Transfer Between Phases
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Composition of Phases at the Interface
Bulk phase concentration
y
Ai

x
Ai

y
AG

x
AL

N
A

Mass Transfer Between Phases
Taking samples from the liquid and gas phases allows
determination of x
AL
and y
AG
, but not x
Ai
and y
Ai
Composition of bulk liquid and gas phases at a specific
location determine an operating point P, which has
coordinates (x
AL
,y
AG
)
Determination of x
Ai
and y
Ai
for a given operating point P requires mass transfer
coefficients in the liquid and gas phases
For equimolar counterdiffusion:
( ) ( )
AG Ai x
A y AG Ai x Ai AL
y AL Ai
y y k
N k y y k x x
k x x
'
' ' = = =
'
The composition of point M is determined by
the intersection of the equilibrium line with a
straight line of the slope determined by the
mass transfer coefficients that passes through
point P.
How do we determine point M analytically?
CHG 3111/B. Kruczek
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Composition of Phases at the Interface
y
Ai

x
Ai

y
AG

x
AL

N
A

Mass Transfer Between Phases
For the case of diffusion of A through stagnant B:
( ) ( )
AG Ai x
A y AG Ai x Ai AL
y AL Ai
y y k
N k y y k x x
k x x

= = =

NB: If one is provided with k mass transfer coefficients, the determination of the composition at the interface in the
case of diffusion of A through stagnant B requires a trial and error procedure. Alternatively, the coordinates of
point M in this case can be determined analytically by solving a system of non-linear equations.
Bulk phase concentration

x
y
k
k

( ) ( )
1 1
where:
y
x
y x
A A
iM iM
k
k
k k
y x
'
'
= =

( )
( ) ( )
( ) ( )
( ) ( )
( ) ( )
( )
1 1
1
1 1
and:
ln ln
AL Ai BL Bi
A B
iM iM
AL Ai BL Bi
x x x x
x x
x x x x

= = =
( (


( )
( ) ( )
( ) ( )
( ) ( )
( ) ( )
( )
1 1
1
1 1 ln ln
Ai AG Bi BG
A B
iM iM
Ai AG Bi BG
y y y y
y y
y y y y

= = =
( (


CHG 3111/B. Kruczek
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Overall Mass Transfer Coefficients

Compositions of phases at the interface during a mass transfer process cannot be
measured experimentally, thus k'
y
and k'
x
((k
y
and k
x
) are difficult to estimate.

Alternatively, the rate of transfer of solute A can be described in terms of the overall
mass-transfer coefficients K'
y
and K'
x

Where: y*
A
= mole fraction of A in gas phase that would
be in equilibrium with x
AL

x*
A
= mole fraction of A in liquid phase that
would be in equilibrium with y
AG

Mass Transfer Between Phases
( ) ( )
* *
' '
A y A G A x A A L
N K y y K x x = =
y*
A

x*
A

Bulk phase concentration
NB: The above overall mass transfer coefficients are applicable for a single point stretching from the bulk liquid
to the bulk gas phase. They are not applicable to describe the mass transfer along the entire column!
CHG 3111/B. Kruczek
13
Overall Mass Transfer Coefficients in terms of Film Coefficients

Driving force for the mass rate equation in terms of the overall mass transfer coefficient
Mass Transfer Between Phases
x
*
A

y
*
A

Slope =m''
E
D
Slope =m'
Approximation of the equilibrium line by the slopes m and m, and unless Henrys
law is applicable, m m
( ) ( ) ( )
* *
G a s p h a s e d r i v i n g f o r c e l e n g t h o f l i n e
A G A A G A i A i A
P E y y y y y y = = = +
( ) ( )
( )
* *
L i q u i d p h a s e d r i v i n g f o r c e l e n g t h o f l i n e
A A L A A i A i A L
P D x x x x x x = = = +
*
slope of
Ai A
Ai AL
y y
EM m
x x

' = =

*
slope of
AG Ai
A Ai
y y
M D m
x x

'' = =

Re-expression od driving forces in terms of m and m

( ) ( ) ( )
*
G a s p h a s e d r i v i n g f o r c e '
A G A A G A i A i A L
y y y y m x x = = +
( )
( )
( )
*
L i q u i d ph a s e d ri v i n g fo rce
"
A G A i
A A L A i A L
y y
x x x x
m

