KIL 2008 / KKEK 2158

Separation Processes 1

1 – Introduction to Separation Processes

Dr. Hanee Farzana Binti Hizaddin

Department of Chemical Engineering
University of Malaya

hanee@um.edu.my

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Learning outcomes
At the end of this class, you should be able to:

• Explain the importance of separation processes

• Categorize different types of separation processes and separation
techniques
• Review thermodynamic fundamentals in relation to separation
process
• Apply vapor-liquid equilibria concepts to solve flash calculation

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Separation in daily life …

Other
examples??

3
More separation applications …

4
Based on the examples given, think about …
• What are the separation techniques used?
• Extraction, distillation, membrane filtration, decantation, absorption, evaporation
…

• What are the separating agents?

• Using mass separating agents? E.g. solvent, adsorbent, filter, membrane
• Using energy separating agents? E.g. heat, centrifugation

• Based on what properties are they being separated?

• Chemical properties e.g. chemical affinity, miscibility/immiscibility, volatility …
• Physical properties e.g. size, shape, density, mass …

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Why separation process?
• To separate mixtures into two or more distinct product mixtures

• To get desired purity of the substance

• There are many reasons for wanting pure substances. Some of these
reasons include:

• Need for pure material in engineering application (semiconductors)

• Preparation of raw materials into their components
• Need to remove toxins or inactive components from solution (e.g. drugs)
• Need for analysis of the components of the mixture (DNA testing)
Fun fact:
50 to 90 percent of capital investment in chemical plant is for separations equipment.
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Mechanical vs. Diffusional Separation Process
Separation of components within a single phase is
Mechanical more difficult -- energy input is required.

New phase has to be created, mass transfer

• Mechanical separations depend primarily on (diffusion) between the phases moves some
differences in particle size, density, velocity, etc. components relative to others. Thus, these are
• Examples include screening, filtration, called diffusional separations.
sedimentation, centrifugation, decanting, etc.
• These techniques are good for separating
phases (e.g. solid from liquid), but not Diffusional
necessarily components within a phase.
• Diffusional separations exploit differences in vapor
pressure, solubility, diffusivity, etc.
• The driving force for these separations is a
difference in chemical activity or concentration
which leads to migration of components across a
phase boundary.
• The phases are then separated (typically
mechanically) to produce products.
• In most separation processes, it is necessary to
create a new phase for transport to occur.
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Diffusional Separation
• In most industrial applications, the new phase Vocabulary
is created by direct energy addition.
Phase creation / phase
• For instance, in evaporation energy boils off •
addition
solvent to produce a new vapor phase. • Energy separating
agent (MSA)
• Energy addition is characteristic of distillation • Mass separating agent
and crystallization. (MSA)

• A new phase can also be created by adding

another component (mass). This characterizes
separation techniques such as extraction and
What are the advantages
absorption. and disadvantages of using
• An efficient separation is thus one that ESA or MSA?

minimizes the energy or mass input required to

reach the desired product purities.
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Types of Separation Processes
Process Characteristics / Mechanism Industrial Example

Distillation • Most popular chemical separation • Oil production,

process • Air separation,
• Capable of producing pure substance • Distillation of wine to cognac
from mixture and spirits
• Requires two phases: liquid and vapor
• Uses energy to accomplish separation

Absorption/stripping • Popular in environmental applications • Scrubbing smokestacks

• Transfer gas component from gas to • Ammonia removal from
liquid or vice versa refinery
• Requires two phases: liquid and gas • CO2 Removal
• Uses the different affinity gas component
for gas and liquid

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Types of Separation Processes
Process Characteristics / Mechanism Industrial Example

Liquid-liquid extraction • Used for processes that requires low • Food processing,
temperature operation • Pharmaceutical separation,
• Transfer soluble component from one • Oil purification
liquid to another
• Requires two phases: two immiscible or
partially miscible liquids
• Uses the different affinity components for
separation

Solid-liquid extraction • Uses liquid to extract component from a • Mining

solid matrix • Food processing
• Transfer soluble component from solid to • Pharmaceutical
liquid
• Requires two phases: solid and liquid
• Uses the solubility of the component for
separation

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Types of Separation Processes
Process Characteristics / Mechanism Industrial Example
Dehumidification • Removal of a pure liquid from a gas carrier • Dehydration of gas
phases by condensation
• The reverse (from liquid to vapor) is drying
Adsorption • Removal of a solute from a fluid by contact • Wastewater purification
with an otherwise inert solid • Gas separation
Crystallization and • Create a new phase by heat transfer • Pharmaceutical product
evaporation • In these methods, usually only one of the purification
product phases is valuable
Membrane • Include reverse osmosis, ultrafiltration, etc. • Reverse osmosis
technologies • Allow one component to pass through a • Gas separation
selective membrane which rejects other
components

The list of different existing separations methods is limitless. Therefore we

will emphasize the fundamentals of separations.

