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CHEMICAL
ENGINEERING
SEPARATIONS: A
HANDBOOK FOR
STUDENTS
Monica Lamm and Laura Jarboe

Iowa State University
Chemical Engineering Separations: A
Handbook for Students (Lamm and Jarboe)
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This text was compiled on 01/13/2024
TABLE OF CONTENTS
About the Authors
Licensing
Preface
1: Chapters
1.1: Performance Metrics for Separation Processes
1.2: Mass Transfer in Gas-liquid Systems
1.3: Liquid-liquid Extraction
1.4: Absorption and Stripping
1.5: Distillation
1.6: Membranes
1.7: Sorption and Chromatography
Index
Glossary
Detailed Licensing
1 https://eng.libretexts.org/@go/page/76387
About the Authors
This handbook was developed by faculty and students at Iowa State University.
Authors
Monica H. Lamm is Associate Professor of Chemical and Biological Engineering at Iowa State University. She teaches courses in
chemical engineering at the undergraduate and graduate levels. Her research interests include molecular simulation and engineering
education.
Laura R. Jarboe is Associate Professor of Chemical and Biological Engineering at Iowa State University. She frequently teaches the
Separations course and Chemical Engineering Thermodynamics. Her research focuses on the engineering of microbial cell factories
for the robust production of fuels and chemicals.
Technical assistants
Samuel M. Rothstein typeset the equations for the handbook. Samuel’s prior experience as a teaching assistant for the separations
course was invaluable during the production of the handbook. Samuel is currently a PhD candidate at Iowa State University in
Chemical and Biological Engineering. Samuel received his BS in Chemical Engineering at the University of Minnesota Duluth. His
current research interests focus on utilizing genome editing techniques in lactic acid bacteria.
Sandeep Kumar, a senior at Iowa State University, produced the illustrations for the handbook. He is majoring in Landscape
Architecture with a minor in Sustainability.
Licensing
A detailed breakdown of this resource's licensing can be found in Back Matter/Detailed Licensing.
Preface
Chemical Engineering Separations: A Handbook for Students is intended for use by undergraduate students who are taking a
course in chemical engineering separations. The handbook assumes that students have taken one or two semesters of chemical
engineering thermodynamics, one semester of heat and mass transfer, and one semester of computational methods for chemical
engineering.
The purpose of this handbook is to introduce students to chemical engineering separations in a way that most closely aligns with
what most entry-level chemical engineers will do in the workplace. Most newly hired chemical engineers will be responsible for
monitoring and troubleshooting existing processes and proposing modifications to improve process performance. For this reason,
we have written the handbook to emphasize how to optimize process conditions, how to retrofit an existing unit to meet a given
separation objective while not exceeding operating capacity, or how to select the best existing or pre-fabricated unit to meet a
separation objective while maintaining safe operation at a reasonable cost.
If you plan to reuse or adapt this text, please notify us by contacting us at [email protected] or [email protected].
CHAPTER OVERVIEW
1: Chapters
1.5: Distillation
1.6: Membranes
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edit history is available upon request.
1
= mass or molar flow rate of species i entering separator k in feed stream (mass time-1 or mol time-1)
(F )
n
i,k
= mass or molar flow rate of species i leaving separator k in first product stream (mass time-1 or mol time-1)
(1)
n
i,k
= mass or molar flow rate of species i leaving separator k in second product stream (mass time-1 or mol time-1)
(2)
n
i,k
SF i,k = split fraction for species i in separator k (dimensionless)

SR i,k = split ratio for species i in separator k (dimensionless)
(1) (F )
SF i,k = n /n (1.1)
i,k i,k
(1) (2)
SR i,k = n /n = SF i,k /(1 − SF i,k ) (1.2)
i,k i,k
 Example
For the process below, compute the split fraction and the split ratio for iC5 H12 . Designate the overhead stream as product
stream 1.
1.1.1 https://eng.libretexts.org/@go/page/76358
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the LibreTexts platform; a detailed edit history is available upon request.
In chemical separations, we can use thermodynamic models to predict the composition in each phase at equilibrium. For example,
Raoult’s Law describes the compositions of vapor and liquid phases at equilibrium. Mass transfer models help us understand how
we can manipulate the process to reach equilibrium in a faster or more economical manner.
This chapter will briefly review fundamentals of mass transfer in gas-liquid systems because many of the separation processes in
this handbook involve the movement of species between gas and liquid phases.
Diffusion-based Mass T ransfer

JAz = molar flux of A relative to the molar-average velocity of the mixture in the z direction
DAB = mutual diffusion coefficient of A in B (= D BA )
cA = molar concentration of A
NA = molar flux of species A
N = total molar flux
xA = mole fraction of species A
c = total molar concentration
dcA
JAz = −DAB (1.1)
dz
dxA
NA = xA N – c DAB (1.2)
dz
Falling Liquid Film with Gaseous Solute ADiffusing into Liquid B

Γ = liquid flow rate per unit width of film = ρū y rH (mass length −1
time −1
)
δ = film thickness (length)
η = metric used in selecting the appropriate equation for calculating k c
μ = dynamic viscosity of the liquid (pressure time)

δ = density of the liquid (mass volume-1)
A = available area for mass transfer = L ∗ W (length2)
cA = concentration of species A in liquid B (mol volume-1)
cAi = concentration of species A in liquid B at the gas/liquid interface (mol volume −1
)
cA0 = concentration of species A in liquid B when the liquid enters the enters (mol volume −1
)
ΔcA = log mean concentration difference driving force (mol volume −1
)
¯
c̄ A
= bulk concentration of species A in liquid B at any position y (mol volume −1
)
¯¯
cAL = bulk concentration of species A in liquid B at any position y = L (mol volume −1
)
DAB = diffusivity of solution A in liquid B (length time 2 −1
)
g = gravitational constant (length time −2
)
HA = Henry’s Law constant for solute A in our liquid at our system temperature (volume pressure mol −1
)
kc,ave = average mass transfer coefficient (length time −1
)
L = film height (length)
nA = molar flow rate of species A (mol time −1
)
NRe = Reynolds number (dimensionless)
NSc = Schmidt number (dimensionless)
NPe, M = Peclet number for mass transfer (dimensionless)
PA = partial pressure of species A in the gas phase (pressure)
rH = flow cross section per wetted perimeter (length)
ūy = bulk velocity of the falling film in the y direction (length time −1
)
W = film width (length)
Reynolds number for a falling film
ρūy 4 rH 4Γ
NRe = = (1.3)
μ μ
Rate
nA = ūy δW ( c̄ AL − cA0 ) (1.4)
nA = kc AΔcA (1.5)
Film thickness
1/2 1/3
¯¯
3 ūyμ 3μΓ
δ =( ) =( ) (1.6)
2
ρg ρ g
Hydraulic radius for a falling film Flow cross section: δW ; wetted perimeter: W
δW
rH = =δ (1.7)
W
Schmidt number
μ
NSc = (1.8)
ρDAB
Peclet number for mass transfer

¯¯
4δūy 4Γ
NPe,M = NRe NSc = = (1.9)
DAB ρDAB
Mass transfer coefficient k c,ave
2 DAB L 8/3 8/3

η = = = (1.10)
2 ¯¯
¯
3δ uy NRe NSc (δ/L) (δ/L)NPe,M
if η < 0.001,
1/2
6 DAB Γ
kc,ave = ( ) (1.11)
πδρL
if η > 0.1,
δ
¯¯
kc,ave = ( ūy ) (0.241 + 5.1213η) (1.12)
L
if η > 1,
DAB
kc,ave = 3.414 (1.13)
δ
Henry’s Law, applies at the interface

PA
cA = (1.14)
HA
Log mean concentration difference
(cAi − cA0 ) − (cAi − c̄ AL )
ΔcA = (cAi − c̄ A )LM = (1.15)
ln[(cA − cA )/(cA − c̄ A )]
i 0 i L
 Example
10 mL/s of water at 25 C flows down a wall that is 1.0 m wide and 3.0 m high. This film is in contact with pure CO2 at 1.0
∘
atm, 25 C. Find the rate of absorption of CO2 into the water (kmol/s).
∘
ρH2O = 998 kg/m3

μH2O = 8.90×10-4 Pa s
DCO2,H2O = 1.96×10-9 m2/s
HCO2,H2O = 29.41 L atm mol-1
Velocity and Concentration Boundary Layers for Laminar Horizontal Flow Across a Flat Plate
δ = thickness (height) of the velocity boundary layer (length)
δc = thickness (height) of the concentration boundary layer (length)
μ = fluid viscosity (pressure time) or (mass length-1 time-1)
ρ = fluid density (mass volume-1)
cA = concentration of species A in fluid B at some point (x, z ) (mol volume-1)
cA0 = initial concentration of species A in fluid B (mol volume-1)
cAi = concentration of species A in fluid B at the interface (mol volume-1)
DAB = diffusivity of solute A in fluid B (length2 time-1)
NRe,x = Reynolds number (dimensionless)
NSc = Schmidt number (dimensionless)
u0 = free-stream velocity of the fluid in the x direction (length time-1)
ux = fluid velocity in the x direction at some point (x, z ) (length time-1)
x = horizontal distance from the leading edge of the flat plate (length)
z = vertical distance from the plate surface (length)
δ 4.96
= (2.1)
0
x N .5
Re,x
x u0 ρ
NRe,x = (2.2)
μ
ux z z 3
= 1.5 ( ) − 0.5 ( ) (2.3)

u0 δ δ
δ
δc = (2.4)
1/3
N
Sc
μ
NSc = (2.5)
ρDAB
3
(cA − cA ) z z
i
= 1.5 ( ) − 0.5 ( ) (2.6)
(cA − cA ) δc δc
i 0
 Example
Air at 100 C and 1.0 atm with a free-stream velocity of 5.0 m/s flows over a 3.0 m long flat plate made of naphthalene.
∘
(a) At what horizontal position does flow become turbulent?
(b) What is the thickness of the velocity boundary layer at that point?
(c) What is the thickness of the concentration boundary layer at that point?
(d) What is the concentration of naphthalene in the air at this horizontal position and vertical position that is half of the height
of the concentration boundary layer?
μair = 2.15×10-5 kg m-1 s-1
ρair = 0.0327 kmol m-3
DAB = 0.94×10-5 m2 s-1
cAi = 4.3×10-3 kmol m-3
Film Theory and Overall Mass Transfer Coefficients

δ = thickness of the film in which c ≠ c (length)
A Ab
c = total concentration of liquid B (mol volume-1)

cAi = concentration of species A in liquid B at the interface (mol volume-1)
cAb = bulk concentration of species A in liquid B (mol volume-1)
c
∗
A
= concentration of species A in liquid B at equilibrium with the bulk gas phase (mol volume-1)
D = diffusivity of species A in liquid B (area time-1)
AB
H = Henry’s Law constant for equation of the form c = H P ;

′
A A
′
A A
(mol volume-1 pressure-1)

-1
k = liquid-phase mass transfer coefficient, with respect to concentration driving force (length time )
c
K = overall mass transfer coefficient, with respect to pressure driving force (mol time area pressure-1)
G
-1 -1
K = overall mass transfer coefficient, with respect to concentration driving force (length time-1)
L
-1
k = gas-phase mass transfer coefficient, pressure driving force (mol time
p area-1 pressure-1)
-1 -1
N = molar flux (mol area time )
A
P Ab=p = partial pressure of species A in the bulk gaseous phase (pressure)

Ab
P
A
= partial pressure of species A in a gas at equilibrium with the bulk liquid phase (pressure) x = mole fraction of species A
∗
Ai
in liquid B at the interface

x = bulk mole fraction of species A in liquid B
Ab
Film Theory
DAB cDAB
NA = ( ) (cAi − cAb ) = ( ) (xAi − xAb ) (3.1)
δ δ
 Example
SO2 is absorbed from air into water using a packed absorption tower. At a specific location in the tower, we know that the
pressure of SO2 is 0.15 atm. Measurements of the gas composition above and below this location in the tower have told us that
the flux of SO2 into the water is 0.0270 kmol SO2 m-2 hr-1. We were able to sample the bulk liquid phase at this location and
found that it contained 3.0×10-4 mol SO2/mol. Assuming that this system fits film theory, find the thickness of the film.
DSO
2
, H2 O = 1.7*10-9 m2 s-1
HSO
2
, H2 O = 1.2 L atm mol-1
Two-Film Theory, Overall Mass Transfer Coefficients, Gas/Liquid

