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dehumidification
humidification
Membrane Separation
Separation by selectively controlling the passage from one side
of the membrane to the other. The membrane serves to:
Prevent intermingling of two miscible
phases
Prevent ordinary hydrodynamic
flow, thus movement of substances
through it is by diffusion
Dialysis is an example of membrane
separation
Mechanism of Mass Transfer
Mass transfer occurs by two basic mechanisms:
Molecular Mass Transfer
Mass is transferred by the molecular in quiescent fluid
Convection
Mass is transferred from a surface of a moving fluid aided by the
dynamic characteristics of the flow
Both mechanisms often act simultaneously
Frequently, one mechanism can dominate
quantitatively so that approximate solutions
involving only the dominant mode can be used
Molecular Mass Transfer
Molecular Mass Transfer in Gases
∑w i =1 A 11 16
B 4 30
C 6 2744
Molar Concentration
The molar concentration of component i (ci) is
the number of moles of component i per unit
volume =c
ni
=
ρi
i
Vol M
i
molecualr weight of species i
Solving 7, 8 gives:
yH2O= 0.1; yN2= 0.72
Solution: Calculation of Mav, c and ρ
g
M av = ∑M i y i = 0.12 x0.44 + 0.06 x 32 + 0.1 x18 + 0.72 x 28 = 29.16 1
mol
110 x10 3
=c =
P
= 26.5
mol
RT 8.314 x 500 m3
mol g g
=ρ c= x 29.16 = 0.772
M av 0.0265
liter mol liter
Average Velocities: Mass Average
In a multi-component system species normally have different velocities
Evaluation of a characteristic velocity for the gas mixture requires the
averaging of the velocities of each species present
Let vi denotes the absolute velocity of species i relative to stationary
coordinate axis
The mass-average velocity for a multi-component mixture is defined in
terms of the mass densities n n
∑ ρ iv i ∑ ρ iv i n
=
=
vω v =
i 1=
n
=
i 1
ρ
∑ i i
∑ i ρ
i =1
i =1
∑c v
i i ∑c vi i n
==
Vi 1=
n
= i 1
= ∑x v i i
∑ci
c i =1
i =1
n
Total molar flux, N =N ∑
= N i cV
1
Diffusion versus Bulk Flow Flux
The flux (molar or mass) is the sum of two
vectors quantities:
Diffusion flux (concentration gradient)
Mass diffusion flux, ji = j i ρi ( v i − v )
Molar diffusion flux, Ji =
J i c i ( v i −V )
The total mass or molar diffusion flux is zero
Bulk flow flux (bulk motion)
Mass ρiv = w i n
Molar c iV = y i N
Mass and Molar Flux Units
Mass flux
m L m
Dimensions n ρ=
= v 3 =
t
x
L L t
2
Molar flux
Dimensions mol L mol
= = 3
N cV x t=
L L t
2
J1 = − c D12 ∇
xi
total concentartion
molar diffusion flux operator del
∂ ∂ ∂
Remember ∇
= + +
∂x ∂y ∂z
Interaction Energy
σ
energy
ε is the minimum energy
ε
σ
D12 for Binary Ideal Gas Mixture
1. Based on the kinetic theory of gases, diffusion in binary
gas mixture can be described using Lennard-Jones
potentials 0.00266 T
3
2
D12 =
σ AB ΩD
1
2
P M AB
2
2. Wilke-Lee Equation
D12
=
( AB )(
)
3.03 − 0.98 / M 12 10 −3 T 3 2
1
P M AB2
σ AB
2
ΩD
T ≡Temperatur e , °K
P ≡ Pressure ,bar
σ AB ≡ Collision diameter
M AB ≡ " Average" molecular weight
Ω D ≡ Diffusion Collision Int egral
D12 for Binary Ideal Gas Mixture
−1 D12 =
0.00266 T
3
2
D12 =
( AB )(
)
3.03 − 0.98 / M 12 10 −3 T 3 2
1 1 P M AB σ AB ΩD
1 1
2
2 P M AB σ AB
2 2
ΩD
= +
M AB 2
M A M B a 1.06036
b 0.15610
σA + σB
σ AB = c 0.19300
2
d 0.47635
a c e g
ΩD = + + + Diffusion Collision Int egral e 1.03587
(T ) *
b
exp dT * ( ) (
exp fT * ) (
exp hT * ) f 1.52996
T*
kT
= ; ε AB ε AεB g 1.76474
ε AB
h 3.89411
Experimental values of ε A and σ A can be obtaine from appendix B , page 439
εA
= 1.15 Tb ; Tb ≡ Normal boiling point
k
1
σ = 1.18V b ; 3
V b ≡ molar volume of species as liq uid at Tb
1
σ = 1.18V b ; 3
V b ≡ molar volume of species as liq uid at Tb
Estimation of Molar Volume
Vb can be obtained from table 1.2, page18
It can also be estimated based on the atomic volume
contributions of the elements forming the component
(table 1.3, page 18)
It can also be estimated from critical volume:
V A = 0.285 V c1.048
Examples: Estimation of Vb
Ethanol (C2H6O):
=
V b 2* 14.8 + 6 * 3.7 + 7.4
= 59.2 cm 3 / mol
phenol : OH
=
V b 6 * 14.8 + 6 * 3.7 + 7.4 −=
15 103.4 cm 3 / mol
Estimation of Diffusion Coefficient for
Gas system
Larson (1964) measured the diffusivity of
chloroform in air at 298°K and 1 atm and
reported its value as 0.093 cm2/s. Estimate
the diffusion coefficient by the Wilke-Lee
equation and compare it to that calculated
using the kinetic theory and to the
experimental value.
ε AB
= ε AεB
= 340.2 *=
97.0 181.66 °K
−1 −1
1 1 1 1
M AB = 2 + = 2 + = 46.9 g / mol
M A M B 119.4 29
a c e g
ΩD = + + + kT T 298
(T )
*
b
(
exp dT *
) (
exp fT *
) (
exp hT *
) =
T* =
ε AB ( ε AB
= = 1.64
/ k ) 181.66
Solution cont’d
1.06036 0.193 1.03587 1.76474
ΩD = + + + =
1.157
0.15610
1.64 exp (0.47635 * 1.64 ) exp ( 1.52996 * 1.64 ) exp ( 3.89411* 1.64 )
D12
=
( AB
)(
3.03 − 0.98 / M 12 10 −3 T 3 2
=
) (
3.03 − 0.98 / 46.9 1 / 2 x10 −3 x 298 3 / 2)
0.0928 cm 2 / s
1 1/ 2 2
PM σ Ω2 2
AB AB D
1 x46.9 x4.5045 x1.157
3
0.00266 T 2 0.00266 x 298 3 / 2
=D12 = 1 1/ 2
= 2
0.100 cm 2 / s
P M AB
2
σ AB Ω D 1 x46.9 x4.5045 x1.157
2
Diffusion in Liquids
Diffusion Coefficient for liquids
For Binary dilute liquid systems Stokes-Einstein
Equation can be used as the theoretical basis for
other correlation: D = 6 π r kT
0
AB
µ
A B
radius of solute viscosity of solvent
=
AB
T V A0.6
0
D AB = diffusivity of A invery dilute solution in solvent B ,cm 2 / s
M B = Molecular weight of solvent B
T =temperature , °K
µB = viscosity of solvent B ,cP
V A = solute molar volume at its normal boiling point ,cm 3 / mol
= 75.6 cm 3 / mol for water as solute
Φ B = association factor of solvent B , dimensionless
= 2.26 for water as solvent
= 1.9 for metahnol as solvent
= 1.5 for ethanol as solvent
= 1.0 for unassociated solvents, e.g. benzene, et her, heptane
Hayduk and Minhas Equation-Aqueous
For aqueous solution
= 0
D AB (
1.25 x10 −8 V A−0.19 − 0.292 T 1.52 µBε )
9.58
ε
= − 1.12
VA
=σ Pc 3 Tc 3 0.132 αc − 0.278 br
9
Tb T ln ( Pc / 1.013 )
=Tbr ; =αc 0.9076 1 + br
Tc 1 − Tbr
Pc = critical pressure , bar
Tc = critical temper ature , °K
Hayduk and Minhas Equation-Restrictions
D µB 7.4 x10 (Φ B M B ) 2
1
0 −8
=AB
T V A0.6
A is ethanol=V =
0.285 V 0.285 =
* 167.1
A c
1.048 1.048
60.9 cm 3 / mol
(D )
0
AB measured
= 1.00 x10 −5 cm 2 / s ( App em dix A )
B is water µ = 1.153 cP
9.58 9.58
ε = − 1.12 = − 1.12 = −0.963
VA 60.9
0
D AB ( )
1.25 x10 −8 60.9 −0.19 − 0.292 288 1.52 x1.153 −0.946
= 0.991 x10 −6 cm 2 / s
Ji =
−c D i ,eff ∇x i
NH 3
→ N2 + H2
Nitrogen
1 3
2 2 Hydrogen
A
→ 12 B + 32 C Nitrogen (B)
n
N A − y A ∑N j Hydrogen (C)
j =1
D A ,eff =
∑ D (y N A − y AN j )
n
1
j
j =1 Aj
j ≠i
N A − y A (N A + N B + N C )
D A ,eff =
1 1
(y BN A − y AN B )+ (yC N A − y AN C )
D AB D AC
= =
y A 0.4; =
y B 0.2; y C 0.4
DAB=0.237 cm2/s
DAC=0.728 cm2/s
Solution Continued
N A +N B +NC =
N A − 12 N A − 32 N A =
−N A
N A − 0.4 ( −N A )
D A ,eff =
1
0.237
( 0.2N A − 0.4(− 12 N A ) +
1
0.728
( 0.4N A − 0.4 ( − 23 N A ) )
N A (1.4 )
=
0.2 + 0.2 0.4 + 0.6
NA + N A
0.237 0.728
1.4
=
0.4 1
+
0.237 0.728
= 0.457 cm 2 / s
Diffusion in Stagnant Gas Mixture
For stagnant gas mixture, the flux of all
component except component A are zeros
The effective diffusivity equation reduces to
N A − y AN A 1− y A
= =
D A ,eff
( ) (y j )
n n
1 1
=
∑
j 1=D
y j N A ∑
j 1 D
Aj Aj
j ≠i j ≠i
1
=
( y 'j )
n
1
∑
j =1 D Aj
j ≠i
yj
where y 'j =
1− y A
Diffusion of Dilute Solute through
Homogenous Solution of Mixed Solvents
n
D 0
1 ,eff µ 0.8
M = ∑ x j D10, j µ 0.8
j
( Perkins and Geankoplis )
j =2
no accumulation, i.e. ∂C i = 0
∂t
no chemical reaction, i.e. RA=0
Then the continuity equation reduces to:
∂N i ,x ∂N i ,y ∂N i ,z
∇=
•Ni + + = 0
∂x ∂y ∂z
For diffusion only in z direction
∂N i ,z
=0 ⇒ N i =N i ,z =constant
∂z
n
.
