Process modules Week 1:

Mass transfer operations

Dr Kevin Li
Kevin.li@uwa.edu.au
Consulting time: 3:00-5:00pm
Thursdays, Room 2.49A
Civil Mechanical Building
1.2 Introduction to columns and towers
28
www.geelongadvertiser.com.au
Why study mass transfer?
Petroleum refining
CO
2
and H
2
S from natural gas
CO
2
capture from flue gas
Whisky making
Desalination
29
2(i). Objectives & expectations for this
section
30
Lecture overview
i. Objectives & expectations for this section
ii. Mass transfer (MT) applications & examples
iii. The 3 steps in MT process design
iv. Review of MT fundamentals
v. Equilibrium exercises
31
Study objectives for mass transfer
operations in this course
1. Principles of MT operations including
thermodynamics, rates, process design and
operating issues
2. Identify types of mass transfer equipment
3. Basic sizing calculations: heights of packings,
number of equilibrium stages (trays), column
diameters
4. Evaluate and diagnose process design and
performance problems
32
Mass Transfer Activities
Lectures
Weeks 1 3 Gas-liquid absorption
Weeks 4 & 5 Distillation
Week 6 Solid-liquid separations
Week 12/13 Review and summary
Assessments
Assignment 1 & Quiz 1 (12.5 % of grade)
Gas-liquid absorption column design written
In-class clicker quiz
ENSC3019 Lab 2 distillation
CHPR8503 Assignment 3 distillation column simulation
Final exam questions (60 % of grade)
33
Assignment 1
Available from LMS/Moodle from 6-08-2013
Written report due: 17:30, 17-09-2013
Groups of 3 students. Check LMS ~ 6-08-2013
PDF or MS Word compatible file
Quiz 1 during 1
st
hr of lectures on 17-09-2013
You will design an absorption process to
remove SO
2
fromair
34
Resources for MT study
In addition to lecture notes, you will find the following
resources useful for mass transfer operations study:
MCCABE, W. L., SMITH, J. C. & HARRIOTT, P. (2005) Unit
Operations of Chemical Engineering, 7th ed. New York,
McGraw-Hill.
BENTEZ, J. (2009) Principles and Modern Applications of
Mass Transfer Operations, 2
nd
ed. Hoboken, Wiley.
GREEN, D. W. & PERRY, R. H. (eds.) (2008). Perry's
chemical engineers' handbook, New York: McGraw-Hill.
TREYBAL, R. E. (1981). Mass-transfer operations,
International Edition ed. Singapore, McGraw-Hill.
35
2(ii) Mass transfer applications & examples
36
Definition:
Mass transfer
Transfer of a substance through
another on a molecular scale
Mass transfer can occur through a single phase, or
between phases
37
Why study mass transfer?
So we can separate mixtures.
38
Seader & Henley (2006)
Separation
process
Feed
Product 1
Product 2
Theres 5 mechanism we could exploit to
achieve the separation.
1. Separation by phase creation
39
Phase
creation
Feed
Phase 1
Phase 2
Creation of a second immiscible phase.
Vapour, liquid, solid
Requires energy input (heat/cool; shaft-work)
Energy input
1. Separation by phase creation
Distillation (Process modules wks 8-9)
separates components by partial condensation or
vaporisation
differences in boiling points & relative volatilities of
components
Industrial examples:
crude oil gasoline, kerosene, desiel
ethanol/water
crystallisation (solid phase)
40
2. Separation by phase addition
41
Phase
creation
Feed
Phase 1
Phase 2
Introduce a second phase
solvent that selectively dissolves some of the
species in the feed
Second phase
2. Separation by phase addition