′ −1
H 1
′ A
NA = (PAb H − cAb ) ( + ) (3.2)
A
kp kc
′
1 H 1
A
= + (3.3)
KL kp kc
∗
NA = KL (c − cAb ) (3.4)
A
−1
1 1
∗
NA = (PAb − P )( + ) (3.5)
A ′
kp H kc
A
1 1 1
= + (3.6)
′
KG kp H kc
A
∗
NA = KG (PAb − P ) (3.7)
A
 Example
We intend to use water to absorb SO2 from air. The incoming air is at 50°C and 2.0 atm and contains 0.085 mol SO2/mol. The
incoming water, also at 50°C, already contains 0.0010 mol SO2/mol.
a. Which phase is most limiting to mass transfer?
b. What is the expected initial flux value?
Solution
kc = 0.18 m hr-1
kp = 0.040 kmol hr-1 m-2 kPa-1
H
′
A
(50°C) = 0.76 mol atm-1 L-1
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Staged Liquid-Liquid Extraction and Hunter Nash Method
En = extract leaving stage n . This could refer to the mass of the stream or the composition of the stream.
F = solvent entering extractor stage 1. This could refer to the mass of the stream or the composition of the stream.
n = generic stage number
N = Final stage. This is where the fresh solvent S enters the system and the final raffinate R leaves the system.
N
M = Composition of the mixture representing the overall system. Points (F and S ) and (E and 1 RN ) must be connected by a
straight line that passes through point M . M will be located within the ternary phase diagram.
P = Operating point. P is determined by the intersection of the straight line connecting points (F , E ) and the straight line
1
connecting points (S , R ). Every pair of passing streams must be connected by a straight line that passes through point P . P is
N
expected to be located outside of the ternary phase diagram.

Rn = raffinate leaving stage n . This could refer to the mass of the stream or the composition of the stream.
S = solvent entering extractor stage N . This could refer to the mass of the stream or the composition of the stream.
S/F = mass ratio of solvent to feed
(xi )n = Mass fraction of species i in the raffinate leaving stage n
(yi )n = Mass fraction of species i in the extract leaving stage n
Process schematic for multistage liquid-liquid extraction.

Determining number of stages N when (1) feed rate; (2) feed composition; (3) incoming solvent rate; (4) incoming solvent
composition; and (5) outgoing raffinate composition have been specified/selected.
1. Locate points F and S on the ternary phase diagram. Connect with a straight line.
2. Do a material balance to find the composition of one species in the overall mixture. Use this composition to locate point M
along the straight line connection points F and S . Note the position of point M .
3. Locate point R on the ternary phase diagram. It will be on the equilibrium curve. Draw a straight line from R to M and
N N
extend to find the location of E on the equilibrium curve.

1
4. On a fresh copy of the graph, with plenty of blank space on each side of the diagram, note the location of points F , S , and R N
(specified/selected) and E (determined in step 3).

1
5. Draw a straight line between F and E . Extend to both sides of the diagram. Draw a second straight line between S and R .
1 N
Note the intersection of these two lines and label as “P ”.

6. Determine the number of equilibrium stages required to achieve the desired separation with the selected solvent mass.
– Stream R is in equilibrium with stream E . Follow the tie-lines from point R to E .
N N N N
– Stream E passes stream R

N N −1 . Connect point E to operating point P with a straight line, mark the location of R
N N −1 .
– Stream R N −1 is in equilibrium with stream E N −1 . Follow the tie-lines from stream R
N −1 to E
N −1 .
– Stream E N −1 passes stream R N −2 . Connect E
N −1 to operating point P with a straight line, mark the location of R N −2 .
– Continue in this manner until the extract composition has reached or passed E . Count the number of equilibrium stages.
1
Watch this two-part series of videos from LearnChemE that shows how to use the Hunter Nash method to find the number of
equilibrium stages required for a liquid-liquid extraction process.
Hunter Nash Method 1: Mixing and Operating Points (9:30)
Hunter Nash Method 2: Number of Stages (6:30)
 Example
1000 kg/hr of a feed containing 30 wt% acetone, 70 wt% water. The solvent is pure MIBK. We intend that the raffinate contain
no more than 5.0 wt% acetone. How many stages will be required for each proposed solvent to feed ratio in the table below?
S/F S (kg/hr) (x_A)_M target (y_A)_1 N
1.0
2.0
0.2
Hunter Nash Method for Finding Smin, Tank Sizing and Power Consumption for Mixer-Settler Units
Staged LLE: Hunter-Nash Method for Finding the Minimum Solvent to Feed Ratio
En = extract leaving stage n . This could refer to the mass of the stream or the composition of the stream.
F = solvent entering extractor stage 1. This could refer to the mass of the stream or the composition of the stream.
N = Final stage. This is where the fresh solvent S enters the system and the final raffinate R leaves the system.
N
M = Composition of the overall mixture. Points (F and S ) and (E and R ) are connected by a straight line passing through M .
1 N
P = Operating point. Every pair of passing streams must be connected by a straight line that passes through P .
Rn = raffinate leaving stage n . This could refer to the mass of the stream or the composition of the stream.
S = solvent entering extractor stage N . This could refer to the mass of the stream or the composition of the stream.
S/F = mass ratio of solvent to feed
Smin /F = Minimum feasible mass ratio to achieve the desired separation, assuming the use of an infinite number of stages.
(xi )n = Mass fraction of species i in the raffinate leaving stage n
(yi )n = Mass fraction of species i in the extract leaving stage n
Pmin = Point associated with the minimum feasible S/F for this feed, solvent and (raffinate or extract) composition. P min is the
intersection of the line connecting points (R , S ) and the line that is an extension of the upper-most equilibrium tie-line.
N
Determining minimum feasible solvent mass ratio (S /F ) when (1) feed composition; (2) incoming solvent composition; and (3)
min
outgoing raffinate composition have been specified/selected.

1. Locate points S and R on the phase diagram. Connect with a straight line.
N
2. Extend the upper-most tie-line in a line that connects with the line connecting points (S and R ). Label the intersection P .
N min
3. Find point F on the diagram. Draw a line from P to F and extend to the other side of the equilibrium curve. Label E @
min 1
S .
min
4. On a fresh copy of the phase diagram, label points F , S , R and E @S . Draw one line connecting points S and F and
N 1 min
another line connecting points E @S 1 min
5. and R . The intersection of these two lines is mixing point M . Note the composition of species i at this location.
N
6. Calculate
Smin (xi )F − (xi )M
= (5.1)
F (xi )M − (xi )S
 Example
We have a 1000 kg/hr feed that contains 30 wt% acetone and 70 wt% water. We want our raffinate to contain no more than 5.0
wt% acetone. What is the minimum mass of pure MIBK required?
Liquid-Liquid Extraction: Sizing Mixer-settler Units

ΦC = volume fraction occupied by the continuous phase
ΦD = volume fraction occupied by the dispersed phase
μC = viscosity of the continuous phase (mass time-1 length-1)
μD = viscosity of the dispersed phase (mass time-1 length-1)
μM = viscosity of the mixture (mass time-1 length-1)
ρC = density of the continuous phase (mass volume-1)
ρD = density of the dispersed phase (mass volume-1)
ρM = average density of the mixture (mass volume-1)
Di = impeller diameter (length)
DT = vessel diameter (length)
H = total height of mixer unit (length)
N = rate of impeller rotation (time-1)
NPo = impeller power number, read from Fig 8-36 or Perry’s 15-54 (below) based on value of N Re (unitless)
(NRe )C = Reynold’s number in the continuous phase = inertial force/viscous force (unitless)
P = agitator power (energy time-1)
QC = volumetric flowrate, continuous phase (volume time-1)
QD = volumetric flowrate, dispersed phase (volume time-1)
V = vessel volume (volume)
Tank and impeller sizing
V
residencetime = (5.2)
QC + QD
Geometry of a cylinder
2
πD H
T
V = (5.3)
4
General guidelines
H
=1 (5.4)
DT
Di 1
= (5.5)
DT 3
Impeller power consumption:

3 5
P = NP o N D ρ (5.6)
i m
2
D Nρ
i M
NRe = (5.7)
μM
ρ =ρ ΦC + ρ ΦD (5.8)
M C D
μC 1.5μD ΦD
μM = [1 + ] (5.9)
ΦC μC + μD
Modeling Mass Transfer in Mixer-Settler Units

Δρ = density difference (absolute value) between the continuous and dispersed phases (mass volume-1)
ϕC = volume fraction occupied by the continuous phase
ϕD = volume fraction occupied by the dispersed phase
μD = viscosity of the dispersed phase (mass time-1 length-1)
μM = viscosity of the mixture (mass time-1 length-1)
ρM = average density of the mixture (mass volume-1)
σ = interfacial tension between the continuous and dispersed phases
(mass time-2)
a = interfacial area between the two phases per unit volume (area volume-1)
,
cD,in cD,out = concentration of solute in the incoming or outgoing dispersed streams (mass volume-1)
c
∗
D
= concentration of solute in the dispersed phase if in equilibrium with the outgoing continuous phase (mass volume-1)
DC = diffusivity of the solute in the continuous phase (area time-1)
DD = diffusivity of the solute in the dispersed phase (area time-1)
Di = impeller diameter (length)
DT = vessel diameter (length)
dvs = Sauter mean droplet diameter; actual drop size expected to range from 0.3d vs − 3.0 dvs (length)
EMD = Murphree dispersed-phase efficiency for extraction
g = gravitational constant (length time-2)
H = total height of mixer unit (length)
kc = mass transfer coefficient of the solute in the continuous phase (length time-1)
kD = mass transfer coefficient of the solute in the dispersed phase (length time-1)
KOD = overall mass transfer coefficient, given on the basis of the dispersed phase (length time-1)
m = distribution coefficient of the solute, Δc C /ΔcD (unitless)
-1
N = rate of impeller rotation (time )
(NEo )C = Eotvos number = gravitational force/surface tension force (unitless)
(NFr )C = Froude number in the continuous phase = inertial force/gravitational force (unitless)
Nmin = minimum impeller rotation rate required for complete dispersion of one liquid into another
(NRe )C = Reynold’s number in the continuous phase = inertial force/viscous force (unitless)
(NSh )C = Sherwood number in the continuous phase = mass transfer rate/diffusion rate (unitless)
(NSc )C = Schmidt number in the continuous phase = momentum/mass diffusivity (unitless)
(NWe )C = Weber number = inertial force/surface tension (unitless)
QD = volumetric flowrate of the dispersed phase (volume time-1)
V = vessel volume (volume)
Calculating N min
0.084
2 2.76 2
N ρM Di DT μ σ
min 0.106 M
= 1.03 ( ) (ϕD ) ( ) (6.1)
5
gΔρ Di D ρM g 2 (Δρ)2
i
ρM = ρC ϕC + ρD ϕD (6.2)
μC 1.5μ ϕ
D D
μM = (1 + ) (6.3)
ϕC μC + μD
Estimating Murphree efficiency for a proposed design

Sauter mean diameter
−0.6
if NWe < 10, 000, dvs = 0.052 Di (NWe ) exp(4 ϕD ) (6.4)
−0.6
if NWe > 10, 000, dvs = 0.39 Di (NWe ) (6.5)
3 2
D N ρC
i
NWe = (6.6)
σ
mass transfer coefficient of the solute in each phase

6.6DD
kD = (6.7)
dvs
(NSh )C Dc
kC = (6.8)
dvs
−5 1/3 2/3 −1/2

(NSh )C = 1.237 × 10 (NSc ) (NRe ) (ϕD ) (6.9)
C C
2 1/2
5/12 Di dvs 5/4
(NFr ) ( ) ( ) (NEo ) (6.9)
C C
dvs DT
μ
C
(NSc )C = (6.10)
ρ DC
C
2
D Nρ
i C
(NRe )C = (6.11)
μC
2
Di N
(NFr )C = (6.12)
g
2
ρD dvs g
(NEo )C = (6.13)
σ
Overall mass transfer coefficient for the solute