= = +
CHG 3111/B. Kruczek
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Mass Transfer Between Phases
CHG 3111/B. Kruczek
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Mass Transfer Between Phases
CHG 3111/B. Kruczek
16
Mass Transfer Between Phases
The solute A is being absorbed from a gas mixture of A and B in a wetted-wall tower with the
liquid flowing as a film downward along the wall. At a certain point in the tower the bulk gas
concentration y
AG
= 0.25 mole fraction and the bulk liquid concentration is x
AL
= 0.05. the tower
is operating at 298 K and 1.01x10
5
Pa and the equilibrium data are as follow.

The solute A diffuses through stagnant B in the gas phase and then through a non-diffusing
liquid. Using correlations for dilute solutions in wetted-wall towers, the film mass-transfer
coefficient for A in the gas phase is predicted as k
y
= 1.465x10
-3
kg mol A/s.m
2
.
.mol frac and for
the liquid phase k
x
= 1.967x10
-3
kg mol A/s.m
2
. mol frac.

Calculate the interface concentrations y
Ai
and x
Ai
and the flux N
A
.

x
A
y
A
x
A
y
A
0 0 0.25 0.187
0.05 0.022 0.30 0.265
0.10 0.052 0.35 0.385
0.15 0.087
0.20 0.131

Example 1: Interface composition
CHG 3111/B. Kruczek
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Equipment for Gas Liquid Contact
Tray tower
General information
Classification of the contact equipment
Tray towers
Gas in
V
N+1
, y
N
Liquid in
L
0
, x
0
Liquid out
L
N
, x
N
Gas out
V
1
, y
1
Liquid out
L
1
, x
1
Gas in
V
1
, y
1
Liquid in
L
2
, x
2
Gas out
V
2
, y
2
Packed towers
Wetted wall towers, spray towers and chambers
Towers are typically run in a countercurrent mode (why?)
Packed tower
Rate equation
Unlike the analysis so far, which were
focused on a single point, we are now
interested in n
A
= N
A
A
s
not just N
A
Purpose of the equipment is to maximize n
A
by:
Maximization of the interfacial area (A
s
) exposed
between the phases
Optimization of the nature and degree of
dispersion of one phase into another

Apart from Absorption and Stripping, packed and tray
towers are used Humidification, Dehumidification,
Adsorption and Distillation applications
CHG 3111/B. Kruczek
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Equipment for Gas Liquid Contact
Tray Towers - types of trays
Sieve tray
Gas bubbles through holes (3 12
mm) in the tray and then through the
liquid flowing over the tray; flowing gas
prevents liquid going into the holes.
Depth of the liquid on the tray.
maintained by overflow, outlet weir.
Overflow liquid flows into downspout
to the next tray below;

bubble-cap tray
sieve tray
Bubble-cap tray
Gas rises through opening through the
openings in tray into the bubble caps,
and then through slots in the periphery
of each cap

Valve tray
Modification of sieve try opening in
the tray are covered by lift-valve cover;
prevents liquid going through the
openings

CHG 3111/B. Kruczek
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Equipment for Gas Liquid Contact
Random packing, for example Raschig rings (a), Berl saddle (b),
Pall ring (c), Intalox metal (d), Jaeger tri-pack (e)
Packed Towers
(a) (b) (c) (d) ( e)
Random
packing
Liquid out
Gas in
Liquid in
Gas out
Liquid
distributor
Liquid
re-distributor
Packing
support
Shell
Packed tower is uniformly filled with a packing material no distinct equilibrium stages
Types of packing
Structured packing assembled into repeatable structural elements,
rather than randomly damped into the column
CHG 3111/B. Kruczek
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Equipment for Gas Liquid Contact
Summary of packing characteristics
NB1: Ceramic Rasching Rings of nominal size 1.5 inch serve as a reference for the determination of mass
transfer coefficient in packed beds
NB2: Packing Factor is a measure of the capacity of the tower, and F
p
a/c
3

CHG 3111/B. Kruczek
21
Equilibrium Stage in Gas Liquid Contact
Tray Towers
The objective: the liquid (L
1
) and gas (V
1
) leaving a tray are in equilibrium
V
1
,y
1