Gas-liquid absorption (week 1-3 + Assignment 1)
Vapour component absorbed in a liquid (or could be solid
phase)
differences in solubility of gas mixture components in the
liquid
Examples:
CO
2
removal from natural gas with amine-based solvents
gas dehydration using TEG solvent
SO
2
scrubbed from flue gas with water
ammonia removed from waste gas with water
42
Liquid extraction and leaching (week 3)
Separation of mixture by contact with an insoluble liquid
phase
differences in solubility of components of mixture in the
second liquid phase
Examples:
fine chemicals and perfume manufacture
making a cup of coffee
(extract flavours &colour from solid coffee bean into the water phase)
43
2. Separation by phase addition
3. Separation by barrier
44
Feed
Phase 1
Phase 2
Barrier restricts and/or enhances movement (flux)
of certain species with respect to other species.
barrier
3. Separation by barrier
Membrane separations
Membrane technologies introduced in ENSC3018 Process
Synthesis and Design (not in ENSC3019/CHPR8503)
Several mechanisms eg. Solution-diffusion, molecular
sieving
Examples:
dialysis
desalination
H
2
purification
45
4. Separation by solid adsorbent
(not covered in ENSC3019/CHPR8503)
46
Feed
Phase 1
Phase 2
Vapour or liquid component adsorbed on a solid
differences in affinity of components of mixture for the solid
Regenerate with pressure or temperature cycles
Examples:
dehydration with silica gels or molecular sieves
odour control with activated carbons
water purification
Solid
adsorbent
5 separation mechanisms
We will study in Process Modules:
1. Phase creation distillation
2. Phase addition absorption, leaching
Not in Process Modules:
3. Barrier membrane separations
4. Solid adsorbent PSA, TSA
5. External field or gradient electrical, magnetic
47
Instructions: in group of 2-3 discuss technologies that
could separate the gas mixtures below.
Consider: reason for the separation, pressure and temperature
required, process equipment
Left side
O
2
and N
2
from air
Centre of room
CO
2
from natural gas
Eg. 10% CO
2
to less
than 2%
Right side
CO
2
from flue gas of
a coal power plant
Eg. 10-14 % CO
2
48
O2 and N2 separation from air
Industrial technologies
Why?
How?
49
Air separation
Air Separation Plant in
Leuna, Germany
www.linde-engineering.com
Distillation
Boiling points N
2
-195.8 C and O
2
-182.95 C
(Lemmon, E.W., M.L. Huber, and M.O. McLinden, REFPROP. 2010)
Cryogenic plants Medium to high flowrates (> 1500 Nm
3
/hr)
high purity N
2
(>99.5 %) & O
2
(>93 %)
Commercial processes include Linde, Air Liquide, Air Products and
Chemicals (APCI) etc
50
Alternatives for air separation
Adsorption on a solid
(not covered in this process modules)
Pressure swing adsorption using molecular sieves
flows < 1500 Nm
3
/hr
when lower purity products are acceptable
Membrane separation units
(not covered in this unit)
51
CO
2
from natural gas
Industrial technologies
Why?
How? Separate CO
2
from CH
4
Gas supply at high pressure (>35 bar)
Feed gas temperature usually < 60C
Typically also removes hydrogen sulphide (H
2
S) as well
Removal to
< 2 % (pipeline) or < 50 ppm(LNG plant feed)
52
CO
2
from natural gas
Absorption using amine-based solvents
CO
2
dissolves and reacts with amine
Hydrolysis and ionisation of dissolved CO
2
CO
2
+ H
2
O HCO
3
-
+ H
+
Protonationof the amine
RNH
2
+ H
+
RNH
3
+