1 1 1
= + (6.14)
KOD kD mkC
Murphree efficiency
−1
KOD aV KOD aV
EMD = (1 + ) (6.15)
QD QD
6ϕD
a = (6.16)
dvs
Experimental assessment of efficiency

cD,in − cD,out
EMD = (6.17)
∗
cD,in − c
D
 Example
1000 kg/hr of 30 wt% acetone and 70 wt% water is to be extracted with 1000 kg/hr of pure MIBK. Assume that the extract is
the continuous phase, a residence time of 5 minutes in the mixing vessel, standard sizing of the mixing vessel and impeller.
Find the power consumption and Murphree efficiency if the system operates at N , controlled at the level of 1 rev/s. Ignoremin
the contribution of the solute and the co-solvent to the physical properties of each phase.
MIBK
density = 802 kg m-3
viscosity = 0.58 cP
diffusivity with acetone at 25°C = 2.90×10-9 m2 s-1
Water
viscosity = 0.895 cP
diffusivity with acetone at 25°C = 1.16×10-9 m2 s-1
The interfacial tension of water and MIBK at 25°C = 0.0157 kg s-2. Use the ternary phase diagram to find m.
Liquid-Liquid Extraction Columns

Δρ = density difference (absolute value) between the continuous and dispersed phases (mass volume-1)
σ = interfacial tension between the continuous and dispersed phases
(mass time-2)
DT = column diameter (length)
H = total height of column (length)
HETS = height of equilibrium transfer stage (length)
m
∗
C
= mass flowrate of the entering continuous phase (mass time-1)
m
∗
D
= mass flowrate of the entering dispersed phase (mass time-1)
N = required number of equilibrium stages
u0 = characteristic rise velocity of a droplet of the dispersed phase (length time-1)
Ui = superficial velocity of phase i (C = continuous, downward; D = dispersed, upward) (length time-1)
V
i
∗
= volumetric flowrate of phase i (volume time-1)
∗
4V
i
Ui = (7.1)
2
πD
T
definition of superficial velocity

∗
UD m ρC
D
= ( ) (7.2)
∗
UC m ρD
C
(UD + UC )actual = 0.50(UD + UC )f (7.3)
for operation at 50% of flooding

0.01σΔρ
u0 = (7.4)
μC ρC
for rotating-disk columns, D = 8 to 42 inches, with one aqueous phase

T
∗ 0.5 ∗ 0.5
4m 4m
D C
DT = ( ) =( ) (7.5)
ρD UD π ρC UC π
H = HETS ∗ N (7.6)
 Example
1000 kg/hr of 30 wt% acetone and 70 wt% water is to be extracted with 1000 kg/hr of pure MIBK in a 2-stage column process.
Assume that the extract is the dispersed phase. Ignoring the contribution of the solute and the co-solvent to the physical
properties of each phase, find the required column diameter and height.
MIBK
viscosity = 0.58 cP
Water
viscosity = 0.895 cP
The interfacial tension of water and MIBK at 25°C = 0.0157 kg s-2.
This page titled 1.3: Liquid-liquid Extraction is shared under a CC BY-NC 4.0 license and was authored, remixed, and/or curated by Monica
Lamm and Laura Jarboe (Iowa State University Digital Press) via source content that was edited to the style and standards of the LibreTexts
platform; a detailed edit history is available upon request.
Overview of Absorption and Stripping Processes
ϕA = fraction not absorbed (unitless)
ϕS = fraction not stripped (unitless)
A = absorption factor (unitless)
K = equilibrium constant, (mole fraction in gas)/(mole fraction in liquid)
L = total liquid flow rate (mol time-1)
V = total gas flow rate (mol time-1)
S = stripping factor (unitless)
x (lowercase) = mol fraction of solute in liquid phase (mol solute/mol total liquid)
X (uppercase) = mol ratio of solute in liquid phase (mol solute/mol solvent)
y (lowercase) = mol fraction of solute in gas phase (mol solute/mol total vapor)
Y (uppercase) = mol ratio of solute in gas phase (mol solute/mol gaseous carrier)
(L/V )
A = (8.1)
K
K 1
S = = (8.2)
(L/V ) A
 Example
K for acetone in an air/water system is 2.0. We intend to absorb 90% of the acetone entering in the gaseous phase into the
liquid phase. How many theoretical stages would be required for (L/V) = 1, (L/V) = 2, and (L/V) = 10?
Finding mole ratio from mole fraction:

y
Y = (8.3)
1 −y
x
X = (8.4)
1 −x
Finding mole fraction from mole ratio:

Y
y = (8.5)
1 +Y
X
x = (8.6)
1 +X
Graphical Method to Find Equilibrium Stages for Absorption Columns

K = equilibrium constant, (mole fraction in gas)/(mole fraction in liquid)
L = liquid flow rate (mol time-1)
L
′
= liquid flow rate on a solute-free basis (mol time-1)
N = total number of stages. For an absorption column, N is the bottom stage. For a stripping column, N is the top stage.
V = gas flow rate (mol total time-1)
V
′
= gas flow rate on a solute-free basis (mol gaseous carrier time-1)
x = mole fraction of solute in liquid phase (mol solute/mol total liquid)
X = mole ratio of solute in liquid phase (mol solute/mol liquid absorbent)
X0 = mole ratio of solute/absorbent in liquid entering the top of the absorption column
XN = mole ratio of solute/absorbent in liquid leaving the bottom of the absorption column
y = mole fraction of solute in gas phase (mol solute/mol total gas)
Y = mole ratio of solute in gas phase (mol solute/mol gaseous carrier)
Y1 = mole ratio of solute/gaseous carrier in gas leaving the top of the absorption column
YN +1 = mole ratio of solute/gaseous carrier in gas entering the bottom of the absorption column
Operating line for absorption column:
′ ′
L L
Yn+1 = Xn ( ) + Y1 − X0 ( ) (9.1)
′ ′
V V
Watch a video from LearnChemE that demonstrates how to determine the number of equilibrium stages required for an absorption
column when given inlet and outlet specifications: Absorption of a Dilute Species (10:43): https://youtu.be/BoPKngZZwVI
 Example
The following equilibrium data is available for water, ammonia, and air at 20°C.
We intend to use fresh water to absorb the ammonia from a stream of air containing 28.5 mol% ammonia, with both streams at
20°C. We intend to absorb 80% of the incoming ammonia. How many equilibrium stages are required for each of the following
design cases?
(a) L /V = 1.0
′ ′
(b) L /V = 1.6
′ ′
(c) L /V = 2.0
′ ′
Determining the Minimum Ratio for Absorbent to Gas Flow Rates and a Mathematical Approach for
Finding the Number of Equilibrium Stages
K = equilibrium constant, (mole fraction solute in gas)/(mole fraction solute in liquid)
L
′
= liquid flow rate on a solute-free basis (mol liquid absorbent time-1)
n = generic equilibrium stage
N = bottom equilibrium stage for an absorption column
V
′
= gas flow rate on a solute-free basis (mol gaseous carrier time-1)
(L / V
′
) = relative molar flowrates of solute-free absorbent and solute-free carrier gas at which an infinite number of
′
min
equilibrium stages is required in order to achieve the desired separation

x = mole fraction of solute in liquid phase (mol solute/mol total liquid)
X = mole ratio of solute in liquid phase (mol solute/mol liquid absorbent)
X0 = mole ratio of solute/absorbent in liquid entering the top of the absorption column
XN = mole ratio of solute/absorbent in liquid leaving the bottom of the absorption column
y = mole fraction of solute in gas phase (mol solute/mol total gas)
Y = mole ratio of solute in gas phase (mol solute/mol gaseous carrier)
Y1 = mole ratio of solute/gaseous carrier in gas leaving the top of the absorption column
YN +1 = mole ratio of solute/gaseous carrier in gas entering the bottom of the absorption column
Equilibrium:
yn Yn /(1 + Yn )
Kn = = (10.1)
xn Xn /(1 + Xn )
Operating line:
′ ′
L L
Yn+1 = Xn ( ) + Y1 − X0 ( ) (10.2)
′ ′
V V
when X ~ x and Y ~ y ,
′
L yN +1 − y1
( ) = (10.3)
′ yN+1
V − x0
min
KN
when X ~ x, Y ~ y and x0 = 0
′
L y1
( ) = KN (1 − ) (10.4)
′
V yN +1
min
 Example
180 kmol/hr of off-gas from a fermentation unit contains 98 mol% CO2 and 2 mol% ethanol. We would like to recover 97% of
this ethanol and have proposed the use of a staged absorption column with water as the absorbent. The incoming water
contains no ethanol and is at 30°C. The incoming gaseous stream is at 30°C, 110 kPa. Assume there is no absorption of CO2
into the water. The activity coefficient at infinite dilution for ethanol in water at 30°C is 6.0 and Psat is 10.5 kPa. Thus, K =
γiPisat/P = 0.57.
(a) What is (L /V
′ ′
)min ?
(b) How many equilibrium stages are required if we operate at 1.5*(L /V ′ ′
)min ?
Stage Efficiency and Column Height

λ = inverse absorption factor (unitless)
μL = liquid-phase viscosity (mass time-1 length-1)
ρL = liquid-phase density (mass volume-1)
a = vapor-liquid interfacial area per volume of combined gas/liquid on the tray (area volume-1)=(length-1)
Ab = portion of the column cross-sectional area dedicated to mixing of the gas/liquid (area)
EMV = Murphree efficiency, calculated on the basis of the vapor phase composition
EO = overall stage efficiency
K = equilibrium constant (gas-phase composition/liquid-phase composition)
KG = overall gas mass-transfer coefficient, partial pressure driving force (mol time-1 area-1 pressure-1)
L = molar flow rate of liquid phase (mol time-1)
ML = molecular weight of the liquid phase
Na = actual number of stages required to achieve the desired separation
NOG = number of overall gas phase mass transfer units
Nt = number of theoretical stages required to achieve the desired separation
P = pressure (force area-1)
T = temperature (temperature)
V = molar flow rate of gaseous phase (mol time-1)
xi,n = the actual mole fraction of species i in the liquid leaving stage n and entering stage n+1
yi = the mole fraction of species i in a gas at some fixed point in the column
yi,n+1 = the actual mole fraction of species i in the gas leaving stage n+1 and entering stage n
yi,n = the actual mole fraction of species i in the gas leaving stage n and entering stage n-1
y
i,n
∗
= the mole fraction of species i in the gas leaving stage n if it had reached equilibrium with the liquid leaving that stage, where
the liquid phase composition is x i,n
Zf = height of combined gas and liquid holdup on the tray (length)

Nt
EO = (11.1)
Na
EO = 19.2 − 57.8 log μL 0.2 < μL < 1.6 cP, μL must be in cP (11.2)
10
0.2 < μ < 1.6 cP, μ must be in cP

L L
2
KML μL KML μL
log10 EO = 1.597 − 0.199 log10 ( ) − 0.0896 [log10 ( )] (11.3)
ρL ρL
Eq 11.3 is applicable for this range of conditions: μ must be in cP, ρ must be in lb ft-3; restricted to D = 2 in – 9 ft, average P =
L L T
14.7 – 485 psi, average T = 60 – 138°F, E = 0.65% – 69%

O
 Example
For our CO2/ethanol/water system, we found that for 97% removal of the ethanol using water as the absorbent and operating at
30°C, 110 kPa, with K = 0.57 and (L /V )
′ ′
= (L /V )
actual = 0.828, 7 theoretical stages required. How many actual stages
′ ′
min
are needed, according to equations 11.2 and 11.3?