∑N
i =1
i = constant
Steady State Diffusion in Gases
For steady-state diffusion in z direction without
chemical reaction in a binary mixture
N=
A J A + y AN
dy A
NA =
−cD AB + y A (N A + N B )
dz
−dy A dz
=
Separating the variables: N A − y A ( N A + N B ) cD AB
⇓
1 N A − y A2 (N A + N B ) z 2 − z 1 z
ln = =
NA + NB N A − y A1 ( N A + N B ) cD AB cD AB
NA
Rearrange and let = ψ A we get
NA + NB
cD AB Ψ − y A 2
NA =ψA ln A
z Ψ A − y A1
z=0.625 mm
Ni(CO)4
CO
NB
NA
Ni
Ni
Solution
D AB p Ψ A − y A 2
NA =ψA ln
RTz Ψ A − y A1
Solution, contd.
yB1=0
y A1 = 1 − y B1 = 1 − 0 = 1
y A2 = 0.5
m2 1.0135 x10 5 Pa
20 mm / s x 1 atm x − 1 − 0.5
2
1 10 6 mm 2 atm 3
NA = − ln
3 2
x Pa − 1 −1
( )
3
8.314 m m
323 K 0.623 mm x 3 3
mol K 10 mm
= 0.189 mol / m 2 .s
Steady State Diffusion through Stagnant
Gas
For diffusion of gas A through stagnant Gas B
NB=0; ΨA=1
Flux equation for binary ideal gas mixture at SS condition becomes
D AB p 1 − y A2
NA = ln
RTz 1 − y A1
It also can be written in terms of linear driving forces:
NA =
D AB p
RTp B ,M z
(
p A2 − p A1 ) z
Mole fraction, y
where p B ,M is the logerithmic mean partial pressur e of B ; yB
p B 2 − p B1
PB ,M =
p B2
.
yA
ln
PB
1
Distance, z
Steady State Equimolar Counter Diffusion
dy A
∴NA =
−cD AB
dz
z2 y A2
N A ∫ dz = −cD AB ∫ dy A
z
z1 y A1
=
N A
D AB P
RTz
( )
y A1 − y =
A2
D AB
RTz
(
p A1 − p A2 )
Steady State Diffusion in Liquids
Unlike the case of gas mixtures, the
concentration and the binary diffusion
coefficient may vary considerably
Nevertheless, we can estimate the molar flux
using an average concentration and best average
diffusion coefficient available
We have:
D c Ψ − x
0
N A =Ψ A
A A
AB
ln 2
z Ψ
A − x
A1
⇓
0
D AB ρ Ψ A − x A2
=Ψ A
z M av Ψ A − x A1
NA ln
Steady-State Diffusion in Liquids
Diffusion of A through Stagnant B:
NB=0, ΨA=1 then
ρ
0
( )
0
D AB ρ Ψ A − x A2 D AB
N A =Ψ A = ⇒ NA x A1 − x A2
z M av Ψ A − x A1
ln
x BM z M av
where x BM is the logarithmic mean mole fraction of B
x BM =
(x B2 − x B1 )
ln ( x B2 / x B1 )
Equimolar Counterdiffusion
NB=-NA, N=0 then
ρ
0
( )
D AB
=NA x A1 − x A2
z M av
Example:
A crystal of Chalcanthite (CuSO4•5H2O) dissolves in a large
tank of pure water at 273° K. Estimate the rate at which the
crystal dissolves by calculating the flux of CuSO4 from the
crystal surface to the bulk solution. Assume that the
molecular diffusion occurs through liquid film uniformly 0.01
mm thick surrounding the crystal. At the inner side of the film,
adjacent to the crystal surface, the solution is saturated with
CuSO4, while at the outer side of the film the solution is
virtually pure water, the solubility of chalcanthite in water at
273° K is 24.3 g of crystal/100 g of water and the density of
the corresponding saturated solution is 1140 kg/m3.
The diffusivity of CuSO4 in dilute aqueous solution
at 273 K can be estimated as 3.6x10-10 m2/s.
The density of pure liquid water at 273° K is
999.8 kg/m3.
CuSO 4 5 H 2 O ( s )
→CuSO 4 ( aq ) + 5 H 2 O ( liq )
CuSO 4 5 H 2 O ( s )
→ A( aq ) + 5 B( liq )
0
D AB ρ Ψ A − x A2
N A =Ψ A ln
z M av Ψ A − x A1
Pure Water
D 0
AB =
z =
xA2 xB2
z=0.01 mm
ΨA =
CuSO4
H2O
NA
X A1 = Boundary Layer
NB
xA1 xB1
X A2 =
Crystal
ρ
M =
1
ρ
M =
2
ρ
M =
av
NA =
Graphical Representation of the
Problem
CuSO 4 5 H 2 O ( s )
→CuSO 4 ( aq ) + 5 H 2 O ( liq )
CuSO 4 5 H 2 O ( s )
→ A( aq ) + 5 B( liq )
Pure Water
xA2 xB2
z=0.01 mm
CuSO4
H2O
NA
Boundary Layer
NB
xA1 xB1
Crystal
Solution
From the reaction equation
N B =5N A ; N=N A +N B =6N A
NA 1
Ψ A= = = 0.167
N A +N B 6
M CuSO 4 159.63
=
Mass of CuSO 4 =24.3x =
24.3 x 15.53 g
(M CuSO 4 +5 M H 2O ) 159.63 + 5 * 18
5M H 2O 5 * 18
=
Mass of Hydration water=24.3x =
24.3 x 8.77 g
(M CuSO 4 +5 M H 2O ) 159.63 + 5 * 18
Total Mass of water =100 + 8.77 =118.77 g
=
Number of moles =
of CuSO 4 15.53 / 159.63 0.973 mol
=
Number of moles =
of H 2 O 118.77 / 18 6.043 mol
0.973
x A1 = = 0.0158
0.973 + 6.043
Solution, Cont’d
Since the other end of the film is virtually pure
water, xB2=1, xA2=0
The molar density of the film ( ρ/M) changes from
point 1 to point 2
At the inner side of the film (near the crystal)
Mav=159.63*0.0158+18*(1-0.0158)= 20.24
ρ/M =1140/20.2=56.32 kmol/m3
At the other end of the film (pure water)
ρ/M =999.8/18=55.54 kmol/m3
( ρ/M )av=(56.32+55.54)/2=55.93 kmol/m3
Solution, Cont’d
For SS binary liquid diffusion
0
D AB ρ Ψ A − x A2
N A =Ψ A ln
z M av Ψ A − x A1
3600 s
=
Rate of dissolution of the crystal ( 3.342 kmol / m 2
)
⋅ s x ( 249.71 kg / kmol )
h
= 30 kg / m 2 ⋅ h
Analogies Among Molecular
Momentum and Mass Transfer
z
Momentum equation
v elocity
shear stress
d u
τ = − μ u
v iscosity
dz
momentum per unit volume
μ d (ρu ) d ( )
uρ
τ =
− −ν
=
ρ
dz dz
K inematic viscosity or
K inematic viscosity or
Momentum diffusivity thermal energy per unit volum
q =
−
k d ρ Tc p ( ) =
−
d Tc ρ
t hermal diffusivity
α
p ( )
cρp dz dz
z
α has same units as mass and momentum diffusivity
This equation is analogous to corresponding equations for momentum
and mass transfer
Prandtl umber is defined as the dimensionless ratio of momentum and
mass diffusivities ν C µ
Pr= = P
α k
Lewis number is defined as the dimensionless ratio of thermal and mass
diffusivities α S
=
Le = c
D AB Pr
Maxwell-Stefan Relations
Momentum balance for binary ideal gas mixture:
∇p 1 =−f 12 y 1 y 2 (v 1 − v 2 )
∇p 1 y 1 y 2 (v 1 − v 2 )
=
d1 =
− Maxwell − Stefan Equation
P D12
P
=D12 Maxwell − Stefan diffusivity
f 12
Convective Mass Transfer
In chapter 1, we discussed the transport of species via
molecular motion (diffusion/microscopic scale)
The Diffusion flux, Ji=-Dijc ∇xi
In addition to transport by molecular motion, mass may
also transported by the bulk motion of fluid
(convective/macroscopic scale)
The convective flux = ci V
Convective mass transfer involves
Transport of species between boundary surface and a moving fluid
Transport of species between two relatively immiscible moving
fluids
This mode of transfer depends both on the transport
properties and on the dynamic characteristics of the
flowing fluid
2
Convective Mass Transfer
When a fluid flows past a solid surface under turbulent flow
conditions:
A laminar condition exists at a region close to the surface
Stagnant layer of the fluid exists near the solid boundary
Molecular diffusion is responsible for mass transfer through
the stagnant and laminar flowing fluid layers
The controlling resistance to convective mass transfer is
often the result of this "film" of fluid.