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Unit Operations in Separation Processes
• Distillation column

• Feed inlet could be liquid, vapor or

mixture of liquid and vapor
• Exploits the difference in volatility
(vapor pressure) among the
components
• Lighter components (more volatile)
will move upwards, heavier
components (less volatile) move
downwards
• https://youtu.be/BaBMXgVBQKk

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Unit Operations in Separation Processes
• Absorption Column / Stripping Column

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Unit Operations in Separation Processes
• Liquid extraction column

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Unit Operations in Separation Processes

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Background materials for separations
• The fundamentals that we will apply to study separations in this
course involve:
• Materials and energy balances: conservation of energy and matter (CPP 1 & 2)
• Thermodynamics: phase equilibrium and solution thermodynamics
(Thermodynamics 1 & 2)
• Transport phenomena (Mass Transfer)
• Chemical reaction kinetics: rate of conversion of one species to another (not
emphasized)

• Most of our analysis of various separations processes will focus on

using phase equilibria and materials and energy balances.

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 Mechanism of Separation
• UNMIXING is not a spontaneous process
Spontaneous means … ??
- A process that requires no external driving force

• Separation techniques rely on the

Unmixing – reduces
ability to enhance the rate of
randomness and
mass transfer of certain species
thus the entropy of
relative to others to affect a
a system
spatial separation of components.

mixed unmixed • Thus, all separation processes

must introduce a thermodynamic
driving force to overcome the
• Usually the mixture to separate is a homogeneous, single phase. increase in the entropy of the
Otherwise, often the mixture will phase separate first system as the components are
being separated.
• Gravity
• Centrifugation
• Filtration
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 Mass Transfer
• General molecular transport equation

driving force
Rate of a transfer process=
resistance

• The basic mass transfer equation is

• Mass transfer rate = (area) × (mass transfer
coefficient) × (driving force)
• Driving force can be represented as a difference in
mole fractions, a difference in partial pressures, a
difference in concentrations etc.
• The value and units of the mass transfer
coefficient depend upon which driving forces are
selected.
• For equilibrium staged separations we would
ideally calculate the mass transfer rate based on
the transfer within each phase (vapor and liquid)
using a driving force that is the concentration
difference between the bulk fluid and the
interface.
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Mass Transfer Theory
• With concentrations measured in mole fractions, we
could use the following rate expressions.
Rate Rate
= 𝐾𝑦 𝑎 𝑦𝐴∗ − 𝑦𝐴 = 𝐾𝑥 𝑎 𝑥𝐴∗ − 𝑥𝐴
volume volume

• Ky and Kx are overall gas and liquid mass transfer

coefficients
• yA* is the mole fraction in the gas in equilibrium
with the actual bulk liquid of mole fraction xA
• xA* is the mole fraction in the liquid in
equilibrium with the actual bulk gas of mole
fraction yA,
• a is the interfacial area per unit volume (m2/m3 )
• Close to equilibrium, the simplified model shows that we need
high values of Ky and Kx and/or “a.”
• Generally speaking, the mass transfer coefficients will be
higher if diffusivities are higher, which occurs with fluids of low
viscosity.