μL = 0.89 cP
M L= 18 lb/lb-mole
ρL = 62.5 lb ft-3
log10 [1 + EMV (λ − 1)]

EO = (11.4)
log10 λ
KV
λ = (11.5)
L
yi,n+1 − yi,n
EMV = = 1 − exp(−NOG ) (11.6)
∗
yi,n+1 − y
i,n
KG aP Zf
NOG = (11.7)
(V / Ab )
Staged Column Height and Diameter
ρV = vapor-phase density (mass volume-1)
σ = liquid-phase surface tension (force length-1)
A = total column cross-sectional area (area)
Aa = active tray area (non downcomer) (area)
Ah = area of the tray open to vapor (area)
Ad = column cross-sectional area dedicated to downcomers (area)
f = fraction of flooding operation; usually we use 0.80
FLV = internal variable, relating the kinetic energy of the liquid and gas streams (unitless)
L = molar flowrate of the liquid stream (mol time-1)
MV = molecular weight of the gaseous stream
ML = molecular weight of the liquid stream
Uf = Vapor velocity that is sufficient to suspend liquid droplets. Vapor velocity greater than U can be associated with entrainment
f
flooding (length time-1)

V = molar flowrate of the gaseous stream (mol time-1)
*Note that many of the parameters can have different values for different stages in the column. Use an appropriate average value
and document and justify your assumptions.
0.5
4V MV
DT = [ ] (12.1)
f Uf π(1 − Ad /A)ρV
0.5
LML ρV
FLV = ( ) (12.2)
V MV ρL
Where A d /A is estimated as follows

if FLV ≤ 0.1 ,
Ad /A ∼ 0.1 (12.3)
if 0.1 ≤ F LV ≤ 1.0 ,
Ad /A ∼ 0.1 + (FLV − 0.1)/9 (12.4)
if FLV ≥ 1.0 ,
Ad /A ∼ 0.2 (12.5)
 Example
180 kmol/hr of fermentation off-gas containing 98 mol% CO2 and 2 mol% ethanol is to be fed to a staged absorption tower that
operates at 30°C, 110 kPa. Fresh water will be supplied to this column at a ratio of 1.5 ∗ (L /V ) = 154 kmol/hr and we
′ ′
min
intend to have a sufficient number of stages so that 97% of the ethanol will be recovered. Ignore the contribution of the solute
to the physical properties of the carrier streams and assume a vapor flooding velocity of 3.12 m/s.
Graphical and Mathematical Determination of Vapor Phase Flooding Velocity

σ = liquid surface tension (dyne cm-1)
Aa = active tray area for contact between the gas and liquid phases (area)
Ah = area of the holes (area)
C = Souders and Brown capacity parameter, also known as vapor velocity factor (ft/s)
C1 = internal parameter for calculation of C S,ult (m s-1)
C2 = internal parameter for calculation of C S,ult (m s-1)
CD = liquid droplet drag coefficient
CF = entrainment flooding capacity, from Figure 6.23 (ft/s)
CS,ult = ultimate capacity parameter (m s-1)
dp = liquid droplet diameter (length)
FF = foaming factor (unitless)
FH A = internal variable based on plate-specific value of Ah/Aa (unitless)
FLV = internal variable, relating the kinetic energy of the liquid and gas streams (unitless)
FST = surface tension factor (unitless)
F = internal parameter for calculation of C S,ult
-2
g = gravitational constant (length time )
LS = superficial liquid velocity (length time-1)
Uf = superficial vapor velocity at flooding (length time-1)
US = superficial vapor velocity (length time-1)
US,ult = superficial vapor velocity at which the vapor velocity exceeds the liquid droplet settling velocity (m s-1)
Graphical Determination of Superficial Vapor Velocity at Flooding

0.5
ρL − ρV
Uf = C ( ) (13.1)
ρV
0.5
4 dP g
C =( ) (13.2)
3CD
we will use
C = FST FF FH A CF (13.3)
0.2
FST = (σ/20 ) (13.4)
σ must be in dyne/cm
if Ah / Aa > 0.10 FHA = 1.0
FH A = 1.0 (13.5)
if 0.06 < A h / Aa < 0.1 FHA = 5(Ah/Aa) + 0.5
FH A = 5(Ah / Aa ) + 0.5 (13.6)
CF is from Fig 6.23, needs F LV and tray spacing
Mathematical Determination of Superficial Vapor Velocity at Flooding

0.5
ρL − ρV
Uf = US,ult = CS,ult ( ) (13.7)
ρV
CS,ult = C1 or C2 , whichever value is smaller
0.25
σ
C1 = 0.445(1 − F )[ ] − 1.4 LS (13.8)
ρL − ρV
0.25
σ
C2 = 0.356(1 − F )[ ] (13.9)
ρL − ρV
−1
0.5
ρL − ρV
F = (1 + 1.4 [ ] ) (13.10)
ρV
for equations 13.8, 13.9, and 13.10, densities must be in kg/m3 and surface tension must be in dyne/cm
−1
LML V MV
LS = US ( ) (13.11)
ρL ρV
*true in all conditions, not just flooding
 Example 1.4.1
180 kmol/hr of fermentation off-gas containing 98 mol% CO2 and 2 mol% ethanol is to be fed to a staged absorption tower that
operates at 30°C, 110 kPa. Fresh water will be supplied to this column at a ratio of 1.5 ∗ (L /V ) = 154 kmol/hr and we
′ ′
min
intend to have a sufficient number of stages so that 97% of the ethanol will be recovered. Assume a foaming factor of 0.90,
trays that have an A /A > 0.10 and a surface tension of 70 dyne/cm and ignore the contribution of the solute to the physical
h a
properties of the carrier streams. Assume a tray spacing of 24 inches. What is U according to f
(a) the graphical method

(b) ultimate superficial velocity computational method?
Staged Column Pressure Drop

ϕe = height of clear liquid/height of froth (unitless)
σ = liquid surface tension (dyne cm-1)
Aa = active tray area, hosting interaction between the gas and liquid phases (area)
Ad = downcomer area, hosting liquid handling (area)
Ah = total area of the holes on each tray (area)
C0 = tray-specific parameter, generally between 0.68 and 0.85
Cl = internal parameter in calculation of h L
DB(max) = maximum bubble size (length). We will use maximum hole diameter D . H

hd = pressure drop due to movement of the gas through tray perforations (inches of our liquid)
hl = pressure drop due to movement of the gas through the liquid hold-up (inches of our liquid)
hσ = pressure drop due to movement of the gas through the liquid surface (inches of our liquid)
ht = total pressure drop for a single actual tray (inches of our liquid)
hw = weir height (inches)
KS = capacity parameter (ft s-1)
Lw = weir length (inches)
qL = liquid flow rate across the tray (gal min-1)
u0 = velocity of the vapor phase through the holes in the tray (ft s-1)
Ua = superficial vapor velocity, calculated based on the active bubbling area (ft s-1)
ht = hd + hl + hσ (14.1)
2
u ρV
0
hd = 0.186 ( )( ) (14.2)
2
C ρL
0
2/3
qL
hl = ϕe [ hw + Cl ( ) ] (14.3)
Lw ϕe
0.91
ϕe = exp(−4.257 K ) (14.4)
S
0.5
ρV
KS = Ua ( ) (14.5)
ρL − ρV
Aa = (A − 2 Ad ) (14.6)
Lw = 0.73 DT (14.7)
Cl = 0.362 + 0.317 exp(−3.5 hw ) (14.8)
hw , L must be in inches, q must be in gal/min, K must be ft/s

w L S
6σ
hσ = (14.9)
gρL DB(max)
To prevent weeping, maintain

hd + hσ > hl (14.10)
 Example
180 kmol/hr of CO2 containing 2 mol% ethanol and 154 kmol/hr of fresh water are fed to a column with a diameter of 0.80m.
The weirs have a height of 2.0 inches, the sieve tray holes have a diameter of 3/16″, C0 = 0.73. Ten percent (10%) of the
column cross-sectional area is occupied by the downcomers and 10% of the active column area is occupied by the sieve tray
holes. What is the pressure drop per tray?
Staged Column Mass Transfer

ϕe = height of clear liquid/height of froth (unitless); equation 14.4 from Lecture 2.2 Staged Column Pressure Drop
ρL = density of the liquid phase (mass volume-1)
ρV = density of the vapor phase (mass volume-1)
a = interfacial gas-liquid area per unit volume of combined gas and liquid hold up (area/volume = length-1)
¯
¯
a
¯
= interfacial gas-liquid area per unit volume of equivalent clear liquid (area/volume = length-1)
Aa = active tray area, hosting interaction between the gas and liquid phases (area)
Ab = active bubbling area of the tray (area)
DL = diffusivity of the solute in the liquid phase (cm2 s-1)
DV = diffusivity of the solute in the vapor phase (cm2 s-1)
EMV = Murphree efficiency of a stage, based on the vapor phase
f = fractional value representing proximity to flooding value, based on U instead of U (unitless)
a f
F = F -factor [(kg/m)0.5s-1]
hl = pressure drop due to movement of the gas through the liquid hold-up, from Lecture 2.2 Staged Column Pressure Drop
(pressure)
kG = gas-phase mass transfer coefficient (length time-1)
kL = liquid-phase mass transfer coefficient (length time-1)
K = equilibrium constant for our system (y/x)
KG = overall mass transfer coefficient, based on partial-pressure driving force (time-1)
L = molar flow rate of the liquid phase (mol time-1)
ML = molecular weight of the liquid phase (mass mole-1)
NG = number of transfer units in the gas phase
NL = number of transfer units in the liquid phase
NOG = number of overall mass transfer units, expressed on a gas-phase basis
P = pressure of the gas phase (pressure)
qL = liquid volumetric flow rate across the tray (volume time-1)
¯
tG = average gas residence time in the froth (time)
¯
tL = average liquid residence time in the froth (time)
Ua = superficial vapor velocity, calculated based on the active bubbling area (length time-1)
Uf = superficial vapor velocity at flooding, found by Souders and Brown or superficial velocity method, Lecture 2.1 Graphical and
mathematical determination of vapor phase flooding velocity (length time-1)
V = molar flow rate of the gas phase (mole time-1)
yi,n+1 = composition (mole fraction) of the gas entering stage n from stage n + 1
yi,n = composition (mole fraction) of the gas leaving stage n
y
∗
i,n
= composition (mole fraction) of the gas leaving stage n if it had reached equilibrium with the liquid leaving stage n
Zf = height of combined gas and liquid hold up (length)
Refer to Lecture 1.13 Stage Efficiency and Column Height for the first part of this topic
yi,n+1 − yi,n
EMV = = 1 − exp(NOG ) (15.1)
∗
yi,n+1 − y
i,n
KG aP Zf
NOG = (15.2)
(V / Ab )
1 1 (KV /L)
= + (15.3)
NOG NG NL
kG aP Zf
NG = (15.4)
(V / Ab )
¯¯ ¯
NG = kG ātG (15.5)
kL aρL Zf
NL = (15.6)
(LML / Ab )
¯
¯¯
NL = kL ātL (15.7)
(1 − ϕe )hl
¯
tG = (15.8)
ϕe Ua
¯
hl Aa
tL = (15.9)
qL
0.5 2
1030 D (f − 0.842 f )
V
¯¯
kG ā = (15.10)
0.5
h
l
f = Ua / Uf (15.11)
¯¯ 0.5
kL ā = 78.8 D (F + 0.425) (15.12)
L
0.5
F = Ua ρ (15.13)
V
In equations 15.12 and 15.13, D and D must be in cm2/s, h must be in cm, F must be in (kg/m)0.5s-1
V L l
 Example
180 kmol/hr of CO2 containing 2 mol% ethanol is fed to an absorption column. 154 kmol/hr of fresh water is used as the liquid
absorbent. The column has a diameter of 0.80m, weir height of 2.0 inches, 3/16” hole diameter, C = 0.73, 10% of the column
0
area is occupied by downcomers, 10% of the active area is occupied by sieve tray holes. Based on mass transfer principles,
what is the expected Murphree efficiency of each stage? Ignore the contribution of the solute.
At the proposed operating conditions, the diffusivity of ethanol in CO2 is 7.85×10-2 cm2 s-1 and the diffusivity of ethanol in
liquid water is 1.81×10-5 cm2 s-1
Packed Columns
ϵ = packing void fraction (volume volume-1), tabulated value
A = absorption factor (unitless)
a = specific surface area of the selected packing (area volume-1), tabulated value
ah = specific hydraulic area of the selected packing (area volume-1)
Ch = dimensionless holdup parameter, tabulated value
DT = packed bed diameter (length)
f = target value of fraction of flooding; for packed columns we typically use 0.5 – 0.7
hL = volume of liquid per unit volume of packed bed (volume volume-1)
HOG = overall height of a gas transfer unit (length) – will be discussed in Lecture 2.7 Packed Bed HOG
K = equilibrium constant for our system at our operating condition
Ky a = overall mass transfer coefficient in gas-phase mole fraction units (mole time-1 volume-1)
L = liquid phase molar flow rate (mole time-1)
lT = depth of packed bed (length)
MV = vapor phase molecular weight
NFr,L = Froude number for the liquid phase, inertial force/gravitational force (unitless)
NOG = number of overall gas-phase mass transfer units
NRe,L = Reynolds number for the liquid phase, inertial force/viscous force (unitless)
S = cross-sectional area of the packed bed (area)
uL = liquid-phase superficial velocity through the packed bed (length time-1)
uV ,f = superficial gas velocity at flooding (length time-1)
V = vapor phase molar flow rate (mole time-1)
xin = mole fraction of the solute in the entering liquid
yin = mole fraction of the solute in the entering vapor
yout = mole fraction of the solute in the exiting vapor
Packed Bed Diameter Sizing