Carbamate formation
RNH
2
+ CO
2
RNHCOO
-
+ H
+
53
CO
2
from natural gas
Amine-absorption process (MDEA)
absorption Amine regeneration
54
CO
2
from flue gas
Industrial technologies
Why? Separate CO
2
from N
2
Whats different to CO
2
from natural gas?
Gas supply at low pressure
Flue gas at high temperature (>140 C, maybe hotter)
Flue gas contains No
x
, SO
x
Bulk removal only required
Its a big challenge to do this economically for
carbon capture and sequestration (CSS)
55
2(iii) The 3 steps in mass transfer
process design for absorption and
distillation columns
1. Equilibrium data for gas-liquid system, and
mass transfer rates.
2. Hydraulic capacity of column
3. Determination of required height of mass
transfer zone or number equilibrium stages
See Chapter 14 of Perry's Chemical Engineers' Handbook
56
Design engineer needs to determine:
57
1. best solvent
2. best gas velocity through the absorber, or
equivalently, the vessel diameter
3. height of the vessel & its internal members
4. solvent circulation rates
5. Temperatures of streams entering & leaving absorber
and stripper (consider heat of solution)
6. Pressures at which absorber & stripper operate
7. Mechanical design of absorber and stripper (flow
distributors, packing supports etc)
You need to do some of each of these tasks in Assignment 1!
1.3 Review of mass transfer fundamentals
58
59
Did you take CHPR2432 Heat & Mass Transfer?
(ENSC3007)
Background reading in texts for that course recommended:
Incropera, F. P. et al. Fundamentals of Heat and Mass
Transfer, 7th edn: J ohn Wiley & Sons 2011
Coulson, J . M. et al. Chemical Engineering Volume 1: Fluid
Flow, Heat Transfer and Mass Transfer, 6th edn: Elsevier
Butterworth Heinemann 1999
Mass transfer definitions
Earlier we stated mass transfer was:
Transfer of a substance through another on a molecular scale
Another definition from BENTEZ, J . (2009):
the transport of one component from a region of higher
concentration to that of a lower concentration
60
MT driving force
a concentration gradient
Molecular mass transfer
Recap basic concepts
Concentrations
Diffusion Ficks law
Mass transfer between 2 phases
Material balances
Equilibrium between two-phases
61
Terminology
62
Separation
process
Feed
V phase
L phase
Operation V phase L phase
Gas-liquid absorption Gas Liquid
Distillation Vapour Liquid
Liquid extraction Extract Raffinate
Leaching Liquid Solid
Strictly speaking, which units match the
definition of molar concentration?
63
0
0
0
0
0
0 of 5
Concentration
1. kg / m
3
2. mol / m
3
3. lb / ft
3
4. kg / mol
5. kPa
Concentrations
64
Strictly, molar concentration defined as:
mole per unit volume mol/L, mol/m
3
Often convenient to use other units:
mass per unit volume () kg/m
3
, lb/ft3 etc
mol/kg solute
mole fraction
Make clear which basis you use
when trying to solve a problem.
Concentrations - problem
65
Calculate for the feed gas the SO
2
concentration as:
(1) mole fraction
(2) parts per million (ppm)
(3) Mass density (kg/m
3
)
Separation
process
Feed
V phase
L phase
Air
1.6 % vol SO
2
T = 298 K
P ~ 1 atm
Concentrations solution (1)
66
Air containing 1.6 %vol SO
2
at 298K, 1 atm
(1) mole fraction y
A
= 0.016
(2) parts per million (ppm)
1.6 % / 100% / * 1 million 16,000 ppm
(3) To get kg SO
2
/m3 takes a few more steps
2
3
2
0.042 kg SO /m
SO
=
67
Further manipulations with concentration units:
A A
A A
A
B B
B B
B
T
n m
p RT C RT RT
V M
n m
p RT C RT RT
V M
n
p RT C RT
V
= = =
= = =
= =
Mass conc.
Eg. g/L
Mole conc.
Eg. mole/L
Concentrations
Daltons Law of partial pressure states:
( )
A B
A B A B
A B
m m
p p p RT C C RT
M M
(
= + = + = +
(