However, under most convective conditions, this film is
extremely thin and its thickness is virtually impossible to
measure or predict theoretically.
Mass transfer rates cannot be calculated
based on the concepts of molecular diffusion turbulent
Fluid
laminar 3
Solid Surface
Flow past solid Surface
u turbulent
laminar
stagnant
Solid surface
4
Flow past solid Surface
In the turbulent region:
Particles of fluid no longer flow in the orderly manner
found in the laminar sub-layer
Instead, relatively large portions of the fluid, called
eddies, move rapidly from one position to another with an
appreciable component of their velocity in the direction
perpendicular to the surface past which the fluid is flowing
These eddies contribute considerably to the mass-transfer process
Because the eddy motion is rapid, mass transfer in the turbulent region is
much more rapid than it would be under laminar flow conditions
This situation cannot be modeled in terms of Fick's law.
Instead, it is explained in terms of a mass-transfer
coefficient, an approximate engineering idea that simplifies
the analysis of a very complex problem
5
Convective versus Molecular Mass
Transfer
As we learned, the mechanism of molecular diffusion, at
least for gases, is fairly well known
cD AB Ψ A − (c A 2 / c )
NA =ψA ln
z Ψ A − (c A1 / c )
6
Flux of Convective Mass Transfer
For convective mass transfer the cDAB/z term of the
general flux equation that characterize molecular diffusion,
is replaced by F, a mass-transfer coefficient:
Ψ A − c A2 /c
A =F ln
NΨ
Ψ − c /c
A
A A1
Since the surface through which the transfer takes place
may not be plane, so that the diffusion path in the fluid may
be of variable cross section, NA is defined as the flux at the
phase interface or boundary where substance A enters or
leaves the phase for which F has been defined
7
Convective Mass transfer: Diffusion of
A through Stagnant B
For diffusion of A through stagnant B in a binary
system: (NB=0; ΨA=1)
1 − c A2 /c
N A = F ln
1 − c /c
For Gases:
A1
y B 2 − y B1
y b ,M =
=NA
FG
y B ,M
(y A1 − y A2 ) yB
ln 2
yB
1
NA=
FG
y B ,M
(y A1 )
− y A2 = k y (y A1 ) (
− y A2 = k G p A1 − p A2 = k c c A1 − c A2 ) ( )
For Liquids
1 − x A2
N= FL ln ⇒ N=
FL
(x − x A= kx ) (x − x A2 )
1 − x A1
A A A1 A1
x B ,M 2
x B 2 − x B1
x b ,M =
xB
ln 2
xB
1
8
Example:
A gas absorber is used to remove benzene (C6H6) vapors
from air by scrubbing the gas mixture with a nonvolatile
oil at 300° K and 1 atm. At a certain point in the absorber,
the benzene mole fraction in the bulk of the gas phase is
0.02, while the corresponding interfacial benzene gas-
phase concentration is 0.00158. The benzene flux at that
point is measured as 0.62 g/m2/s.
a) Calculate the mass transfer coefficient in the gas phase at that
point in the equipment, expressing the driving force in terms of i)
mole fractions, ii) molar concentrations, kmol/m3.
b) If the benzene fraction in the bulk of the liquid phase is 0.125,
while the corresponding interfacial benzene liquid-phase
concentration is 0.158. Calculate the mass-transfer coefficient in
the liquid phase, expressing the driving force in terms of mole
fractions.
9
Solution part a: Gas Absorber
T=300° K, P= 1 atm Air
yA1=0.02; yA2=0.0156
nA=0.62 g/m2.s
a) g
0.62 2
n
N A= A = m ⋅ s =7.94x10 -3 mol
MA g m2 ⋅s Air-Benzene
78.1
mol
Oil-Benzen
=NA ky (y A1 − y A2 ) interface
Oil
mol
7.94x10 -3 2
ky =
NA
= m ⋅ s = 1.89 mol Benzene
(y A1 − y A2 ) (0.02 − 0.0156 ) m2 ⋅s 2 1
Air + benzene
10
Solution Part b: Gas Absorption
b)=
N A (
k c c A1 − c A2 )
pA y AP
=
cA =
RT RT
p A1 y A1 P 0.02 x1 ( atm )
=
cA 1 = = = 0.81 mol / m 3
RT RT atm ⋅ m 3
0.0825 x10 −3 x 300 ( K )
mol ⋅ K
p A2 y A2 P 0.0158 x1
c=
A2 = = −3
= 0.64 mol / m 3
RT RT 0.0825 x10 x 300
mol
7.94x10 -3 2
NA m ⋅ s 46.8 x10 −3 m
kc = = =
(c A1 − c A2 ) mol
(0.81 − 0.64 ) 3
s
m
11
Solution Part c: Gas Absorption
mol
7.94x10 -3 2
kx=
NA
= m ⋅ s = 0.24 mol
(x A1 − x A2 ) (0.158 − 0.125 ) m2 ⋅s
12
Convective Mass transfer: Equimolar
Counterdiffusion
For equimolar counter diffusion (N =-N , Ψ =undefined)
A B A
For Gases:
( ) ( ) ( ) (
N A= FG y A1 − y A2 = k y′ y A1 − y A2 = k G′ p A1 − p A2 =k c′ c A1 − c A2 )
P
= P k c′ = k 'y
FG k= '
G
RT
For Liquids
NA =
= ( )
k x′ x A1 − x A2 =
FL x A1 − x A2 = ( )
k L′ c A1 − c A2 ( )
=
FL k=
'
Lc k x′
13
Example:
A packed bed distillation column is used to adiabatically
separate a mixture of methanol and water at a total
pressure of 1 atm. Methanol, the more volatile of the two
components, diffuses from liquid toward the vapor phase,
while water diffuses in the opposite direction. Assuming
that the molar latent heat of vaporization of both
components are similar, this process is usually modeled as
one of the equimolar counterdiffusion . At point a in the
column, the mass transfer coefficient is estimated as
1.62x10-5 kmol/m2-s-kPa. The gas phase methanol mole
fraction at the interface is 0.707, while at the bulk gas it is
0.656. Estimate the methanol flux at that point.
14
Solution
Methanol
Equimolar counterdiffusion
Let A is methanol; B is water
Gas side of the interface V L
N = F (y − y =
A G ) k ′ ( y − y =) k ′ ( p
A1 A2 y A1 A2 G A1 ) (
− p A2 =k c′ c A1 − c A2 ) Water-Methanol
vapor
pA = y AP 2 1
M
= =
p A1 0.707 atm ; p A2 0.656 atm W
kmol 101.325 kPa
( )
N A= k G′ p A1 − p A2 = 1.62 x10 −5 2 (0.707 − 0.656 )( atm )
m ⋅ s ⋅ kPa atm
kmol
= 8.37 x10 −5 2 Liquid
m ⋅s
15
Analogy Between Heat and Mass
Transfer
There are similarities between mass and heat transfer
governing equations when expressing the driving force in
terms of dimensionless variables
There are more experimental data available for heat
transfer than for mass transfer
There are also many similar dimensionless groups that
contain the heat and mass transfer coefficient
These dimensionless groups can be used to convert
equations or correlation of data on heat transfer to
correlation on mass transfer by replacing the
corresponding groups of heat transfer with groups of mass
transfer
16
Analogy between Heat and Mass
Transfer
Mass transfer Heat transfer
These analogies should be used Reynolds number
when the flow conditions and Re =
v ρ
µ
geometry are the same Schmidt number Prandtl number
If the heat transfer data is based Sc =
µ
ρ D AB
Pr =
CPµ
k
Chilton-Colburn j- Chilton-Colburn j- 2
factor j = St Sc factor j = St pr
2
3
3
D H
D D
17
Heat transfer Mass transfer
j D = St H pr 3
j D = St D Sc
2
3
Example: Flow Normal to Cylinder
For flow normal to a cylinder, the average heat-transfer coefficient-
averaged around the periphery of the cylinder- is given by
Nu av = 0.43 + 0.532 Re 0.5 Pr 0.31 ; 1 ≤ Re ≤ 4000
where Nuav and Re are computed using the cylinder diameter as the
characteristic length, and the fluid properties are evaluated at the
average conditions of the stagnant fluid film surrounding the solid
(average temperature and average concentration). Estimate the rate of
sublimation of a cylinder of UF6 (M= 352), 1.0 cm diameter and 10 cm
long exposed to an air stream that flows normal to the cylinder axis at
a velocity of 1.0 m/s. The surface temperature of the solid is 303° K, at
which temperature the vapor pressure of UF6 is 27 kPa. The bulk air is
at 1 atm and 325 K.
19
Phase Diagram for UF6
UF6 is a solid below a temperature of 134°F (57°C)
and a gas at temperatures above 134°F.
20
Solution
For heat transfer we have:
Nu av = 0.43 + 0.532 Re 0.5 Pr 0.31 ; 1 ≤ Re ≤ 4000
Or F v ρ
0.5
µ
0.31
=
0.43 + 0.532 +
cD AB µ ρ D AB
Air
The properties are calculate at average Solid
Air
=
M av ∑ y=
M i i 0.133 x 352 + ( 1 − 0.133 )=
x 29 71.96
i
21
Solution: average Properties
PM av 101.325 x71.96
ρav
= = = 2.8 kg / m 3
RT av 8.314 x 314
Air
Air
Solid
µav can be estimated using Lucas Corresponding states method UF6
1 2 UF6
µrM = 0.807T rM0.618 − 0.357 exp ( −0.449T rM ) + 0.340 exp ( −4.058T rM ) + 0.018
ξM µ =
T
1
6 ∑y Zi ci
T O2 N2 UF6
ξM 0.176 3cM= ;TcM ∑
= y T ;P RTcM i
= ;T
∑y V
4 i ci cM rM
M av PcM i i ci TcM
Yi 0.182 0.685 0.133
i
22
Solution Continue: DUF6-air
( )(
P 1.013 bar
3.03 − 0.98 / M 12 10 −3 T 3 2
AB )
D12 = W ilke − Lee Equat ion
σ AB ΩD
1
2
P M AB
2
T 314 K
σA +σB T* 2.07
σ AB = ;
2
a c e g
ΩD = + + + a 1.06 e 1.04
( )
T*
b
(
exp dT * ) (
exp fT * ) (
exp hT * )
b 0.156 f 1.53
ε AB = ε A ε B c 0.193 g 1.76
d 0.476 h 3.89
23
Solution continued: Dimensionless
Numbers
kg
m kg 2.29 x10 −5
dv ρ
0.01 ( m ) x1 x 2.8 3 µ m ⋅ s 0.905
=
Re =
s m = =Sc = =
1223
µ ρ D AB kg −4 m
2
kg
2.29 x10 −5
m ⋅s
2.8 m 3 x0.09 x10 s
Fav
=
Shav = 0.43 + 0.532 Re 0.5 Sc 0.31
cD Ab
Fav cD Ab 0.43 + 0.532 x ( 1223 ) x (0.905 )
0.5 0.31
=
P 101.3
= = 0.09 x10 −4 x18.4 x0.09 x10 −4 x18.4
RT av 8.314 x 314
kmol
= 6.52 x10 −4
m2 ⋅s
2 πd 2
The flux is based on the surface area of the cylinder; S= + π dl= 3.3 x10 −3 m 2
4
24
Solution continued: Dimensionless
Numbers
To calculate the flux of A through stagnant B
1 −0 −4 kmol
=N A F=
av ln 2.021 x10
1 − 27 m2 ⋅s
101.3
25
Convective Mass Transfer Correlations
26
Mass Transfer Coefficient for Flat
Plates
Examples
Evaporation from a free liquid surface
Sublimation of a flat solid surface
The following correlation can be used:
1
or
J D = 0.664 Re L−0.5 Re L < 3 x10 5 ( Laminar ) L
J D = 0.036 Re −0.2
L Re L ≥ 3 x10 5
(Turbulent )
27
Example
Liquid Benzene flows in a thin film down the outside surface
of a vertical plate, 1.5 m wide and 3 m long. The liquid
temperature is 300° K. Benzene-free nitrogen at 300° K and 1
bar flows across the width of the plate parallel to the surface
at a speed 5 m/s. Calculate the rate at which the liquid should
be supplied at the top so that the evaporation will just prevent
it from reaching the bottom of the plate. The density of liquid
benzene at 300° K is 0.88 g/cm3. The vapor pressure of
benzene at 300° K is 106 mmHg, the diffusion coefficient
Dbenzene-Nitrogen=0.0986 cm2/s and the viscosity benzene-
Nitrogen mixture is 161 µP.
28
Solution
3m
1 − y A2
N A = Fav ln
1 − y A1 N2
1.5 m
29
yA2= 0
Nitrogen is free from benzene
yA1 corresponds to the vapor pressure of benzene
at 300°K (106 mmHg)
yA1=106/760=0.139
Average properties at the interface Wall
can be estimated benzene
F can be estimated based on Interface
flat-plate correlations
. Re
= =
ρvL 1.26 x 5 x1.5
L
µ 1.61 x10
= 5.87 x10
−5
5
( Turbulent )
Bulk Nitrogen
µ1.61 x10 −5
=
Sc = = 1.29
ρ D AB 1.26 x0.099 x10 −4
[0.6 < Sc < 2500 ]
30
Solution Cont’d
1
F
ShL =
c D AB
1 − y A2 −4 1 −0 kmol
=N A F= ln 4.25 x10 = ln 6.34 x10 −5 2
1 − y A1 1 − 0.139 m ⋅s
av
kg
=
Total mass vaporation ,W A N=
A SM A 6.37 x10 −5 x ( 3 x1.5
= ) x78 0.022
= 1.34 kg / min
s
31
Mass Transfer Coefficient for a Single
Sphere: No natural convection
General equation contains terms for molecular diffusion
and forced convection 1
=
Sh Sh0 + C Re m Sc 3
For low Re, Sh approaches theoretical value of 2
1
Sh= 2 + C Re Sc m 3
32
Mass Transfer Coefficient for a Single
Sphere: with natural convection
Natural convection is negligible only when
1 −1
R e ≥ 0.4Gr D 2 Sc 6
33
Mass Transfer Coefficient for Single
Cylinders
Sublimation from solid cylinder into air flowing
normal to its axis
Dissolution of solid cylinders into turbulent water
(other liquids) stream
Bedingfield and Drew Correlation
k G PSc
= 0.281 Re −0.4 400 < Re < 2500 and 0.6 < Sc < 2.6
GM
34
Example:
Air
Air
Solid
UF6
1 2 UF6
35
Solution
The properties are calculate at average temperature and average
concentration inside the stagnant film:
This image cannot currently be displayed.