• By definition, at equilibrium we have yA* = yA and xA*=
xA. Note that as yA→yA* and xA→xA* the driving forces
approach zero and mass transfer rates decrease.
• Mass transfer rates will also be increased if there is more
interfacial area/volume between the gas and liquid (higher
“a”). This can be achieved by having significant interfacial
turbulence or by using a packing material with a large surface
area
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Thermodynamics of Separation
• Remember that there is an “infinite” driving force
associated with removing the last impurity atom from
a pure substance:
• Since the driving force to mix will eventually equal the
driving force we introduce to cause the separation,
the extent of separation will be limited by
thermodynamics equilibrium
Rate of Separation
Although the extent of a separation is determined by
thermodynamics, the rate of separations is limited
by the differential rate at which the different species
are moved;
- i.e. the rate of separation is limited by mass
transport.
Thus, the limits of a separation process are:
• Extent of separation (thermodynamics)
• Rate of separation (mass transport)
In this course we will focus on the
thermodynamic fundamentals governing
separations.
Transport issues will be addressed,
but not a focus.
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Review of Chemical Thermodynamics
• What is equilibrium? • Before we proceed further, these are the
• At “equilibrium”, there are no changes in any important thermodynamic concepts that
properties with time and there are no you need to review
differences in any properties within the system
• Equilibrium
• The driving forces causing material or heat • Entropy
transfer are balanced at equilibrium
• Solution Thermodynamics
• Activity and Activity Coefficients
• What is steady state? • Equilibrium Phase Diagrams
• At “steady state”, there are no
changes in any properties with time
only, implying that there may be
differences in any properties within
the system Please read the materials uploaded in Spectrum
to review these concepts yourselves

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Driving force for mass transfer – gas vs. liquid phases
Gas Liquid

• Driving force: molecules in motion • Driving force: dominated by intermolecular forces

• Velocity increases with T  Momentum
increases with T  either P or V increases
• No intermolecular forces (except in collisions)
• Pressure of gas results from collisions of
molecules with boundary
• Pressure = measure of tendency of molecules
to escape = fugacity, fG = P
• Molecules in restrained motion
• Motion leads to tendency to escape
• We measure gas pressure at equilibrium as a function
of T, known as vapour pressure of liquid.
• Vapour pressure = fugacity, fL = P*
• Saturated vapour pressure is a property of the liquid,
although it is measured for vapour in equilibrium with
the liquid

Equilibrium as force balance

• If fG > fL — net transfer into liquid
• If fG < fL — net transfer into vapour
• If fG = fL — no net transfer (equilibrium)
If force imbalance is maintained we end up solely with liquid or vapor phase
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Phase Rule & Phase Equilibria
• Important variables affecting equilibrium of a solute are:
• Temperature (T), pressure (P), concentration (x)

• The equilibrium between two phases is restricted by the phase rule

• F=C–P+2

• Example:
• For a gas-liquid system of CO2-air-water,
• C = 3, P = 2. Thus, F = 3-2+2 = 3. There are 3 degrees of freedom.
• If T and P are set, then only one variable is left that can be set arbritarily.
• E.g. if the mole fraction of CO2 in liquid phase is set, then we can obtain the
mole fraction of CO2 in the gas phase or the partial pressure of CO2.
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 Phase Equilibria
• Many processes in chemical engineering do not • When a mixture begins to boil, the vapor does not,
only involve a single phase but a combination of in general, have the same concentration as the liquid.
two immiscible liquids, or a stream containing both Instead, the substance with the lower boiling
temperature (or higher vapor pressure) will have a
gas and liquid. vapor concentration higher than that with the higher
• There are three important criteria for different boiling temperature, though both will be present in
phases to be in equilibrium with each other: the vapor.
• A similar argument applies when a vapor mixture
condenses.
• The temperature of the two phases is the same at
• The concentrations of the vapor and liquid when the
equilibrium.
overall concentration and one of the temperature or
• The partial pressure of every component in the two pressure are fixed can easily be read off of a phase
phases is the same at equilibrium. diagram
• The Gibbs free energy or (chemical potential) of
every component in the two phases is the same at Vapor phase At equilibrium,
equilibrium. Tvapor Pvapor Tvapor =Tliquid
yA yB
Pvapor=Pliquid
Liquid phase 𝑣𝑎𝑝𝑜𝑟 𝑙𝑖𝑞𝑢𝑖𝑑
Pliquid 𝜇𝑖 = 𝜇𝑖
Tliquid

xA xB
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VLE Modeling & Calculation
Dalton’s Law Raoult’s Law Henry’s Law