Tray efficiency Murphree efficiency (E
M
)
Represents the average tray efficiency and can be
expressed in terms of liquid or gas phase compositions
What can be done to maximize try efficiency?
2 1 1 0
2 1 1 0
' '
or
MG ML
y y x x
E E
y y x x

= =

NB: If tray efficiency is 100%, the spacing between the trays determines the length of the tower to achieve
one full equilibrium stage
V
1
,y
1

V
2
,y
2

V
2
,y
2

L
1
,x
1

L
1
,x
1

L
0
,x
0

L
0
,x
0

M

N

MNP = Incomplete Equilibrium Stage
y
1
y
2
x
1
x
0
N

M

y
1
x
1
MNP = Complete Equilibrium Stage
CHG 3111/B. Kruczek
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Equilibrium Stage in Gas Liquid Contact
Packed Towers
Liquid out
Gas in
Liquid in
Gas out
Height of transfer unit is equivalent to one full equilibrium stage in a packed tower
V
1,
y
1
V
2
,y
2
L
2
,x
2

L
1
,x
1

H M

N

MNP = Equilibrium Stage
y
2
y
1
x
1
x
2
Parameters affecting the size of transfer unit include:
Mass transfer coefficients in the liquid and gas phases
The operating conditions, i.e., flow rates of gas and
liquid, and temperature
Properties of the packing material (Table 10.6-1)
Solubility of solute in the liquid and gas phases
CHG 3111/B. Kruczek
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Equilibrium Stage in Gas Liquid Contact
Height of transfer unit can be expressed in different ways
NB: In packed beds the surface area for mass transfer is unknown, therefore, mass transfer coefficient is
combined with the specific surface of bed
Height Transfer Unit (H) in Packed Towers
( )
1 '
G
y y
iM
V V
H
k aS k a y S
= =

Height of transfer unit based on the gas film:

( )
1 '
L
x x
iM
L L
H
k aS k a x S
= =

Height of transfer unit based on the liquid film:

( )
1 '
OG
y y
iM
V V
H
K aS K a y S
= =

Overall height of a gas-phase transfer unit:

Overall height of a liquid-phase transfer unit:
( )
1 '
OL
x x
iM
L L
H
K aS K a x S
= =

Where: V and L are the average molar flows of gas and liquid phases respectively, S is the
cross sectional area of the tower, and a is the specific surface of packing
Question: Are H
G
, H
L
, H
OG
, H
OL
the same?
CHG 3111/B. Kruczek
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Equilibrium Stage in Gas Liquid Contact
Recall the analysis for the determination of the conditions at the gas liquid interface
NB: In the literature the terms H
y
, H
x
, H
Oy
, H
Ox
are used instead of H
G
, H
L
, H
OG
, H
OL
; they are identical to
each other
Correlations between height transfer units
Since in packed beds the exact area of contact
between the phases is not known, k [mol/m
2
s]
is replaced by ka [mol/m
3
s] and:
( ) ( )
and
OL L G OG G L
H H L mV H H H mV L H = + = +
x
*
A

y
*
A

Slope =m''
E
D
Slope =m'
slope ' '
x y
k a k a =
1 1
y y x
m
K a k a k a
'
= +
' ' '
1 1 1
"
x x x
K a k a m k a
= +
' ' '
NB: for dilute solutions:
m = m = m
Using the definitions of heights of transfer units (H
G
, H
L
, H
OG
, H
OL
) it can be shown that:
CHG 3111/B. Kruczek
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Mass Transfer Coefficients in Packed Towers
Complexity of prediction of individual film coefficients empirical approach
Correlations for Height of Transfer Unit
Since the transport of solute A in absorption/stripping processes involves two phases, the
experimentally determined mass transfer coefficients are the overall (K'
y
a and K'
x
a) rather
than the individual (k'
y
a and k'
x
a) film coefficients.
For K'
y
a k'
y
a the solute must be highly soluble in the liquid phase, e.g.: NH
3
Air Water
system, the liquid phase resistance is roughly 10% of the total resistance.
For K
x
a k
x
a the solute must very insoluble in the liquid, e.g.: CO
2
Air Water system,
the gas phase resistance is practically negligible.
For the design packed beds, it is more practical to use the correlations for height of transfer
unit rather than for mass transfer coefficient (why?)
0 35
0 5 0 5
0 226
0 660 6 782 0 878
.
. .
.
For the gas film coefficient:
. . .
y
Sc x
G y
p
G
N G
H H
f