and
1
T A B
A B
C C C
y y
= +
= +
Mass transfer definitions.
Molar flux of A (moles per unit area per unit time)

Concentration of A (moles per unit volume)

Diffusivity or diffusion coefficient of A in B (?)

Distance in direction of transport (length)

Mole fraction component A in vapour phase

Mole fraction component A in liquid phase (or on
solid phase)
68
A
N
A
C
AB
D
z
A
y
A
x
Diffusion example:
mixture 2 gases, assumed ideal
69
Initial concentration gradient
between A & B

Concentration gradient
diffusion = mass transfer
Diffusion by random motion of
molecules leads to mixing to
achieve uniform concentration.
Video Demo
Steady-state diffusion (1)
70
For mixture of two gases A and B assumed to be ideal we can
apply Fickss 1
st
law of steady state diffusion
d
A
A AB
dC
N D
dz
=
d
B
B BA
dC
N D
dz
=
We can write a similar equation for B:
D
BA
is diffusivity of B in A
71
For an ideal gas mixture, at constant pressure (why?)

A B
dC dC
dz dz
=
0
d d
A B
N N + =
d d
If pressure & molar concentration (for system) are constant no
net gain or loss of molecules - we refer to process as
Equimolar Counterdiffusion
Satisfied if:
BA AB
D D =
Then we can drop the subscripts and use just D
Steady-state diffusion (2)
Video demo
Mass transfer across a phase
boundary
In most important applications mass transfer is
across a phase boundary (interface)

Examples
Gas absorption (gas-liquid)
Liquid-liquid (2 immiscible liquids)
Distillation (gas-liquid)
Dissolution of a crystal

Resistance of phase boundary (interface) to transfer is
not very high, except in crystallisation
72
Mass transfer across a phase boundary
Dynamic equilibrium exists between 2 phases
For given T, P set of equilibrium relationships for concentrations
between 2 phases
For system in equilibrium there is no net diffusion of
components between phases
For system not in equilibrium, diffusion components occurs to
bring condition into equilibrium



73
Mole
fraction
A in the
gas = y
A
Mole fraction A in the liquid = x
A
Equilibrium-
distribution curves,
f(T,P)
Concentration in gas at
equilibrium does not have to
be the same as concentration
in liquid
Local 2-phase mass transfer
Where 2 phases interface:
Gas y
AG
in bulk falls to y
Ai

Liquid x
Ai
falls to bulk
concentation x
AL

The bulk concentrations
are not the same as those
at equilibrium.

74
So, which concentrations do we use to calculate rates of mass
transfer?
Whats the real driving force for transfer across interface?
Across a phase boundary
Transfer rate between 2 fluid phases depends on:

Physical properties of the 2 phases
Concentration difference
Area of interface
Degree of turbulence

Mechanisms proposed to represent conditions in the
phase interface region include. Recall (not going into
this here):
1. The two-film theory
2. The penetration theory
75
Material balances
76 See attachment for solutions
The process needs to remove SO
2
so that there is less than
400 ppmin the product air.
Calculate the number of moles SO
2
we need to transfer to
the water phase.
Separation
process
Feed
V phase
L phase
Air
1.6 % vol SO
2
T = 298 K
P ~ 1 atm
Flow = 0.062 kmol/s
Water (second phase)
400 ppmSO
2
To get the flow rate of water required we
need equilibrium data.
Equilibrium between two phases
Equilibrium relationships tutorial last hour for tonight
77
Equilibrium question:
I know Raoults law and Henrys law and
could apply these to mass transfer problems.
78
a) Yes. Im all over the equilibrium problems.
b) Raoult and Henry sound familiar, but I
could do some revision.
c) Are those fellows Spanish soccer players?
Rate of mass transfer
Overall mass-transfer coefficients
If we know an equilibrium relationship



79
( ) ( )
, ,
* *
A y A G x A L
N K y y K x x = =

are overall mass transfer coefficients

for vapour and gas phases
( )
* * y f x =
Recap lecture
80
Mass transfer definition
The 3 steps in mass transfer process design:
1. Equilibrium data, mass transfer rates
2. Hydraulic constraints
3. Determine height of mass transfer zone or
number equilibrium stages
The driving force for mass transfer is concentration
Concentration units be consistent in the problem
Material balances and equilibrium data
Diffusion
Literature cited in this lecture:
1. Lemmon, E.W., M.L. Huber, and M.O. McLinden, REFPROP. (2010), NIST
National Institute of Standards and Technology,. p. Reference Fluid
Thermodynamic and Transport Properties.
2. GREEN, D. W. & PERRY, R. H. (eds.) (2008). Perry's chemical engineers'
handbook, New York: McGraw-Hill.
3. SEADER, J . D. & HENLEY, E. J . (2006). Separation Process Principles,
Hoboken, USA, J ohn Wiley & Sons.
4. BENTEZ, J . (2009). Principles and Modern Applications of Mass Transfer
Operations, Hoboken, USA, J ohn Wiley and Sons.
81