For a mixture of gases, for each • Assumptions: vapor phase is • For a very dilute solute in the
gas we have ideal gas, liquid phase is ideal liquid phase
𝑃1 𝑉 = 𝑛1 𝑅𝑇 solution
• Partial pressure of species A in
𝑃2 𝑉 = 𝑛2 𝑅𝑇 • P is not too high, mixture the vapor phase is directly
should be in similar chemical proportional to its mole fraction
nature & molecular size in the liquid phase
𝑃𝑖 𝑉 = 𝑛𝑖 𝑅𝑇
• Requires Pisat at the operating
∴ 𝑃𝑡𝑜𝑡𝑎𝑙 𝑉 = ෍ 𝑛𝑖 𝑅𝑇 T, thus not applicable for
𝑃𝐴 = 𝐻𝐴 𝑥𝐴
𝑖 species where Tc<T
𝑃𝑖 𝑛𝑖
= = 𝑥𝑖
𝑃 σ𝑖 𝑛𝑖
𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃1 + 𝑃2 + ⋯ + 𝑃𝑖

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K-values and Relative Volatility
• K-value is also known as phase equilibrium ratio i.e. the ratio of mole fractions of
a species in two phases at equilibrium

• For vapor-liquid systems,

𝑦𝑖
𝐾𝑖 =
𝑥𝑖
• The relative volatility, αij measures the separation factor between two
components i and j. It is the ratio of the K-values of i and j:
𝑦𝑖
𝐾𝑖 ൗ𝑥
𝛼𝑖𝑗 = =𝑦 𝑖
𝐾𝑗 𝑗
ൗ𝑥𝑗

• For ideal mixtures that satisfy Raoult’s law we have:

𝑦𝑖
𝐾𝑖 ൗ𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 𝑇
𝛼𝑖𝑗 = = = 𝑠𝑎𝑡
𝐾𝑗 𝑦𝑗ൗ 𝑃𝑗 𝑇
𝑥𝑗

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Equilibrium Relation
𝛼𝑥
VLE for an ideal binary mixture: 𝑦=
𝑦𝑖 1+𝑥 𝛼−1
𝐾𝑖 ൗ𝑥 𝑥𝑗 𝑦𝑖
𝛼𝑖𝑗 = =𝑦 𝑖=
𝐾𝑗 𝑗
ൗ𝑥𝑗 𝑥𝑖 𝑦𝑗

For a binary mixture,

𝑦𝑗 = 1 − 𝑦𝑖 𝑥𝑗 = 1 − 𝑥𝑖

𝑦𝑖 1 − 𝑥𝑖 Mole fraction of
∴ 𝛼𝑖𝑗 = light component
𝑥𝑖 1 − 𝑦𝑖 in the vapor phase
Rearrange,
𝑥𝑖 𝛼𝑖𝑗 − 𝑥𝑖 𝑦𝑖 𝛼𝑖𝑗 = 𝑦𝑖 − 𝑦𝑖 𝑥𝑖

𝑥𝑖 𝛼𝑖𝑗 = 𝑦𝑖 1 − 𝑥𝑖 + 𝑥𝑖 𝛼𝑖𝑗

Mole fraction of
𝑥𝑖 𝛼𝑖𝑗 light component in
𝑦𝑖 = the liquid phase
1 + 𝑥𝑖 𝛼𝑖𝑗 − 1

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Dew Point & Bubble Point Calculation with Raoult’s Law
• Given the mole fraction of a substance in • Given the mole fraction of a substance in
liquid phase (xi) and T, we can calculate vapor phase (yi) and T, we can calculate a
the bubble-point P dew-point P

Conversely, Conversely,

• Given the mole fraction of a substance in • Given the mole fraction of a substance in
liquid phase (xi) and P, we can calculate gaseous phase (yi) and P we can calculate
the bubble-point T a dew-point T

In summary … Need iterative calculation

/ trial and error
Bubble P : calculate (yi, P) given (xi, T)
Dew P : calculate (xi, P) given (yi, T)
Bubble T : calculate (yi, T) given (xi, P)
Dew T : calculate (xi, T) given (yi, P)
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Dew Point & Bubble Point Calculation with Raoult’s Law
Bubble Point Dew Point
Calculation Calculation

• At bubble point, the relation σ 𝑦𝑖 = 1 • At dew point, the relation σ 𝑥𝑖 = 1

must be satisfied must be satisfied
𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
𝑦𝑖 𝑃
𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 𝑥𝑖 =
𝑦𝑖 = 𝑃𝑖𝑠𝑎𝑡
𝑃
𝑦𝑖 𝑃
𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 ෍ 𝑥𝑖 = ෍
෍ 𝑦𝑖 = ෍ 𝑃𝑖𝑠𝑎𝑡
𝑖 𝑖 𝑃
𝑦𝑖
1 1 = 𝑃෍
1 = ෍ 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡
𝑃 𝑖
1
𝑃=
𝑃 = σ𝑖 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 𝑦𝑖
σ 𝑠𝑎𝑡
𝑃𝑖