0.5
4V MV
DT = ( ) (16.1)
f uV ,f π ρV
Depth of Packing Required

lT = HOG NOG (16.2)
V
HOG = (16.3)
Ky aS
A A−1 yin − K xin 1

NOG = ( ) ln[( )( + )] (16.4)
A−1 A yout − K xin A
(L/V )
A = (16.5)
K
 Example
180 kmol/hr of a fermentation off-gas stream (98 mol% CO2, 2 mol% ethanol) is fed to a packed absorption column. We aim to
recover 97% of the incoming ethanol using 154 kmol/hr of fresh water. If HOG = 2.0 ft, what is the required depth of packed
bed? K = 0.57.
Liquid Hold-up in a Packed Bed, Operating in Pre-loading Region

1/3
12NFr,L ah 2/3
hL = ( ) ( ) (16.6)
NRe,L a
2
u a
L
NFr,L = (16.7)
g
uL ρL
NRe,L = (16.8)
aμL
if N Re,L <5
ah
0.15 0.1
= Ch N N (16.9)
Re,L Fr,L
a
if N Re,L ≥5
ah
0.25 0.1
= 0.85 Ch N N (16.10)
Re,L Fr,L
a
 Example
For our CO2/water/ethanol system, we have proposed to use 50-mm metal Hiflow rings as our packing material and a column
diameter that results in a superficial liquid velocity of 0.01 m/s. Find the specific liquid holdup and specific volume available
for the gas for this proposed design. Ignore the contribution of the solute.
Parameters for 50mm Hiflow Metal Rings: a = 92.3 m2/m3, C = 0.876, ϵ = 0.977 m3/m3
h
V = 180 kmol/hr
L = 154 kmol/hr
ρL = 1000 kg/m3
μL = 8.9×10-4 kg s-1 m-1
Packed Bed Pressure Drop by the Graphical Method
μL = viscosity of the liquid phase (mass time-1 length-1)
ρH2 O,L = density of liquid water (mass volume-1)
FLV = internal variable (unitless)
FP = packing factor (area volume-1), tabulated value
L = liquid phase flow rate (mole time-1)
ML = liquid phase molecular weight
uL = liquid-phase superficial velocity through the packed bed (length time-1)
uV = superficial gas velocity (length time-1)
uV ,f = superficial gas velocity at flooding (length time-1)
Y = internal variable for the GPDC method, y-axis value of Figure 6-35 (unitless)
Generalized Pressure Drop Correlation (GPDC) for Finding Flooding Velocity

0.5
LML ρV
FLV = ( )( ) (17.1)
V MV ρL
2
u Fp ρV
V
Y =( )( ) f [ ρV ]f [ μL ] (17.2)
g ρH2 O,L
 Example
180 kmol/hr of CO2 containing 2.0 mol% ethanol is fed to a packed column operating at 30°C and 110 kPa. 97% of the ethanol
is to be removed via the addition of 154 kmol/hr of fresh water. The packed column contains 1” ceramic Raschig rings.
Find:
(a) the superficial gas velocity associated with flooding
(b) the necessary column diameter if we operate at 70% of flooding
(c) the pressure drop per foot of packing. Ignore the contribution of the solute to the magnitude and physical properties of each
phase.
For 1” ceramic Raschig rings: F = 179 ft2/ft3
p
Packed Bed Pressure Drop by the Mathematical Method

ΔP = actual pressure drop across a packed bed during operation at your condition (pressure)
ΔP0 = pressure drop across your packed bed during dry operation (pressure)
ξl = internal parameter for pressure drop calculation at the loading point (unitless)
μL = viscosity of the liquid (mass time-1 length-1)
μV = viscosity of the vapor phase (mass time-1 length-1)
Ψ0 = resistance coefficient of dry packing (unitless)
Ψl = internal parameter for pressure drop calculation at the loading point (unitless)
C = internal parameter for pressure drop calculation at the loading point (unitless)
Cp = packing parameter, tabulated value
Cs = packing parameter (unitless)
Dp = effective packing diameter (length)
DT = packed bed diameter (length)
hL = liquid hold-up (volume volume-1)
KW = wall factor (unitless)
lT = depth of packed bed (length)
ML = liquid phase molecular weight
NFr,L = Froude number, inertial force/gravitational force (unitless)
NRe,V = Reynold’s number of the vapor phase, inertial force/viscous force (unitless)
ns = internal parameter for pressure drop calculation at the loading point (unitless)
uL = liquid phase superficial velocity (length time-1)
uL,l = liquid phase superficial velocity at the loading point (length time-1)
uV = vapor phase superficial velocity (length time-1)
uV ,f = vapor phase superficial velocity at the flooding point (length time-1)
uV ,l = vapor phase superficial velocity at the loading point (length time-1)
(3/2) 0.5
ΔP ϵ 13, 300N
Fr,L
( ) =( ) exp ( ) (18.1)
1.5
ΔP0 ϵ − hL a
2
u a
L
NFr,L = (18.2)
g
2
ΔP0 a u ρV 1
V
= Ψ0 ( )( )( ) (18.3)
3
lT ϵ 2 KW
64 1.8
Ψ0 = CP ( + ) (18.4)
0.08
NRe,V N
Re,V
uV DP ρV KW
NRe,V = (18.5)
(1 − ϵ)μV
1 −ϵ
DP = 6 ( ) (18.6)
a
1 2 1 DP
=1+ ( )( ) (18.7)
KW 3 1 −ϵ DT
ρ
*at any operating condition: u L = uV (
LML
ρL
)(
V MV
V
)
Vapor flooding velocity

uV ,l
uV ,f = (18.8)
0.7
At the loading point:

1/2 1/2
g ϵ 1/3 1/6
ρL
0.5
uV ,l = ( ) [ −a ξ ]ξ ( ) (18.9)
1/6 l l
Ψl a ρV
−2ns
0.4
g μL
Ψl = [ FLV ( ) ] (18.10)
C2 μV
0.5
LML ρV
FLV = ( )( ) (18.11)
V MV ρL
If FLV ≤ 0.4 , liquid is disperse, C = CS ,n S = −0.326
0.1588
μL
If FLV > 0.4 , liquid is continuous, C = 0.695(
μV
) CS ,n S = −0.723
μL uL,l
ξl = 12 (18.12)
gρL
 Example 1.4.1
180 kmol/hr of CO2 containing 2.0 mol% ethanol and 154 kmol/hr fresh liquid water are fed to a packed column containing 1”
ceramic Raschig rings. Find (a) superficial gas velocity at flooding; (b) column diameter, if we intend to operate at 70% of the
flooding velocity; (c) pressure drop per foot of packing at loading point.
Determining the Overall Height of a Gas-liquid Transfer Unit for a Packed Column
μV = viscosity of the vapor phase (mass time-1 length-1)
σ = surface tension of the liquid phase (force length-1)
aP h = specific area of the gas/liquid interface (area volume-1)
CV = packing parameter, tabulated value
CL = packing parameter, tabulated value
DG = diffusivity of the solute in the gas phase (length2 time-1)
dh = packing hydraulic diameter (length)
DL = diffusivity of the solute in the liquid phase (length2 time-1)
HG = height of gas-phase transfer unit, with partial pressure driving force (length)
hL = liquid hold-up (volume volume-1)
HL = height of liquid-phase transfer unit, with mole fraction driving force (length)
HOG = overall height of gas/liquid transfer unit, on a gas phase basis (length)
K = equilibrium constant for our species in our selected operating condition
NFrL ,h = Froude number of the liquid phase with the hydraulic diameter as the characteristic length (unitless)
NReL ,h = Reynold’s number of the liquid phase, hydraulic diameter as the characteristic length (unitless)
NRe
V
= Reynold’s number of the vapor phase, inertial force/viscous force (unitless)
NSc V = Schmidt number of the vapor phase (unitless)
NWe
L
,h = Weber number of the liquid phase with the hydraulic diameter as the characteristic length (unitless)
uL = liquid phase superficial velocity (length time-1)
uV = vapor phase superficial velocity (length time-1)
KV
HOG = HG + ( ) HL (19.1)
L
0.5 0.75 1/3

1 0.5
4ϵ 1 1 uV a
HG = (ϵ − hL ) ( ) ( ) ( ) ( ) (19.2)
4
CV a NReV NScV DG aP h
uV ρV
NReV = (19.3)
aμV
μV
NScV = (19.4)
ρV DG
0.75
aP h 1.5N
We,L,h
= (19.5)
0.5 0.2 0.45
a (adh ) N N
ReL ,h FrL ,h
4ϵ
dh = (19.6)
a
uL dh ρL
NRe ,h = (19.7)
L
μL
2
u ρL dh
L
NWeL ,h = (19.8)
σ
2
u
L
NFrL ,h = (19.9)
gdh
1/6 0.5
1 1 4 hL ϵ uL a
HL = ( ) [ ] ( )( ) (19.10)
CL 12 DL auL a aP h
 Example
180 kmol/hr of CO2 containing 2.0 mol% ethanol and 154 kmol/hr liquid water are fed to a packed column with diameter of
1.1m containing 1” (25mm) ceramic Raschig rings, with a pressure drop of 1.1 kPa/m. Find the necessary column height and
total pressure drop if we aim to recover 97% of the incoming solute and the column is operated at the loading point. Ignore the
contribution of the solute.
Packing properties: a =190 m2/m3, ϵ=0.680, C = 0.577, C = 1.329, C = 1.361, C = 0.412, c = 2.454
h P L V s
-2 2
Diffusivity of ethanol in CO2 at 30°C D = 7.85×10 cm /s
G
Diffusivity of ethanol in water at 30°C D = 1.81×10-5 cm2/s

L
ρL = 1000 kg/m3
ρV = 1.92 kg/m3
σL = 70 dyne/cm
μL = 8.9×10-4 kg m-1s-1
μV = 1.53×10-5 kg m-1s-1
This page titled 1.4: Absorption and Stripping is shared under a CC BY-NC 4.0 license and was authored, remixed, and/or curated by Monica
1.5: Distillation
Introduction to Distillation
B = mass or molar flow rate of the bottoms stream leaving the systems (mass time-1 or mole time-1)
D = mass or molar flow rate of the distillate stream leaving the system (mass time-1 or mole time-1)
F = mass or molar flow rate of the feed stream entering the system (mass time-1 or mole time-1)
L = mass or molar flow rate of the liquid reflux returned to the column from the condenser (mass time-1 or mole time-1); also
generic flow rate of the liquid phase in the rectifying section
= mass or molar flow rate of the liquid leaving the bottom of the column and entering the reboiler (mass time-1 or mole time-1);
¯
¯¯¯
L
also generic flow rate of the liquid phase in the stripping section
n = generic stage number, stage 1 is at the top of the column
R = reflux ratio
V = mass or molar flow rate of vapor leaving the top of the column and entering the condenser (mass time-1 or mole time-1); also
generic flow rate of the vapor phase in the rectifying section
¯
¯¯
V
¯
= mass or molar flow rate of the gaseous boilup returned to the column from the reboiler (mass time-1 or mole time-1); also
generic flow rate of the vapor phase in the stripping section
x = mass or mole fraction of the light key in a liquid stream
xB = mass or mole fraction of the light key in the bottoms stream
xD = mass or mole fraction of the light key in the distillate stream
xn = mass or mole fraction of the light key in the liquid leaving stage n
y = mass or mole fraction of the light key in vapor stream
yn = mass or mole fraction of the light key in the vapor leaving stage n
zF = mass or mole fraction of the light key in the feed stream
Overall material balance
F = D+B (20.1)
Material balance on light key
F zF = xD D + xB B (20.2)
Combination of material balances in Equations 20.1 and 20.2

zF − xB
D =F ( ) (20.3)
xD − xB
L
R = (20.4)
D
¯
¯¯¯
V
VB = (20.5)
B
Material balance on stages 1 − n , the rectifying section of the column