303 + 325 27 + 0
T=
av = 314 °K ( p=
av )UF = 13.5 kPa
2 6
2
( p av )UF 13.5
( y=
A )av = 6
= 0.133 ;
P 101.3
T 6
1
∑y Zi ci
T
O2 N2 UF6
=ξ M 0.176 3cM= 4
;TcM ∑
= y i Tci ; PcM RTcM i
= ;T
∑y V
rM
M av PcM i i ci TcM Yi 0.182 0.685 0.133
i
M, g/mol 32 28 352
36
kg
m kg 2.29 x10 −5
dv ρ
0.01 ( m ) x1 x 2.8 3 µ m ⋅ s 0.905
=
Re =
s m = =Sc = =
1223
µ ρ D AB kg −4 m
2
kg
2.29 x10 −5
m ⋅s
2.8 m 3 x0.09 x10 s
400 < Re < 2500 0.6 < Sc < 2.6
k G PSc
= 0.281 Re −0.4
GM
ρ m 2.8 kmol kmol
G M= vc
= v av= 1 x 3
= 0.039 2
M Av s 71.96 m m ⋅s
G 0.039
kG P =
0.281 xRe −0.4 x M 0.281 x1223
= −0.4
x 0.56
6.75 x10 −4 kmol / m 2 ⋅ s
Sc 0.905
1 − ( 1 − 0.266 )
=F k=
y y B ,M ( k G P=
) y B .M 6.75 x10 −4 x = 5.81x10 -04 kmol / m 2 ⋅ s
1
ln
1 − 0.266
Compared to 6.52x10-4 kmol/m2.s using analogy between
mass and heat transfer
37
Turbulent Flow in Pipes
Mass transfer from the inner wall of a tube to a moving
fluid (wetted wall towers)
Gilland and Sherwood correlation
Different fluids in air
2000 < R e < 35000
Sh = 0.023 Re 0.83 Sc 0.44 0.6 < Sc < 2.5
The characteristic length is the tube diameter
The properties are evaluated at the bulk conditions
of the flowing gas stream
Best for gases only
Linton and Sherwood Correlation Gas
38
Mass Transfer in Packed and Fluidized
beds
Packed and fluidized beds offer a dramatic increase
in surface area
Used in industrial mass transfer operations
Adsorption, ion exchange, chromatography, drying,
humidification, distillation, and catalytic reaction
For mass transfer of a species from the solid surface
of a packed bed to a flowing gas, or vise versa, use
the Sherwood et. al. correlation:
J D = 1.17 Re −0.415 [10 < Re < 25000 ]
d pG y
Re =
. µ
d p is the diamter of the sphere with the same surface area as the particle
G y is the gas mass velocity based on total cross section area
39
Mass Transfer in Packed and Fluidized
beds
For mass transfer in both gas and liquid and fixed
and fluidized beds of spherical particles, use Gupta
and Thodos correlation:
0.863
ε J D 0.010 +
= [1 < Re < 2100 ]
Re 0.58 − 0.483
d dP
ε =
0.406 + 0.571 P for ≤ 0.14 ε is the void fraction of t he b ed
D D
Sh F
= =
j D St D Sc
2/3
= Sc 2/3 Sc 2/3
ReSc cv
The surface are for packed and fluidized bed are expressed
6 (1 − ε )
in terms of a a=
d P
40
Mass Transfer in Hollow-Fiber
Membrane Modules
Hollow-fiber membrane modules are the mass
transfer equivalent to tube and shell heat
exchangers
One fluid flows through the lumen (inside the fiber
bundle) the other flows through the shell. Mass is
transferred from one stream to the other across
the fiber wall
Mass transfer may involve both diffusion and
convection, depending on the
membrane type
41
Mass Transfer in Hollow-Fiber
Membrane Modules
Fiber bundle
42
Mass Transfer Coefficient for Hollow
Fiber Membrane
Bao et. al. Correlation (Liquid through Shell Side)
−0.47
1 − φ 1 −φ
Sh 0.53 ( 1 − 1.10 φ )
= Re 0.53 Sc 0.33 [ 30 < 100 φ < 75 ] and 20 < Re < 350
φ φ
2 Rk L
Sh = ; R ≡ Fiber Radius ; φ ≡ Fiber packing fraction
D AB
2 Rv 0 ρ
=Re ; v 0 ≡ superficial velocity based on empty shell
µ
Flow through lumen corresponds to laminar flow inside a circular pipe
Constant wall concentration
1
d 3
( Pe D ) i 1.62 (G z ) [ R e < 2100 ]
1 1
= =
Sh 1.62 3 3
L
di kL d iv ρ
=Sh = ; Re ; v ≡ average fluid velocity
D AB µ
d
G z ≡ Graetz number =
Pe D i
L
Constant wall flux concentration
43
Packed-Bed: Mass transfer from solid
surface to the gas stream
Wilke and Hougan reported the mass transfer in beds of granular
solids. Air was blown through a bed of porous celite pellets wetted
with water, and by evaporating this water under adiabatic conditions,
they reported gas-film coefficients for packed beds. In one run, the
following data were reported:
Effective particle diameter 5.71 mm
Gas stream velocity 0.816 kg/m2-s
Temperature at the surface 311 K
Pressure 97.7 kPa
kG = 4.415x10-3 kmol/m2-s-atm
With the assumption that the properties of the gas mixture are the
same as those of air, calculate the gas film mass transfer coefficient and
compare the result with the value reported by Wilke and Hougan.
Assume the film viscosity, µ =1.91x10-5 kg/m.s.
44
Solution
This image cannot currently be displayed.
Air 45
Solution Continued
P 97.7 x10 3
ρair cM
= = air M = 28.8 = 28.8 (0.0378
= ) 1.09 kg / m 3
RT 8.314 x 311
µ 1.91 x10 −5
=Sc = = 0.697
ρ D AB 1.09 x 2.52 x10 −5
Sh jD 0.120
=
St D = = 2
= 2
0.152
Re Sc Sc 3 0.697 3
Fd P
=
Sh = St D Re= = 25.84
Sc 0.152 x 244 x0.696
D AB
F 25.84 kmol
=
kG = = 4.47 x10 −3 2
Py b ,M ( 97.7/101.3 ) x1 m ⋅ s ⋅ atn
46
yA, G
xA,i
yA,i xA,G
Interface
Bulk NH3-Air Water
Equilibrium Relation
=
p A y=
AP γ A x A PA =
pA y=
A P xA γ
A PA
activity coefficient
Distribution-law (liquid-liquid)
c A, liquid 1 = Kc A, liquid 2
Diffusion Between Phases
Consider the absorption of ammonia from a Water
Interface
Bulk NH3-Air Water
Phase Transfer Coefficients
yA, G
NNH3 can be expressed in terms of
xA,i
k-type coefficients:
N A= k y ( y A ,G − y A ,i )= k x ( x A ,i − x A ,L )
yA,i xA,G
Interface
k ( y A ,G − y A ,i )
− x =
Bulk NH3-Air Water
ky ( x A ,L − x A ,i ) yA,G
W her e :
y A ,i is the interface concentration in the gas phase side
x A ,i is the interface concentration in the liquid phase side
k y is the gas − phase mass transfer coefficient
k x is the liquid − phase mass transfer coefficient
yA,i= f(xA,i)
xA,L xA,i
5
Overall-Mass Transfer Coefficient
x*A
The interface concentration is yA, G
Interface
of overall mass transfer coefficient
as follow
Bulk NH3-Air y*A Water
yA,G
N=
A ( )
K y y A ,G − y = K x x − x A ,L
*
A ( *
A )
W here :
y *A is in equilibrium with x A ,L yA,i
x *A is in equilibrium with y A ,G
yA*
= (
N A K y y A ,G − y *A )
1 y A ,G − y *A y A ,G − y A ,i y A ,i − y *A y A ,G − y A ,i m ( x A ,i − x A ,L )
= = + = +
Ky NA NA NA NA NA
1 1 m 1 1 1
= + Similarly = +
Ky ky kx K x mk y k x
⇓
1 1
Resistance in gas phase ky Resistance in liquid phase k
= = x
Total Resistance in both phases 1 Total Resistance in both phases 1
Ky KX
Effect of the Gas Solubility in the Mass
Transfer Coefficients
For highly soluble gas (the slope of the equilibrium
line, m, is small)
The major resistance is in the gas phase
1 1 m 1
= + ≈
Ky ky kx ky
phase
1 1 1 1
= + ≈
K x mk y k x k x
XA
Example
In an experimental study of the absorption of NH3 by water in
a wetted-wall column, the value of KG was found to be
2.75×10-6 kmol/(m2-s-kPa). At one point in the column, the
composition of the gas and liquid phases were 8.0 and 0.115
mol% NH3, respectively. The temperature was 300° K and the
total pressure was 1 atm. 85% of the total resistance to mass
transfer was found to be in the gas phase. At 300° K, NH3-
water solution follows Henry’s law up to 5 mol% NH3 in the
liquid with m = 1.64 when the total pressure is 1 atm.
Calculate:
1. Flux of NH3
2. Individual film coefficients
3. Interfacial Compositions (yA,i and xA,i)
Solution
Given
T=300 K; P=1 atm
KG= 2.75x10-6 kmol/m2-s-kPa
yA,G=0.080; xA,L=0.00115
.k1 = 0.85 K1
y y
(
.N A K y y A ,G − y *A
= )
K y =K G P = 2.75x10 -6 x 101.3 = 2.786x10 -4 kmol/m 2 -s
= =
y *A mx A ,L = 1.886 x10 −3
1.65 * 0.00115
= (
N A K y y A ,G − y=
*
A )
2.786 x10 −4 (0.08 − 0.001886
= ) 2.18 x10 −5 kmol / m 2 ⋅ s
10
Solution
1 0.85
ky.=
Ky
Ky 2.786 x10 −4
=ky = = 3.28 x10 −4 kmol / m 2 .s
0.85 0.85
. 1
=
Ky
1
+
ky kx
m
.