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Flash Calculation
Vapor, V
• A liquid that is at a pressure equal to or yi
greater than its bubble pressure will
partially evaporate, or “flash”, when Feed, F
the pressure is reduced. T, P
zi
Liquid, L
xi
• The result is a two phase system of
vapor and liquid at equilibrium.
• F, Feed
• zi = the overall feed composition
• L = moles of liquid, with mole fractions xi
• Consider the T,P flash. Given a • V =moles of vapor, with mole fractions yi
temperature and pressure and an • Ki =
Psat
i
=
yi
P xi
overall composition, the mole fraction
of each species in the liquid and vapor
phases can be determined.
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Material Balance in Flash Calculation

Overall balance: 𝑧𝑖 𝑧𝑖
𝑥𝑖 = ෍ 𝑥𝑖 = ෍ =1
𝑉 𝑉
𝐹 =𝑉+𝐿 1 + 𝐹 𝐾𝑖 − 1 1 + 𝐹 𝐾𝑖 − 1

Balance on species i :

Derive:
𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿𝑥𝑖

K-value relation: 𝐾𝑖 𝑧𝑖 𝐾𝑖 𝑧𝑖
𝑦𝑖 = ෍ 𝑦𝑖 = ෍ =1
𝑉 𝑉
1 + 𝐹 𝐾𝑖 − 1 1 + 𝐹 𝐾𝑖 − 1
𝑦𝑖
𝐾𝑖 =
𝑥𝑖

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Example of Flash Calculation
A system of acetone (1) /acetonitrile (2) / nitromethane
(3) at 80°C and 110 kPa have an overall composition of
z1 = 0.45; z2 = 0.35; z3 = 0.20. Vapor, V
yi

Using a basis of 1 kmol feed (F), determine the values of

L, V, xi and yi of each species following flash . The vapor Feed, F
pressures of each species (in kPa) are given by the T, P
zi
Antoine equation below where T is in °C.
Liquid, L
xi
2795.82
𝑃1𝑠𝑎𝑡 = exp 14.3916 −
𝑇 + 230.0
2945.47
𝑃2𝑠𝑎𝑡 = exp 14.2724 −
𝑇 + 224.0
2972.69
𝑃3𝑠𝑎𝑡 = exp 14.2403 −
𝑇 + 209.02
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Solution

• Step 1: Can Raoult’s law be applied? Justify.

• Step 2: Do we have a two-phase region? How to determine?

• Step 3: If we confirmed that we have a two-phase region,

what’s next?

• Step 4: Use the material balance equation derived for the

flash calculation to find L, V, xi and yi of each species  need
to do iteration!

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Solution
• Check if we have a two-phase region by calculating the bubble point and dew point of the mixture
• Calculate the vapor pressure using the Antoine equations given
• P1sat=215.4709 kPa; P2sat=188.9058 kPa; P3sat=104.2593 kPa

Bubble point calculation: Dew point calculation:

Set xi = zi Set yi = zi

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Solution
Determine Ki for each species at 110 kPa and 80°C

K1 K2 K3

Use the mass balance equation for flash calculation to obtain L, V, xi and yi

𝑧𝑖 𝐾𝑖 𝑧𝑖
෍ 𝑥𝑖 = ෍ =1 OR ෍ 𝑦𝑖 = ෍ =1
𝑉 𝑉
1 + 𝐾𝑖 − 1 1 + 𝐾𝑖 − 1
𝐹 𝐹

𝑧1 𝑧2 𝑧3 𝐾1 𝑧1 𝐾2 𝑧2 𝐾3 𝑧3
+ + =1 + + =1
𝑉 𝑉 𝑉 𝑉 𝑉 𝑉
1+ 𝐾 −1 1+ 𝐾 −1 1+ 𝐾 −1 1 + 𝐾1 − 1 1 + 𝐾2 − 1 1 + 𝐾3 − 1
𝐹 1 𝐹 2 𝐹 3 𝐹 𝐹 𝐹

An iteration on V would give L, xi, yi as follows in the following table:

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Solution

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