L L
yn+1 = ( ) xn + y1 − ( ) x0 (20.6)
V V
Rectifying section operating line

R xD
yn+1 = ( ) xn + ( ) (20.7)
R+1 R+1
Stripping section operating line
VB + 1 xB
yn+1 = ( ) xn − ( ) (20.8)
VB VB
McCabe-Thiele Method for Finding N and Feed Stage Location
ΔH
vap
= enthalpy change of vaporization of the feed stream at the column operating pressure (energy mole-1)
CPL = heat capacity of the liquid feed stream (energy mole-1 temperature-1)
CP
V
= heat capacity of the vapor feed stream (energy mole-1 temperature-1)
F = molar flow rate of the feed stream entering the system (mole time-1)
L = molar flow rate of the liquid phase in the rectifying section (mole time-1)
= molar flow rate of the liquid phase in the stripping section (mole time-1)
¯
¯¯¯
L
LF = molar flow rate of the liquid portion of the feed stream (mole time-1)
n = generic stage number, stage 1 is at the top of the column
q = metric that reflects the physical state of the feed stream (unitless)
R = reflux ratio
Tb = bubble-point temperature of the feed stream at the column operating pressure (temperature)
Td = dew-point temperature of the feed stream at the column operating pressure (temperature)
TF = temperature of the feed stream (temperature)
V = molar flow rate of the vapor phase in the rectifying section (mole time-1)
¯
¯¯
V
¯
= molar flow rate of the vapor phase in the stripping section (mole time-1)
VF = molar flow rate of the vapor portion of the feed stream (mole time-1)
xB = mole fraction of the light key in the bottoms stream
xD = mole fraction of the light key in the distillate stream
xn = mole fraction of the light key in the liquid leaving stage
zF = mole fraction of the light key in the feed stream
Finding the Theoretical Number of Stages from known Reflux Ratio, Boilup Ratio, Distillate Composition and Bottoms
Composition
Rectifying section operating line
R 1
yn+1 = ( ) xn + ( ) xD (21.1)
R+1 R+1
Stripping section operating line

VB + 1 1
yn+1 = ( ) xn − ( ) xB (21.2)
VB VB
Plotting the q-line
F = LF + VF (21.3)
¯
¯¯¯ ¯
¯¯¯
(L − L) V −V
q = = 1 +( ) (21.4)
F F
For sub-cooled liquid, q > 1

CP (Tb − TF )
L
q =1+ (21.5)
vap
ΔH
For a saturated liquid,

q =1 (21.6)
For a mixture of liquid and vapor, 0 < q < 1

LF
q = (21.7)
F
For a saturated vapor, q = 0
q =0 (21.8)
For sub-heated vapor, q < 0

CPV (Td − TF )
q = (21.9)
vap
ΔH
q-line
q 1
y =( ) x −( ) zF (21.10)
q −1 q −1
Watch this two-part video series from LearnChemE that demonstrates how to use the McCabe-Thiele graphical method to
determine the number of equilibrium stages needed to meet a specified separation objective: McCabe-Thiele Graphical Method
Example Part 1 (8:21): https://youtu.be/Cv4KjY2BJTA and McCabe-Thiele Graphical Method Example Part 2 (6:35):
https://youtu.be/eIJk5uXmBRc
Watch this video from LearnChemE for a conceptual demonstration of how to relate stepping off stages to distillation column
design: McCabe-Thiele Stepping Off Stages (7:02): https://youtu.be/rlg-ptQMAsg
McCabe-Thiele Method for Finding the Minimum Number of Stages, the Minimum Reflux Ratio, and
the Minimum Boilup Ratio
α = relative volatility of the light key and the heavy key at a given temperature (unitless)
αF = relative volatility of the light key and the heavy key at the feed temperature (unitless)
γH K = activity coefficient of the heavy key; can be a function of x and/or T ; 1 for an ideal solution (unitless)
γLK = activity coefficient of the light key; can be a function of x and/or T ; 1 for an ideal solution (unitless)
B = molar flow rate of the bottoms leaving the system (mol time-1)
D = molar flow rate of the distillate leaving the system (mol time-1)
F = molar flow rate of the feed stream (mol time-1)
L = molar flow rate of liquid within the rectifying section, assumed constant in McCabe-Thiele model (mol time-1)
¯
¯
L
¯¯
= molar flow rate of liquid within the stripping section, assumed constant in McCabe-Thiele model (mol time-1)
Nt,min = minimum required number of theoretical stages for a given combination of equilibrium data, x and x D B
P
HK
sat
= saturated vapor pressure of the heavy key at a given temperature, i.e. by Antoine equation (pressure)
P
LK
sat
= saturated vapor pressure of the light key at a given temperature, i.e. by Antoine equation (pressure)
q = metric that indicates that physical state of the feed stream, i.e. q = 1 for saturated liquid (unitless)
R = reflux ratio = L/D (unitless)
Rmin = reflux ratio that requires an infinite number of stages in the rectifying section (unitless)
V = molar flow rate of vapor within the rectifying section, assumed constant in McCabe-Thiele model (mol time-1)
= molar flow rate of vapor within the stripping section, assumed constant in McCabe-Thiele model (mol time-1)
¯
¯¯¯
V
¯
¯¯¯
VB = boilup ratio = V /B
VB,min = boilup ratio that requires an infinite number of stages in the stripping section (unitless)
VF = molar flow rate of the vapor component of the feed stream (mol time-1)
xB = target mole fraction of the light key in the bottoms product
xD = target mole fraction of the light key in the distillate product
xH K = mole fraction of the heavy key in the liquid phase
xLK = mole fraction of the light key in the liquid phase
yH K = mole fraction of the heavy key in the vapor phase
yLK = mole fraction of the light key in the vapor phase
zF = mole fraction of the light key in the feed stream
(L/V )min
Rmin = (22.1)
1 − (L/V )min
(L/V )min = slope of the line that connects (x , x ) to the intersection of the q-line and the equilibrium curve
D D
sat
yLK / yH K γLK P
LK
α = = (22.2)
sat
xLK / xH K γH K P
HK
1
VB,min = (22.3)
¯
¯¯¯ ¯
¯¯¯
(L/ V )max − 1
¯
¯¯¯ ¯
¯¯¯
(L/ V )min = slope of the line that connects (x , x ) to the intersection of the q-line and the equilibrium curve
B B
L + D − VF D(R + 1) − VF
VB = = (22.4)
B B
when q ≤ 0 , V F =F ; when 0 < q < 1 , VF = (1 − q)F ; when q ≥ 1 , V F =0
*we will use Eq 22.4 to calculate V as a function of our selected R

B
 Example
xD = 0.80 , q = 0, z F = 0.25
(L/V )min =
Rmin =
 Example
xD = 0.90 ,x
B = 0.20
Nt,min =
Distillation Energy Demand and Correlations for Efficiency
α = relative volatility of the light key and heavy key (unitless). For equation 23.2, this is evaluated at the average column
temperature.
ΔH
vap
= average heat of vaporization for the stream entering the condenser or reboiler (energy mole-1)
ΔH
vap
S
= average heat of vaporization for the steam entering the reboiler (energy mole-1)
μ = liquid phase viscosity (cP). For eqs 23.1 and 23.2, this is the viscosity of the feed stream at the average column temperature.
B = bottoms flow rate (mole time-1)
CP , H2 O = heat capacity of liquid water (energy mole-1 temperature-1) or (energy mass-1 temperature-1)
D = distillate flow rate (mole time-1)
EO = stage efficiency (unitless)
L = liquid flow rate in the rectifying section (mole time-1)
= liquid flow rate in the stripping section (mole time-1)

¯
¯¯¯
L
mcw = flow rate of cooling water to condenser (mass time-1) or (mole time-1)
ms = flow rate of steam to reboiler (mass time-1) or (mole time-1)
QC = energy demand (cooling) for the condenser (energy time-1)
QR = energy demand (heating) for the reboiler (energy time-1)
R = reflux ratio = L/D (unitless)
Tin = temperature of cooling water entering the condenser (temperature)
Tout = temperature of cooling water leaving the condenser (temperature)
VB = boilup ratio = V ¯
¯¯¯
/B (unitless)
VF = molar flow rate of the vapor portion of the feed (mole time-1)
Correlations for Stage Efficiency

Drickamer and Bradford
EO = 13.3 − 68.8 log10 μ (23.1)
Restrictions on eq 23.1: μ = 0.066– 0.355cP, T = 157– 420 °F, P = 14.7– 366 psia, E
O = 41– 88 %
O’Connell
50.3
EO = (23.2)
0.226
(αμ)
when 0.1 ≤ αμ ≤ 1 , adjust E calculated by 23.2 with correction factor from Table 7.5
O
Restriction on eq 23.2: α = 1.16– 20.5
Condenser and Reboiler Energy Demand

total condenser
vap
QC = D(R + 1)ΔH (23.3)
partial reboiler
vap
QR = BVB ΔH (23.4)
for partially vaporized feed (0 < q < 1) and total condenser

VF
QR = QC [1 − ] (23.5)
D(R + 1)
QC
mcw = (23.6)
CP , H2 O (Tout − Tin )
if using saturated steam for the reboiler

QR
mS = (23.7)
vap
ΔH
S
Distillation Packed Column Depth

HETP = height of equivalent theoretical plates
HOG = x (length)
λ = local slope of equilibrium curve/local slope of operating line
ln λ
HETP = HOG (24.1)
λ −1
 Example
We aim to distill benzene and toluene to a distillate that contains 95 mol% benzene and a bottoms stream that contains 95%
toluene. The feed stream is 100 kmol/hr of an equimolar mixture with q = 0.50. We will be operating at 1.0 atm, R/R of min
1.8 with a packed column containing 25-mm metal Bialecki rings. Assume operating at 70% of the flooding velocity. What
depth of packing is needed to achieve this separation?
For Antoine equation of the form log 10
∗
p = A– B/(T + C ) , where T is in °C and p is in mmHg
∗
Benzene: A = 6.89 , B = 1204, C = 220

Toluene: A = 6.96 , B = 1350, C = 220
25-mm metal Bialecki rings: a = 210 , ϵ = 0.956, C = 0.692, C = 0.891, C = 1.461, C = 0.331, C = 2.521
h p l v s
Toluene: MW = 92.14, ρ = 0.87 g/mL, μ = 0.590 cP, σ = 27.73 dyne/cm

L L L
Benzene: MW = 78.11, ρ = 0.88 g/mL, μ = 0.652 cP, σ = 28.88 dyne/cm

L L L
D L = 1.85 ∗ 10 cm2/s (Table 3.4, Seader)