m 1 1 1 0.85 0.15
= − = − =
kx K y ky Ky Ky Ky
mK y 1.64 x 2.75 x10 −6
=
kx = = 3.05 x10 −3 kmol / m 2 .s
0.15 0.15
N. A k y ( y A ,G − y A ,i
= )
NA 2.18 x10 −5
y A ,i = y A ,G − = 0.08 − = 0.01362
ky 3.28 x10 −4
y A ,i 0.01362
x A ,i =
= = 8.305 x10 −3
m 1.64
Local Mass Transfer Coefficients
Ψ A ,L FL
Ψ A ,G − y A ,i Ψ A ,L − x A ,L Ψ A ,G FG
=
Ψ A ,G − y A ,G Ψ A ,L − x A ,i
Example
A wetted-wall absorption tower is fed with water as the wall
liquid and an ammonia air mixture as the central-core gas. At
a particular point in the tower, The ammonia concentration
in the bulk gas is 0.60 mole fraction and that in the bulk
liquid is 0.12 mole fraction. The temperature is 300° K and
the pressure is 1 atm. Ignoring the vaporization of water,
calculate the local ammonia mass-transfer flux. The rates of
flow are such that FL = 0.0035 kmol/m2-s. and FG = 0.0020
kmol/m2-s. The equilibrium-distribution data for the system
at 300° K and 1 atm is:
yA = 0.156 + 0.622 x A ( 5.765 x A − 1 ) ;
10.51 γ A x A ; γ A = x A ≤ 0.3
Solution
Given
T=300 K; P=1 atm
yA,G=0.60; xA,L=0.12
FL = 0.0035 kmol/m2-s; . FG = 0.0020 kmol/m2-s
y. =
A 0.156 + 0.622 x ( 5.765 x − 1 ) ;
10.51 γ x ; γ =A A A x ≤ 0.3 A A A
Ψ A ,G − y A ,G Ψ A ,L − x A ,i
A ,G G A ,L L
FL
1 − y A ,i 1 − x A ,L 1 − x A ,L FG
=N A F=
G ln FL ln ⇒ y A ,i =1 − ( 1 − y A ,G )1 − x
1 − y A ,G 1 − x A ,i A ,i
Solution
FL
1.75
1 − x 0.88
y A ,i =1 − ( 1 − y A ,G ) 1 − xA ,L
FG
⇒ y A ,i =0.6
A ,i
1 − x A ,i
Graphically or numerically
yA,i=0.49; xAi=0.23
1 − y A ,i
N A = FG ln
1 − y A ,G
1 − 0.49
= 2 x10 −3 ln
1 − 0.6
= 0.4.7 x10 −4 kmol / m 2 ⋅ s
Material Balance
Consider steady state mass transfer L2, x2, X2 V2, y2, Y2
V 1 y 1 + Lx =Vy + L 1 x 1
L1, x1, X1 V1, y1, Y1
LS
VS
Y −Y 2
= 1
X1 − X2
or LS
VS
Y −Y
= 1
X1 − X
Z=z 1
20
Material Balance
Masses, mass fraction, and mass ratio can be substitute
consistently for moles, mole fractions, and mole ratios in
the mass balance equations
Cocurrent flow
'
LS '
Y 1 −Y 2
'
=
V S' X 1' − X '2
Counter Flow
L'S Y 1' − Y 2'
− ' =
VS X 1' − X '2
If twice the minimum gel rate is to be used, calculate the gel mass flow
rate and the composition of the gel leaving the process for:
i. Counter flow operation
ii. Cocurrent flow operation
Solution:
Countercurrent
1. Plot the equilibrium data Gel Air/NO2
kg NO 2
( 1 − 0.85 ) xY 1' =
Y 2' = 0.15 * 2.42 =
0.0036
kg Air
kg NO 2
X '2 = 0.00
kg gel
1 1
= 1 ωB 1
V s' V= 0.5 x = = 0.488 kgAir / s
'
0.5
1 +Y 1
'
1 + 0.0242
L'S (min) = 0.268 kg gel / s
=L'S 2=
x0.268 0.536 kg gel / s
X= X +V
' ' '
(Y '
1 )
− Y 2'
= 0.00 + 0.488 x
0.024 − 0.0036
= 0.0186 kg NO 2 / kg gel
1 2 S '
LS 0.536
Cocurrent Flow
Cocurrent
Gel+NO2 Air/NO2
Y1’=0.024
Y2’=0.036
X1’=0.00
For (LS)min, (X2’)max can be
Air/NO2 Gel
X=
'
X '
+ V '
(Y '
1 − Y 2' )
2 1 S
L'S
0.024 − 0.0036
=
0 + 0.488 x =
0.00168 kg NO 2 / kg gel
5.92
• To reach the same degree of removal of NO2, countercurrent flow is
much more effect compared to cocurrent
• The amount of gel needed for cocurrent flow (5.92 kg/s) is about 11
times of that needed if countercurrent flow is used (0.536 kg/s)
Equilibrium-Stage Operation
In many instances mass transfer devices are assembled by
interconnecting individual units (stages)
The material passes through each one of these stages
Two material streams moves countercurrently (cascades)
In each stage the two streams are contacted, mixed, and then
separated
As the stream moves between stage they come close to equilibrium
conditions
If the leaving streams from a certain stage is in equilibrium, this
stage is an ideal stage
If the stage are connected cocurrently they represent a single stage
Batch mass-transfer operations are also a single stage
Stage-Operations
V1 V2 VN VN+1
VS VS VS VS
Y1 Y2 YN YN+1
Stage Stage n Stage Stage
1 2 N-1 N
L0 L1 LN-1 LN
LS LS LS LS
X0 X1 XN-1 XN
X − Y N +1 / m Y − mX 0 1 1
ln 0 (1 − A ) + A ln N +1 1 − +
X N − Y N +1 / m Y 1 − mX 0 A A
N = A ≠1 A ≠1
ln ( 1 / A )
N
ln A
X0 − X N Y N +1 − Y 1
N = =A 1 N = A 1
X N − Y N +1 Y 1 − mX 0
1
Equipment for Gas Liquid Mass Transfer Operations
The equipment for gas liquid contact disperse either the gas or
the liquid in the other phase
Flexigrid
0.6
Liquid redistribution every 3-10 D ε
or at least every 6-7 m is provided
0.4
0.2
0
0 1 2 3 4 5 6
Distance from wall, r*=r/dp
a and Ch are characteristic of the particular Type of Packings vL, min, mm/s
packing type and size
Ceramics 0.15
The superficial liquid velocity must exceeds
the following values to ensure complete Oxidized/etched 0.3
metals
wetting of the packing:
Bright metals 0.9
Plastics 1.2
CHEG351: Mass Transfer Chapter 4
Liquid holdup: Example
A tower packed with 25-mm ceramic Raschig rings is to be used
for absorbing benzene vapor from a dilute mixture with inert
gas using wash oil at 300° K. the viscosity of the oil is 2.0 cP
and its density is 840 kg/m3. the liquid mass velocity is Gx=2.71
kg/m2.s. Estimate the liquid holdup, the void fraction and the
hydraulic specific area of the packing.