| |
| |
| | | |
| = = |
| |
|
|
\ . \ .
\ .
\ .
0 3
0 5
3
0 357
372 6 782 0 8937 10
.
.
.
For the liquid film coefficient:
. .
x Sc
L x
p
G N
H H
f

| |
| |
| |
| = = |
|
|
|

\ .
\ .
\ .
where: G
x
and G
y
are the mass fluxes [kg/m
2
s] of liquid and gas, and f
p
is the relative mass transfer
coefficient (Table 10.6-1)
CHG 3111/B. Kruczek
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Operation of Packed Towers
Flow Rates of Gas and Liquid
Flow rates of liquid and gas directly affect the Height of Transfer Unit, but also they
determine the pressure drop and the operation mode in the tower
Liquid out
Gas in
Liquid in
Gas out
Liquid holdup and loading point
Liquid holdup is the quantity of liquid contained in the packed bed.
For a given liquid velocity (L) the loading point is the upper limit of
the gas velocity (V) for a reasonably constant liquid holdup.
Below the loading point, gas phase is continuous and liquid phases
is dispersed.
Above the loading point (loading region), liquid pools form at the top
of the column gas pressure drop sharply increases as G increases.
In the loading region liquid entrainment is observed, liquid holdup
sharply increases, mass transfer efficiency decreases, and column
operation is unstable.
Flooding point continuous liquid layer at the top of the column;
pressure drop increases infinitely with increasing G.

Therefore: Although a packed column can operate in the loading region, most columns are designed
to operate below the loading point, in the preloading region
CHG 3111/B. Kruczek
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Operation of Packed Towers
Prediction of Pressure Drop
Pressure drop in random and structured packing
Random Packing
3
m
-1
superficial gas velocity [ft/s]
and densities of gas and liquid lb ft
packing factor ft can be found in Table 10.6-1
G
G L
p
F
u

=
(
=

(
=

2
m
3
m
kinematic viscosity of liquid centstokes
and mass velocities of gas and liquid [lb /s ft ]
and densities of gas and liquid lb ft
G L
G L
G G
v

= (

=
(
=

where:

Structured Packing
Regardless of packing the pressure at flooding:
1 0 7
1
60 0 115
60 2
.
2
2
for ft : in. H O/ft .
For ft : in. H O/ft
p flood p
p flood
F P F
F P

< A = (

> A = (

CHG 3111/B. Kruczek
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Operation of Packed Towers
Design Factors
Preliminary design procedure type of packing, G
L
/G
G
, and total gas flow are known
The ratio of tower diameter to the random packing size should be 10:1 or greater
For every 3 m height of packing, a liquid redistribution should used to prevent liquid
channeling.
For random packing tower diameter should be less than 1.0 m
Loading in packed towers starts at 65 70% of the flooding velocity
Adsorption should be run at 50 70% of flooding velocity (upper end at high flow
parameter)
Therefore: The first step in the design of a packed tower is to determine the limiting
flow rates and hence the tower diameter
1. Knowing G
L
/G
G
the flow parameter can be evaluated
2. Determination of flooding pressure drop, which along with the flow parameter are used to
estimate the capacity parameter
3. Using the capacity parameter, the maximum G
G
is established.
4. For the suitable % of the flooding, the actual G
G
, G
L
, and D
P
are calculated.
5. Knowing the total gas flow rate and G
G
the tower internal diameter is calculated
CHG 3111/B. Kruczek
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Mass Transfer in Design Calculations
Predict H
G
, H
L
, and H
OG
and the percent resistance in the liquid phase for absorption of ammonia
from air by water in a dilute solution in a packed tower with 1.5 in. metal Pall rings at 303 K and
101.32 kPa pressure. The flow rates are G
x
= 4.069 kg/s m
2
and G
y
= 0.5424 kg/s m
2
.

Example 2: Height of Transfer Units