−5
2
D V = 0.0565 cm /s (estimated via eq 3-36, Seader)
μ V= 0.0133 cP, estimated from online gas viscosity calculator (LMNO Engineering) as a function of T (94°C)
This page titled 1.5: Distillation is shared under a CC BY-NC 4.0 license and was authored, remixed, and/or curated by Monica Lamm and Laura
1.6: Membranes
Introduction to Membrane Processes and Modeling Porous Membranes
ΔP = pressure driving force across the membrane (pressure)
Δz = membrane thickness (length)
ϵ = membrane porosity; volume of pores per unit volume of membrane (unitless)
μ = permeate viscosity (cP) or (mass length-1 time-1)
ρ = fluid density (mass volume-1)
τ = membrane tortuosity factor (>1)
AM = membrane cross-sectional area (area)
aV = total pore surface area per volume of membrane solid material (area volume-1)
D = pore diameter (length)
dH = hydraulic pore diameter (length)
J = permeate flux (vol area-1 time-1) or (length time-1)
k = permeability of component i (length2)
L = pore length
lM = membrane thickness (length)
n = number of pores per unit of flow area (i.e. top down, not a cross-section) of membrane
Ni = molar flux through the membrane per unit area (mol time-1 area-1)
NRe = Reynold’s number (unitless)
P = pressure (pressure)
P0 = pressure at the surface of the pore (pressure)
PL = pressure at position L within the membrane pore (pressure)
PMi = permeability of the membrane to species i (length2 time-1)
¯
¯¯
P
¯
Mi = permeance of the membrane to species i (length time-1)
Rc = resistance of the filter cake (length-1)
Ri = resistance of component i (length-1)
Rm = resistance of the membrane (length-1)
t = time (time)
u = superficial velocity of the permeate (length time-1)
v = flow velocity (length time-1)
V (t) = cumulative volume of permeate collected since the start of the filtration (volume)
z = direction of flux (length)
General Flux Equation

PM ¯
¯¯¯
i
Ni = ( ) ∗ [driving force] = P Mi ∗ [driving force] (25.1)
lM
Dead-end Filtration
1 dV (t) −k dP
J = =( ) (25.2)
AM dt μ dz
Δzi
Ri = (25.3)
ki
ΔP
u =J = (25.4)
μ(Rm + Rc )
Modeling of Porous Membranes

Hagen-Poiseuille Law
2
D
v= (P0 − PL ) (25.5)
32μL
*eq 25.5 is restricted to N Re < 2100 , where N

Re = Dvρ/μ
2
nπD
ϵ= (25.6)
4
Ideal porous membrane: straight pores of uniform diameter

2 4
D ρϵ nπ D ρ
N = vρϵ = (P0 − PL ) = (P0 − PL ) (25.7)
32μ lM 128μ lM
Compensation for tortuous pores and variation in pore diameter

L = lM τ (25.8)
4ϵ
dH = (25.9)
aV (1 − ϵ)
3
ρϵ (P0 − PL )
N = (25.10)
2 2
2(1 − ϵ) τ a μ lM
V
 Example
A membrane of thickness 0.003 cm will be used to filter room-temperature water. In order to justify the cost of the membrane,
we need to filter 200 m3 of water every day per m2 of membrane purchased. We are able to maintain a pressure of 50 kPa on
the permeate side. What pressure do we need to apply on the retentate side? Ignore any resistance from the retentate. Assume
operation with an ideal porous membrane with a porosity of 35% and pore diameter of 0.2 μm.
Porous Membranes
α = internal parameter (length mass-1)
ΔP = pressure driving force across the membrane (pressure)
ΔPUL = pressure across the membrane during the constant pressure segment of combined operation (pressure)
ϵc = filter cake porosity; volume of void space per unit volume of filter cake (unitless)
μ = permeate viscosity (cP) or (mass length-1 time-1)
ρc = filter cake density (mass volume-1)
Ac = surface area of the accumulated filter cake (area)
AM = surface area of the membrane (area)
cF = concentration of solid material per unit volume of feed (mass volume-1)
Dp = effective diameter of cake particles (length)
J = permeate flux (volume area-1 time-1) or (length time-1)
K = internal parameter used in modeling constant pressure operation (volume2 hr-1)
K1 = internal parameter, function of effective particle diameter (length-2)
K2 = parameter used in modeling combined constant flux/constant pressure operation, equals α (length mass-1)
lc = thickness of accumulated filter cake (length)
Rc = resistance of the accumulating filter cake (length-1)
Rm = resistance of the membrane (length-1)
t = time (time)
tC F = total time elapsed during the constant flux operation mode (time)
u = target permeate flux value (volume time-1)
V (t) = cumulative volume of permeate collected since the start of the filtration (volume)
V0 = internal parameter for modeling constant pressure operation (volume)
VC F = total permeate collected during the constant flux operation mode (volume)
Resistance from Filter Cake

2 2
150 lc (1 − ϵc ) K1 lc (1 − ϵ)
Rc = = (26.1)
32 3
D ϵc ϵc
P
\begin{displaymath}
\tag{26.2}
K_1=\frac{150}{D_P^2}
\end{displaymath}
for large, relatively flat membranes
K1 (1 − ϵc )cF V (t) α cF V (t)
Rc (t) = = (26.3)
3
ϵc ρc Ac Ac
An equation for the cake resistance, R c (t) , for capillary or hollow fiber membranes given in Seader (14-22).
Operation with Constant Pressure (Flux Decreases with Time)

t V (t) + 2V0
= (26.4)
V (t) K
2
2 Ac ΔP
K = (26.5)
α cF μ
Rm Ac
V0 = (26.6)
αcF
K1 (1 − ϵ)
α = (26.7)
3
ϵc ρc
150
K1 = (26.8)
2
D
P
Operation with Constant Flux (Applied Pressure Drop Increases with Time)
α cF μ 2
Rm μ
ΔP (t) = ( ) u t +( )u (26.9)
2
Ac Ac
Combined Operation: Constant Flux to Maximum Pressure Drop, Then Continue at Constant Pressure with
Decreasing Flux
2
−Rm AM AM Rm
V (t) = + [( ) (26.10)
K2 cF K2 cF
2
2AM 0.5K2 cF V AM ΔPUL (t − tC F )
CF 0.5
+ ( Rm VC F + + )]
K2 cF AM μ
2
AM ΔPUL AM RM
J(t) = [( ) (26.11)
K2 cF μ K2 cF
2
2AM 0.5K2 cF V AM ΔPUL (t − tC F )
CF −0.5
+ ( Rm VC F + + )]
K2 cF AM μ
K2 = α (26.12)
 Example
We aim to use a flat, porous membrane to filter milk. The membrane has a surface area of 17.3 cm2; the membrane resistance
and thickness are not known. The milk contains 4.3 kg/m3 solids and has a viscosity of 0.001 Pa-s. We previously filtered this
milk at an applied pressure drop of 20 psi and the following data was collected:
Time (hr) 0.5 1.0 1.5 2.0
Total volume collected

0.31 0.40 0.53 0.61
(L)
1. How much filtered milk could be collected over a 12-hour period if we operate at ΔP = 20 psi?
2. How much filtered milk could be collected over a 12-hour period if we operate at ΔP = 40 psi?
3. If we operate in constant flux mode at 0.1 L/hr, how long will it take to reach our maximum allowable ΔP of 40 psi?
How much permeate would be collected during this time?
4. If we operate in combined mode for 24 hours with a constant flux of 0.1 L/hr and maximum allowable pressure drop
of 40 psi, how much permeate would be collected?
Nonporous Membranes Gas Permeation

α
∗
A,B
= ideal separation factor of species A and B (unitless)
αA,B = actual separation factor of species A and B (unitless)
Di = diffusivity of species i in the membrane (length2 time-1)
Hi = Henry’s Law coefficient of species i in the membrane (mol volume-1 pressure-1)
Ni = molar transmembrane flux of species i (mol area-1 time-1)
PF = total pressure of the feed (pressure)
pi0 = partial pressure of species i at the membrane on the feed side (pressure)
piF = partial pressure of species i in the bulk feed (pressure)
pi
L
= partial pressure of species i at the membrane on the permeate side (pressure)
piP = partial pressure of species i in the bulk permeate (pressure)
PM
i
= permeability of the membrane to species i (length2 time-1)
= permeance of the membrane to species i (length time-1)

¯
¯¯¯
P Mi
PP = total pressure of the permeate (pressure)
r = pressure ratio (unitless)
xi = mole fraction of species i on the feed side
yi = mole fraction of species i in the permeate
Gas through a non-porous membrane
Hi Di
Ni = (pi0 − piL ) (27.1)
lM
if film resistance is negligible

Hi Di
Ni = (piF − piP ) (27.2)
lM
yA / xA
αA,B = (27.3)
yB / xB
HA DA PMA
∗
α = = (27.4)
A,B
HB DB PMB
(xB / yB ) − rαA,B
∗
αA,B = α [ ] (27.5)
A,B
(xB / yB ) − r
r = PP / PF (27.6)
when A and B are the only components of the feed and permeate, so that
xA + xB = yA + yB = 1 (27.7)
xA (αA,B − 1) + 1 − rαA,B
∗
αA,B = α [ ] (27.8)
A,B
xA (αA,B − 1) + 1 − r
 Example
A certain membrane has an ideal separation factor of 5.12 for O2 (A) and N2 (B). It has been proposed to use this membrane to
separate O2 from air. If our feed pressure is 5.0 atm and our permeate pressure is maintained at 0.25 atm, what is the
composition of our product gas?
Dialysis
(Δci )LM = log mean concentration difference (mol volume-1)
AM = area of membrane cross-sectional to the flow path (area)
ci
F
= concentration of species i on the feed side of the membrane (mol volume-1)
ciP = concentration of species i on the permeate side of the membrane (mol volume-1)
ciR = concentration of species i in the retentate (mol volume-1)
cI,wash = concentration of species i in the wash solution (mol volume-1)
kiF = mass transfer coefficient of species i in the feed (length time-1)
ki
P
= mass transfer coefficient of species i in the permeate (length time-1)
Ki = overall mass transfer coefficient of species i (length time-1)
lM = thickness of the membrane (length)
ni = rate of mass transfer of species i (mol time-1)
PMi = permeability of the membrane to species i (length2 time-1)
Transport across a small membrane segment
dni = Ki (ci − ci )dAM (28.1)
F P
1 1 lM 1
= + + (28.2)
Ki kiF PMi kiP
ni = Ki AM (Δci )LM (28.3)
For counter-current operation:

(ciF − ciP ) − (ciR − ci,wash)
(Δci )LM = (28.4)
( ci −ci )
F P
ln[ ]
( ci −ci,was h )
R
Water (solvent) transport number = water (solvent) flux / solute flux
 Example
We aim to recover 30% of the H2SO4 from a 0.78 m3/hr feed containing 300 kg/m3 of H2SO4 and smaller amounts of CuSO4
and NiSO4. We have up to 1.0 m3/hr of water available as a wash stream. The process is to run counter-current and at 25°C.
The available membrane has an H2SO4 permeance of 0.025 cm/min, negligible permeance to the other sulfates, and a water
transport number (mass) of +1.5. Previous experience suggests that 1/k + 1/k = 1/(0.020 cm/min). What is the required
F P
membrane area and the volumetric flowrate of the two streams exiting the dialysis unit?
Reverse Osmosis
ΔP = pressure drop across the membrane (pressure)
Δπ = osmotic pressure drop across the membrane (pressure)
γ
1
A
= activity coefficient of the solvent on the feed/retentate side (unitless)
Γ = concentration polarization factor (unitless)
μ = viscosity of the feed solution (cP)
π = osmotic pressure (pressure)
ρ = density of the feed solution (mass volume-1)
a = internal parameter used in estimating ki (unitless)
b = internal parameter used in estimating ki (unitless)
c
1
i
= concentration of species i in feed/permeate (mol volume-1)
(csalt)permeate = concentration of solute in the permeate (mol volume-1) or (mass volume-1)
(csalt)f eed = concentration of solute in the feed (mol volume-1) or (mass volume-1)
d = internal parameter used in estimating k (unitless)
i
D = tube diameter (length)

dH = hydraulic diameter (length)
Di = diffusivity of species i in the indicated solvent (length2 time-1)
h = height of flow channel (length)
ki = mass transfer coefficient of species i (length time-1)
NA = molar flux of solvent A through the membrane (mol area-1 time-1)
NRe = Reynold’s number of the feed/retentate (unitless)
NSc = Schmidt number of the feed/retentate (unitless)
R = universal gas constant (pressure volume mol-1 temperature-1) or (energy mol temperature-1)
SP = salt (solute) passage number (unitless)
SR = salt (solute) rejection factor (unitless)
T = system temperature (temperature)
v = velocity of the feed (length time-1)
vA
L
= specific volume of the solvent (volume mol-1)
w = width of flow channel (length)
x
1
i
= mole fraction of species i on the feed/retentate side (unitless)
−RT
1 1
π = ln (x γ ) (29.1)
A A
vAL
when γ 1
A
∼1 and ln(1 − x 1
B
) ∼ −x
1
B
then
1
RT x
B
π = (29.2)
vA
L
if x is sufficiently small, then x