Given Data:
T=300 K
ρL=840 kg/m3; µL=2.0 cP
Gx=2.71 kg/m2.s
dP=25 mm
Required:
hL, ε, and ah
v = = =3.226 x10 -3 m / s
L
ρL 840
From table 4.1, for 25 mm ceramic Raschig rings:
a =190 m2/m3; Ch=0.577; ε =0.680
v L ρ L 3.226 x10 -3 x840
Re L = = = 7.13
a µL 190 x 2 x10 −3
ah
C h Re L0.25 Fr L0.1 =0.85 x 0.577 (7.13 )( )
0.1
0.202 x10 −3
0.25
=
0.85 0.342
a
ah =
0.342 x190 65 m 2 / m 3
1 2 1/ 3
Fr L 3 ah 3 0.202 x10 −3
[ ]
2/ 3
hL =
12 12 = 0.342 0.034 m 3 holdup / m 3 packed bed
Re L a 7.13
0.1
− 3.5021 + 1.028 ln X + 0.11093 ( ln X )
) ( µL )
2
lnY flooding =
50
2
where :
Y =FP (C S
packing Factor 1
ρG 2
Y flooding =
FP C S2 µL0.1 ; C S vG
ρ L − ρG 0.01 Gas Pressure Drop
0.5 Pa/m packing
L' ρ
X = G
V ' ρ L
Pressure drop at 1
200
0.1
) ( µL )
50
2
Y =FP (C S
0.01 Gas Pressure Drop
Pa/m packing
0.001 0.5
1.5
∆P ε Re v L ρL
= exp L Re L =
∆P0 ε − hL 200 a µL
v d ρ K
ReG = 1 − ε µ
G p G W
( ) G
Liquid rate
High liquid velocity: Weeping Satisfactory
Operation
Sieve tray
Sieve tray
Perforated tray deck with uniform hole
diameter of less than 1 mm to 25 mm
Most economical in terms of cost and
maintenance
Fixed
Valve trays
Valve trays
Offers more flexibility over sieve trays
More expensive
Caged
Can be fixed or floating
Bubble cap trays
Valve Tray
Sieve Tray
Column internals
Tray layout
Downcomer area Tray above
Column diameter
Column height
clear
liquid
Froth
Tray efficiency
Tray spacing
Gas Flow
clear
liquid
Weir Froth
Plate
θ
centers (p`=2.5-5 do)
Downcomer area
Lw weir
hW
rw
p` p`
p`
2
Ah π d o d o
= 0.907
Aa 4 sin (60 ) p'
p'
=
inlet Downcomer
buoyancy
1/ 2
Q ρ − ρG
vGF = G = C L
An ρG
gravity
σ
0.2
1
=C F α log + β
X
=α 0.0744t + 0.01173
(t = tray spacing )
= β 0.0304t + 0.015
0.5
L' ρG
= =
X flow param eter ρ (Use 0.1 for 0.01<X <0.1 )
G' L
f v GF ( 1- Ad At ) π θ
Where
Ad At is chosen based on the value of X ½ r2θ ½ r2sinθ
0.1 X ≤ 0.1
Ad X − 0.1 Ad
= 0.1 + 0.1<X ≤ 1 r θ r θ
Ar 9 = - rw
0.2 X ≥1
1 2
r (θ − sin θ )
Ad 2 θ − sin θ
= =
At πr 2 2π
θ 1 θ
Lw = D sin ; rW = cos
2 2 2
where
hd = dry tray head loss
do
hl = equivalent head for liquid in tray plate
hσ = head loss due to surface tension
vapor
do
plate
ρW Ah
2 2
vo
=hd 0.0051 ρG 1 −
C o ρ L Aa
v o is hole velocity
φe effective relative froth density (height of clear liquid/froth height) =exp ( -12.55 K s0.91 )
1
ρG 2
K s ≡ (capacity parameter , m / s ) =
va
ρ L − ρG
v a ≡ sperficial gas velocity based on tray active area
50.12 + 43.89 exp ( −1.378 hw
Cl = )
t = tray spacing
h2 φ = height of two-phase region on the tray
hl do
1.85
k s2
= + 7.79 1 + 6.9
φe hl A
φe g h
Aa
h
ks =
0.5 1 − tanh 1.3 ln l − 0.15
do
t = tray spacing
h2 φ = height of two-phase region on the tray
hl do K2
1.85
= + 7.79 1 + 6.9 s
φe hl A
φe g h
Aa
h
k =
0.5 1 − tanh 1.3 ln l − 0.15
do
where Re Fe =
ρG v o hl
µG φe
a1 = 0.4136
a 2 = 0.6074
a3 = −0.3195
m = local slope of the equilibrium curve
cG ,c L = molar concentration of gas and liquid, respectively
DG , D L = diffusivity of gas and liquid , respectively
1
ρG
φe =exp ( -12.55 K s0.91 ) ; K s = v a
2
ρ L − ρG
λ EOG
N
1 + N − 1
E MG =
λ
Pe L + 2
N =
2
4 q L rw2
Pe L =
Aa hl D E ,L
0.5
D E ,L = 0.1 gh23φ liquid eddy diffusivity
Liquid Vapor
To get FHA we need Ah/Aa T, °K 368
Ah d o
2
6
2 P, kPa 101.3
=
0.907 p' =
0.907 12 0.23 Rate, kmol/s 0.25 0.1
Aa
Ah composition 15 mass% 18 mole%
> 0.1 ⇒ FHA =
1
Aa Density, kg/m3 961 -
σ, dyne/cm 40 -
Diffusivity, cm2/s 5.70x10-5 0.213 cm2/s
Viscosity, cP 0.3 125x10-4
Foaming Factor 1 -
CHEG351: Mass Transfer Chapter 4
Flood Velocity
=
C= =
FST FF FHAC F 1.15 x1 x1 x0.09 0.091
1/ 2
ρ − ρG
0.5
Q 961 − 0.68
v GF = G==C L =
0.103 0.68 3.42 m / s
An ρG
GF d t
QG 3.02
=
vo = = 15.36 m / s
Ah 0.2
2 2
d 6
Co =
0.85032 − 0.04231 o =0.85032 − 0.04231 =0.74
2
2
15.36 961
=hd 0.0051 =
0.68 1 − 0.23 2 1.48 cm liquid
0.74 1000
2
2. Clear Liquid head presure drop =
hl φe hW + C t
q L
φ
W e
L
3
1 1 1
ρG 2 Q G ρG 2 3.02 0.68 2
K s ≡va = = = 0.09
ρ L − ρG Aa ρ L − ρG 0.87 961 − 0.68
2
2
(0.2 x19.27 ) / 961 3
φe hW + C t L =
q 3
hl = 0.24 5 + 50.16 =2.19 cm liquid
LW φe
0.85 x0.24
Entrainment:
k
hl
1.1 0.5
h2 φ ρL
E = 0.00335
t ρG h2 φ
hl do
1.85
K2 0.0409 6
1.85
h2 φ =+ 7.79 1 + 6.9 s
= + 7.79 1 + 6.9 = 0.3 m
φe hl Ah 0.24 40.9
φe g
a
A
h 40.9
k =0.5 1 − tanh 1.3 ln l − 0.15 =0.5 1 − tanh 1.3 x ln − .015 =0.044
do 6
k
hl
1.1 0.5
h2 φ ρL
1.1 0.5 0.007
0.3 961 0.0409
=
E 0.00335 =0.00335 = 0.06= 6%
t ρG h2 φ 0.6 0.68 0.3
Weeping: 0.5
0.68x15.36
0.5
ρG v o2
Fro = = = 0.61 >0.5
g ρ L hl 9.8x961x 4.61
100
Packed Column
Low pressure drop (vacuum service)
Corrosion concerns
Low liquid holdup Liquid in Vapor out
Tray columns
1
Tray Towers
Liquid out Vapor in 2
Other equipment
Liquid out Vapor in
Bubble column Spray column Centrifugal Contactor
Spray towers
Sparged (bubble) columns
Centrifuge contactors
LS/VS
CHEG351: Mass Transfer Chapter 4
Tray Efficiency and Actual (Real) Number of Trays
x0 − x N y N +1 − y 1
N = =
A 1 N = A 1
x N − y N +1 y 1 − mx 0
x0 − x N y N +1 − y 1
N = =
A 1 N = A 1
x N − y N +1 y 1 − mx 0
P=1atm; T=300° K
x0=0.1
Stripping
yN+1=0 L0 (H2O+NH3) V1 (air+NH3)
(ML,av)0=0.1*17+0.9*18=17.9
1
V/L=(1.873x100/22.4)/(1/17.9) 2
x − y N +1 / m
ln 0 (1 − A ) + A
x N − y N +1 / m
N A ≠1
ln ( 1 / A )
Gas
CHEG351: Mass Transfer Chapter 4
Countercurrent Continuous Contact Equipment
d (Vy ) Vdy G My dy
dz= = =
1 − y i 1 − y i 1 − y i
SFG ah ln SFG ah ( 1 − y ) ln FG ah ( 1 − y ) ln
1−y 1−y 1−y
G My ( 1 − y
)i ,M dy
y1
G My dy
∫
y1
Z=
y2 1 − y i
FG ah ( 1 − y ) ln
⇒ Z= ∫ FG ah (1 − y )( y − y i )
y
1−y
2
y1
G My ( 1 − y ) i ,M dy y1
( 1 − y )i ,M dy
Z= ∫ = tG ∫
H= H tG N tG
y2 G h (
F a 1 − y )( y − y i ) y2 (
1 − y )( y − y i )
height of gas phase number of gas phase
transfer unit transfer unit
constant
H tG
Where
(1 − y ) − (1 − y i )
( 1-y )i.,M = logarithmic mean average of ( 1 − y ) , ( 1 − y i )
(1 − y )
ln
(1 − y i )
If arithmetic mean average is used
1 − y2
y1
dy
=
N tG ∫
y2
y − yi
+ 12 ln
1 − y1
approximate value
Z= H tG N tG Z= = H tL N tL
height of gas phase number of gas phase height of liquid number of liquid
transfer unit transfer unit transfer unit transfer unit
G My G Mx
H tG = H tL =
FG ah FL ah
y1
( 1 − y )i ,M dy x1
( 1 − x )i ,M dx
N tG = ∫ N tL = ∫ 1 − x )( x i − x )
x (
y (
2
1 − y )( y − y i ) 2
1 − y2 1 − x2
y1 x2
dy dx
=
N tG ∫ + 12 ln approximate value N tL = ∫ + 12 ln
y2