B B / vAL = cB and
1
π ∼ RT c (29.3)
B
PMA
NA = (ΔP − Δπ) (29.4)
lM
b 0.33 d
aN N (dH /L)
Re Sc
ki = (29.5)
(dH / Di )
dH vρ
NRe = (29.6)
μ
μ
NSc = (29.7)
ρDi
for a circular tube, d H =D
for a rectangular channel, d H = 2hw/(h + w)
during turbulent flow (N Re > 10, 000) a = 0.023, b = 0.8, d = 0
during laminar flow, circular tube (N Re < 2, 100) a = 1.86, b = 0.33, d = 0.33
during laminar flow, rectangular channel (N Re < 2, 100) a = 1.62, b = 0.33, d = 0.33
(csalt)permeate
SP = (29.8)
(csalt)f eed
SR = 1 − SP (29.9)
Nsolvent (SR)
Γ = (29.10)
ksolute
Watch a video from LearnChemE that explains osmotic pressure: Osmotic Pressure Derivation (5:00).
 Example
We intend to use reverse osmosis on a feed stream containing 1.8 wt% NaCl to produce water containing 0.05 wt% NaCl. The
separation is to take place at 25°C with a feed side pressure of 1,000 psia and a permeate-side pressure of 50 psia. The
proposed membrane has permeance of 1.1 × 10 g/cm2-s-atm for water.
−5
(a) Ignoring resistances to mass transfer, how much water can be produced per day per unit area of membrane?
(b) If k salt = 0.005 cm/s, what is the concentration polarization factor?
Pervaporation
γi = activity coefficient of species i (unitless)
A12 , A21 = system-specific parameters for the van Laar model
P
i
sat
= saturated vapor pressure of species i, function of temperature and Antoine equation coefficients (pressure)
PM
i
= permeability of the membrane to species i (length2 time-1)
PP = total pressure on permeate side (pressure)
xi = mole fraction of species i on the feed/retentate side (unitless)
yi = mole fraction of species i on the permeate side (unitless)
PM
i sat
Ni = (γi xi P − yi PP ) (30.1)
i
lM
van Laar model for activity coefficients, binary system

A12
ln γ1 = (30.2)
2
x1 A12
[1 + ]
x2 A21
A21
ln γ2 = (30.3)
2
x2 A21
[1 + ]
x1 A12
 Example
We have obtained a potential pervaporation membrane and we aim to use it to separate ethanol and water. We tested this
system at 60°C, a permeate pressure of 76 mmHg and a feed containing 8.8 wt% EtOH. Using 1.0 cm2 of membrane, we
collected 0.25 g/hr of permeate that was found to contain 10.0 wt% EtOH.
(a) What is the permeance of our membrane to ethanol and to water?
(b) What is the expected product composition and flowrate (g/hr) for a feed containing 10.0 wt% EtOH at 60°C with operation
at a permeate pressure of 100 mmHg?
AEtOH,H2O = 1.6276
AH2O,EtOH = 0.9232
PEtOHsat(60°C) = 352 mmHg
PH2Osat(60°C) = 149 mmHg
This page titled 1.6: Membranes is shared under a CC BY-NC 4.0 license and was authored, remixed, and/or curated by Monica Lamm and Laura
Adsorption, Ion Exchange, and Chromatography
ci = concentration of species i in the mobile phase (mass volume-1) or (mole volume-1)
ki = empirical constant for species i for isotherms (units vary)
Ki = adsorption equilibrium constant for species i
ni = internal parameter for isotherms (units vary)
pi = partial pressure of species i (pressure)
qi = amount of species i adsorbed per unit mass of adsorbent at equilibrium (mass mass-1) or (mole mass-1)
qm = amount of species i adsorbed per unit mass of adsorbent at maximum loading, where maximum loading corresponds to
i
complete surface coverage (mass mass-1) or (mole mass-1)

linear isotherm:
qi = ki pi (31.1)
Freundlich isotherm:
1/ni
qi = ki p (31.2)
i
Langmuir isotherm:
Ki qm pi
i
qi = (31.3)
1 + Ki pi
chromatography equilibrium:
qi
Ki = (31.4)
ci
Watch a video from LearnChemE for an explanation about the concept of adsorption: Adsorption Introduction (8:49)
Modeling Differential Chromatography

αi = average partitioning of species i between the bulk fluid and sorbent (unitless)
ϵb = sorbent porosity, ranges from 0 to 1 (unitless)
ϵ
∗
p,i
= inclusion porosity, accounts for accessibility of sorbent pores to species i (unitless)
τf = sorbent tortuosity factor, usually approximately 1.4 (unitless)
ωi = fraction of solute in the mobile phase, relative to sorbed solute, at equilibrium (unitless)
A = cross-sectional area of the column (area)
cf ,i = concentration of species i in the mobile phase (mass volume-1) or (mol volume-1)
De,i = effective diffusivity of species i within the sorbent pores (length2 time-1)
Ei = coefficient that accounts for axial diffusion of species i and non-uniformities of flow (length2 time-1)
Hi = height of theoretical chromatographic plate for species i (length)
ka,i = kinetic rate constant of adsorption of species i to the sorbent (time-1)
kc,i = mass transfer coefficient of species i in the mobile phase (length time-1)
kc,i,tot = overall mass transfer coefficient of species i (length time-1)
Kd,i = equilibrium distribution coefficient of species i between the mobile phase and sorbent (unitless)
L = length of column (length)
m0i = amount of solute i fed to column (mass) or (mol)
R1,2 = resolution of species 1 and 2 in the proposed operating condition (unitless)
Rp = radius of sorbent particles (length)
si = variance of the Gaussian peak of the distribution of species i along the column length (time)
t = elapsed time since loading of the column (time)
¯
ti = mean residence time of species i in the column (time)
u = actual fluid velocity through the bed (length time-1)
us = superficial fluid velocity through the bed (length time-1)
z = position along the length of the column, in the direction of flow (length)
z0,i = mean position of species i along the length of the column as a function of time (length)
z0,i (t) = ωi ut (32.1)
1
ωi = (32.2)
1−ϵb
1+
ϵb αi
1
αi = (32.3)
∗
ϵ (1 + Kd,i )
p,i
u = us / ϵb (32.4)
¯
L
ti = (32.5)
ωi u
2
m0 ωi −(z − z0 )
i
cf ,i (z, t) = exp ( ) (32.6)
0.5
Aϵb (2π Hi z0 ) 2Hi z0
Ei ωi (1 − ωi )Rp u
Hi = 2 [ + ] (32.7)
u 3αi kci,tot
2 Rp u ϵb
NPe,i = NRe NSc,i = (32.8)
Di
if N Pe,i << 1
Di
Ei = (32.9)
τf
else
2 Rp u ϵb
Ei = (32.10)
NP e,E,i
NPe,E,i calculated by 15-61 or 15-62, Seader

2
1 1 Rp 3 Kd,i
= + + [ ] (32.11)
∗ ∗
kci,tot kc,i 5ϵ De,i Rp ka,i ϵ 1 + Kd,i
p,i p,i
¯
ti Hi
2
s = (32.12)
i
ωi u
¯ ¯
abs(t1 − t2 )
R1,2 = (32.13)
2(s1 + s2 )
 Example
1.0 g of species A is added to a chromatography column of cross-sectional area 1.0 m2 and length 1.0 m. Mobile phase is
added at a flowrate of 4.0 × 10 m3/s. Species A has a mass transfer coefficient of 2.0 × 10 m/s in this solvent. The
−3 −5
selected sorbent has a porosity of 0.40 m and average particle radius of 5.0 × 10 m. For species A in this sorbent, the
−6
inclusion porosity is 0.80, K = 50 , E = 2.0 × 10 m2/s, k = 100 s-1 and the effective diffusivity is 3.5 × 10
d
−8
a m2/s. −12
(a) When is mean expected elution time for species A?

(b) Plot the concentration profile for species A at 0.05 m increments along the column length in 10-minute increments, until all
of the solute has eluted.
(c) Find the variance of the peak for species A in the proposed operating condition.
(d) The column feed also contains 1.0 g of species B. Species B has a mass transfer coefficient of 1.0 × 10 m/s in the mobile
−5
phase, inclusion porosity of 0.50, K = 60 , E = 3.0 × 10 m2/s, effective diffusivity of 4 × 10

d
−8
m2/s and k = 200 s-1.
−12
a
What is the resolution of these two species in the proposed operating condition?
This page titled 1.7: Sorption and Chromatography is shared under a CC BY-NC 4.0 license and was authored, remixed, and/or curated by Monica
Index
D
dire
Glossary
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CHEMICAL

Monica Lamm and Laura Jarboe

SF i,k = split fraction for species i in separator k (dimensionless)

Diffusion-based Mass T ransfer

Falling Liquid Film with Gaseous Solute ADiffusing into Liquid B

μ = dynamic viscosity of the liquid (pressure time)

Peclet number for mass transfer

Mass transfer coefficient k c,ave

2 DAB L 8/3 8/3

Henry’s Law, applies at the interface

Log mean concentration difference

ρH2O = 998 kg/m3

= 1.5 ( ) − 0.5 ( ) (2.3)

(a) At what horizontal position does flow become turbulent?

Film Theory and Overall Mass Transfer Coefficients

c = total concentration of liquid B (mol volume-1)

H = Henry’s Law constant for equation of the form c = H P ;

(mol volume-1 pressure-1)

P Ab=p = partial pressure of species A in the bulk gaseous phase (pressure)

in liquid B at the interface

Two-Film Theory, Overall Mass Transfer Coefficients, Gas/Liquid

expected to be located outside of the ternary phase diagram.

Process schematic for multistage liquid-liquid extraction.

extend to find the location of E on the equilibrium curve.

(specified/selected) and E (determined in step 3).

Note the intersection of these two lines and label as “P ”.

– Stream E passes stream R

S/F S (kg/hr) (x_A)_M target (y_A)_1 N

outgoing raffinate composition have been specified/selected.

another line connecting points E @S 1 min

Liquid-Liquid Extraction: Sizing Mixer-settler Units

Impeller power consumption:

Modeling Mass Transfer in Mixer-Settler Units

Estimating Murphree efficiency for a proposed design

mass transfer coefficient of the solute in each phase

−5 1/3 2/3 −1/2

Overall mass transfer coefficient for the solute

Experimental assessment of efficiency

Liquid-Liquid Extraction Columns

definition of superficial velocity

(UD + UC )actual = 0.50(UD + UC )f (7.3)

for operation at 50% of flooding

for rotating-disk columns, D = 8 to 42 inches, with one aqueous phase

Finding mole ratio from mole fraction:

Finding mole fraction from mole ratio:

Graphical Method to Find Equilibrium Stages for Absorption Columns

equilibrium stages is required in order to achieve the desired separation

Stage Efficiency and Column Height

Zf = height of combined gas and liquid holdup on the tray (length)

0.2 < μ < 1.6 cP, μ must be in cP

14.7 – 485 psi, average T = 60 – 138°F, E = 0.65% – 69%

are needed, according to equations 11.2 and 11.3?

log10 [1 + EMV (λ − 1)]

flooding (length time-1)

Where A d /A is estimated as follows

Graphical and Mathematical Determination of Vapor Phase Flooding Velocity

Graphical Determination of Superficial Vapor Velocity at Flooding

if 0.06 < A h / Aa < 0.1 FHA = 5(Ah/Aa) + 0.5

FH A = 5(Ah / Aa ) + 0.5 (13.6)