y − yi 1 − y1 x1
xi − x 1 − x1
G My H
H=
tOG = H tG + tL
K y ah A G Mx
H tOL =
y1
dy 1 −y2 K x ah
=
N tOG ∫ y −y* + 1
2 ln
1 − y1 y1
x2 − m
y2
y − mx 2
ln 1
1 1
1 − +
ln ( 1 − A) + A
y 2 − mx 2 A A x − y1
= 1 m
1 N toL =
1− 1−A
A
L n +V N +1 =L N +V n +1 L0 V1
Energy Balance
L n H L ,n +V N +1 HV ,N +1 =
L N H L ,N +V n +1 HV ,n +1 N
LN
Energy balance around the entire column VN+1
L0 H L ,0 +V N +1 HV ,N +1 =
L N H L ,N +V 1 H V ,1
1. Enthanlpy
Take a reference temperature of 273 K
HL =( 1 − x ) c p ,oil M oil (T L − 273 ) + xc p ,C 5 (T L − 273 ) + ∆ H solution Oil Methane
L0 V1
=( 1 − x )( 1.884 )( 200 )(T L − 273 ) + x ( 177.5 )(T L − 273 )
(T L − 273 )( 376.8 − 199.3 x )
= kJ / kmole
1
HV =( 1 − y ) c p ,C 2 (TG − 273 ) + y c p ,C 5 (TG − 273 ) + ∆ H vap 2
=( 1 − y )( 35.6 ) (TG − 273 ) + y ( 177.5 ) (TG − 273 ) + 278200
(TG − 273 ) ( 35.6 + 84.2 y ) + 27820
= kJ / kmole
2. Equilibrium LN
N
VN+1
Raoult’s law =
i
y
PA x i
= mx i
Oil+C4 C1+C4
P
2477.07
=PA exp 13.8183 − from Antoine equation
T − 40
2477.07
exp 13.8183 −
T − 40
m (T ) =
101.3
CHEG351: Mass Transfer Chapter 4
Solution Continued
3. Flow rates:
Calculate required liquid flow to achieve 98.6%
removal of pentane
Pentane entering with the incoming gas kmol
=1
s
kmol
x 0.25=0.25 s
kmol
Pentane absorbed =0.25
s
kmol
x 0.986=0.2465 s
2 x13190 + 1 x8480
= 2.2465 H L ,N + 0.7535 x1405
H L ,N = 15050 kJ / kmole
VS 0.75
=
VN = = 0.867 kmole / s 1
1 − y N 1 − 0.135
2
L N = V N + L N −V N +1 = 0.867 + 2.2465 − 1 = 2.144 kmole / s
LN-1 n VN
Repeat the same steps for the next tray N
-G M,B dY C =N C ah dz = ψ C FG, C ah ln
(ψ C - y C ,i ) dz mole
Y A= A ;
VB
YC = C
VB
A+B
. (ψ C - yC ) s
.q G ah dz =hG,c ah (TG − T L ) dz
qG is heat flux kJ/m2-s
hG,c is gas phase convective heat transfer coefficient corrected for
mass transfer
At Steady State
dL=dV
V=VB+VA+VC=(VB+YAVB+YCVB)=VB(1+YA+YC)
dL=dV=VB(dYA+dYC)
Mole
T, K Fraction
Height of Packing
CHEG351: Mass Transfer Chapter 4
1
V
y1 m Lm Vm+1
xm ym+1
m+1
1 L1 V2 L0
x1 y2
D
2 x0=xD xD VN
yN
N
Vn LN VN+1 B
yn xN yN+1 yW
n
Ln Vn+1 W
xn Yn+1
xW
1 1
Subcooled liquid
Saturated liquid
0.9 0.9
0.8 0.8 1
0.7
Partial vaporized
0.7 2
0.6 0.6 3
y0.5 Saturated vapor
y0.5
4
0.4 0.4
Bottoms
Reboiler
CHEG351: Mass Transfer Chapter 6
Flash Vaporization
Single-Stage Operation
Liquid mixture is partially vaporized
Vapor is allowed to equilibrate with liquid
The residual liquid and the resulting vapor are
separated and removed from the apparatus
The product D is richer in the volatile components
Vapor
The bottom W is richer in the least Heat
volatile components
Flash Drum
Exchanger
Feed
Valve
Q kW
Liquid
F= D + W
Flash Drum
F moles/s
F=z F D y D + W xW zF
Energy balance HF
F H F +=
Q D H D +W HW Q kW W moles/s
xW
HW
Solving the energy and material Balance
equations
Q
HD −HF +
W yD −zF F
−= =
D xW −zF Q
HW − H F +
F
xF 0.5 Pj
ln
A j χ j + B j χ 1.5
=
j + C j χ j3 + D j χ 6j
; χ j= 1 −
T
Pc , j 1 − χj Tc , j
P 101325 Pa P j = Pc , j
A j χ j + B j χ 1.5
exp
j + C j χ j3 + D j χ 6j
1 − χj
D/F 0.6
W/F 0.4
Component Tc, K Pc, bar A B C D
N-heptane 540.3 2.74E+06 -7.675 1.371 -3.536 -3.202
W/D 0.667 N-octane 568.8 2.49E+06 -7.912 1.38 -3.804 -4.501
P P Pheptane
xW= 1 − octane
P yD = xW
P heptane − Poctane P
W yD −zF
− =
D xW − z F
Assume T
Calculate χhepatne, χoctane, Poctane, Poctane
Calculate xW T 385.89
d
-(W/D)estimate -0.67
Q
HD −HF +
W yD −zF F
−= =
D xW − z F Q
HW −HF +
F
vapor
Small capacity
Separation is to be done only
L, x
occasionally QB Distillate
Material balance
condenser
dD, y*
dL = −dD
vapor
d ( Lx ) =
0 − y * dD = Ldx + xdL
y *=
dL Ldx + xdL QB W, xw Distillate
Rearranging and intergrating D(t), y=yD=xD
F xF
dL F dx
∫L
W
= =
ln
W ∫
xW
y * −x
Rayleigh Equation
w here
F is the moles of charge of composition x F
W is the moles of residual liquid of composition xW
Start with y* = zf
Find xW by using goal seek function in excel and adjusting T to yield y*
Change y* and repeat the last step
Make a table for y*, xw
Plot 1/(y*-xw) versus xw
Curve fit the plot using polynomial fit
Integrate the equation
Evaluate the integration at x=zF and another lower value
Estimate the difference of the integration at zf and the other x value
Adjust the difference to be ln(F/W) i.e. 0.916 by changing x
This is the final xw
Find yD,ave=(FzF-WxW)/D
xF 0.5
P 1.0132739
D/F 0.6
W/F 0.4
Use Goal Seek Function to adjust y* by changing T
W/D 0.667
∫
dx
y * −x
( )
=0.916 =∫ 22.54 x 2 − 18.96 x + 9.214 dx =
22.54 3 18.96 2
3
x −
2
x + 9.214 x
xW xW xw
5.9
(y*-xw)-1
Using Goal-Seek
5.5
5.4
xW=0.327 5.3
5.2
F z F −W xW 1 x0.5 − 0.4 x0.327
=y D ,av = = 0.615
D 0.6 5.1
0.250 0.300 0.350 0.400 0.450 0.500 0.550 0.600
xW
Rectifying Section
D
Stripping
Section
Feed (F, zF)
Bottom stage N
Distillate (D, xD) Boilup
Material Balance: y1
V n +=
1 D + Ln
V n +1 =
y n +1 D x D + L n x n 1 L1 V2 L0
x1 y2
D
Ln D 2 x0=xD xD
=
y n +1 xn + xD
V n +1 V n +1
L0 L
Reflux Ratio, =
R =
D D
L D L/ D D/ D
y n +1 = xn + xD = xn + xD
L +D L +D L/ D +D/ D L/ D +D/ D
R 1
=
y n +1 xn + xD Operating line for rectifying section
R +1 R +1
2 1 L1 V2 L0
x1 y2
D
2 x0=xD xD
3
5 4
Vn
yn
n
Ln Vn+1
xn Yn+1
Material Balance: m Lm
xm
Vm+1
ym+1
L= W +V m + 1 m+1
m
L=
m xm W xW +V m +1 y m +1
Lm W VN
=
y m +1 xm − xW yN
V m +1 V n +1 N
LN VN+1 B
For constant molar overflow: xN yN+1 yW
= = V st and
V m +1 constant = L m constant =L st W
L st W xW
=
y m +1 xm − xW
V st V st
V st L st −W
Boilup Ratio, V=
B =
W W
V st + W W V st / W + W / W W /W
y m=
+1 xm − x=
W xm + xW
V st V st V st / W V st / W
VB + 1 1
=
y m +1 xm + xD Operating line for Stripping section
VB VB
Energy Balance F
f
Lst Vst
zF
FH F + LH L ,f −1 +V st H G ,f +1 =
VH G ,f + L st H L ,f xf yf+1
f+1
( L st − L ) H L ,f =
(V st −V ) H G ,f + FH F
L st − L H G ,f − H F
= = q ( the energy required to convert 1 mol of the feed to saturated vapor )
F H G ,f − H L ,f
Partial vaporized
Saturated Vapor 0 0.7
q-line equation
0.5
0.4
q z
= x− F
Superheated vapor
y 0.3
1 −1 q −1
0.2
0.1
xD
The intersection of the operating 0
0
xW
1
0.9
0.9 1
0.8
1
0.8 2
0.7
0.7
0.6 3
2
0.6 y
y 0.5
4
0.5
0.4
0.4 3 5
0.3
0.3
0.2 6
0.2 4
0.1
0.1 5 xW xF xD
0
xW xF xD 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
x
0.9
0.8
0.7
0.6
y 0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Reflux ratio, R
D
1
xD
F
f
zF
Lst=W Vst
xW y=0
EO =
1
ln
A