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01 - 1 - Introduction To Separation Processes
01 - 1 - Introduction To Separation Processes
01 - 1 - Introduction To Separation Processes
Separation Processes 1
hanee@um.edu.my
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Learning outcomes
At the end of this class, you should be able to:
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Separation in daily life …
Other
examples??
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More separation applications …
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Based on the examples given, think about …
• What are the separation techniques used?
• Extraction, distillation, membrane filtration, decantation, absorption, evaporation
…
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Why separation process?
• To separate mixtures into two or more distinct product mixtures
• There are many reasons for wanting pure substances. Some of these
reasons include:
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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
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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
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For each of the following binary mixtures, a separation
operation is suggested. Explain why the operation will or
will not be successful.
• Separation of air into oxygen-rich and nitrogen-rich products by
distillation.
• Separation of m-xylene from p-xylene by distillation.
• Separation of benzene and cyclohexane by distillation.
• Separation of isopropyl alcohol and water by distillation.
• Separation of penicillin from water in a fermentation broth by
evaporation of the water.
• Separation of salt from seawater by evaporation vs. by membrane
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Unit Operations in Separation Processes
• Distillation column
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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)
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Mechanism of Separation
• UNMIXING is not a spontaneous process
Spontaneous means … ??
- A process that requires no external driving force
driving force
Rate of a transfer process=
resistance
• By definition, at equilibrium we have yA* = yA and xA*= • Mass transfer rates will also be increased if there is more
interfacial area/volume between the gas and liquid (higher
xA. Note that as yA→yA* and xA→xA* the driving forces “a”). This can be achieved by having significant interfacial
approach zero and mass transfer rates decrease. turbulence or by using a packing material with a large surface
area
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Thermodynamics of Separation
Rate of Separation
• Remember that there is an “infinite” driving force
associated with removing the last impurity atom from Although the extent of a separation is determined by
a pure substance: 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.
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Driving force for mass transfer – gas vs. liquid phases
Gas Liquid
• 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 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙
Pliquid 𝜇𝜇𝑖𝑖 = 𝜇𝜇𝑖𝑖
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
𝑃𝑃1 𝑉𝑉 = 𝑛𝑛1 𝑅𝑅𝑅𝑅 solution
• Partial pressure of species A in
𝑃𝑃2 𝑉𝑉 = 𝑛𝑛2 𝑅𝑅𝑅𝑅 • 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
𝑃𝑃𝑖𝑖 𝑉𝑉 = 𝑛𝑛𝑖𝑖 𝑅𝑅𝑅𝑅
• Requires Pisat at the operating
∴ 𝑃𝑃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑉𝑉 = � 𝑛𝑛𝑖𝑖 𝑅𝑅𝑅𝑅 T, thus not applicable for
𝑃𝑃𝐴𝐴 = 𝐻𝐻𝐴𝐴 𝑥𝑥𝐴𝐴
𝑖𝑖 species where Tc<T
𝑃𝑃𝑖𝑖 𝑛𝑛𝑖𝑖
= = 𝑥𝑥𝑖𝑖
𝑃𝑃 ∑𝑖𝑖 𝑛𝑛𝑖𝑖
𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠
𝑃𝑃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑃𝑃1 + 𝑃𝑃2 + ⋯ + 𝑃𝑃𝑖𝑖
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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
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Example
T-x-y Diagram for MeOH-EtOH at 101.3 kPa
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T (K)
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0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xMeOH, yMeOH
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Equilibrium Relation
𝛼𝛼𝛼𝛼
VLE for an ideal binary mixture: 𝑦𝑦 =
𝑦𝑦𝑖𝑖 1 + 𝑥𝑥 𝛼𝛼 − 1
𝐾𝐾𝑖𝑖 �𝑥𝑥 𝑥𝑥𝑗𝑗 𝑦𝑦𝑖𝑖
𝛼𝛼𝑖𝑖𝑖𝑖 = = 𝑦𝑦 𝑖𝑖 =
𝐾𝐾𝑗𝑗 𝑗𝑗
�𝑥𝑥𝑗𝑗 𝑥𝑥𝑖𝑖 𝑦𝑦𝑗𝑗
Mole fraction of
𝑥𝑥𝑖𝑖 𝛼𝛼𝑖𝑖𝑖𝑖 light component in
𝑦𝑦𝑖𝑖 = the liquid phase
1 + 𝑥𝑥𝑖𝑖 𝛼𝛼𝑖𝑖𝑖𝑖 − 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
• At bubble point, the relation ∑ 𝑦𝑦𝑖𝑖 = 1 • At dew point, the relation ∑ 𝑥𝑥𝑖𝑖 = 1
must be satisfied must be satisfied
𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 𝑦𝑦𝑖𝑖 𝑃𝑃 = 𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠
𝑦𝑦𝑖𝑖 𝑃𝑃
𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 𝑥𝑥𝑖𝑖 =
𝑦𝑦𝑖𝑖 = 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠
𝑃𝑃
𝑦𝑦𝑖𝑖 𝑃𝑃
𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 � 𝑥𝑥𝑖𝑖 = �
� 𝑦𝑦𝑖𝑖 = � 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠
𝑖𝑖 𝑖𝑖 𝑃𝑃
𝑦𝑦𝑖𝑖
1 1 = 𝑃𝑃 �
1 = � 𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠
𝑃𝑃 𝑖𝑖
1
𝑃𝑃 = 𝑦𝑦𝑖𝑖
𝑃𝑃 = ∑𝑖𝑖 𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 ∑ 𝑠𝑠𝑠𝑠𝑠𝑠
𝑃𝑃𝑖𝑖
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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. zi
T, P
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
Balance on species i :
Derive:
𝐹𝐹𝑧𝑧𝑖𝑖 = 𝑉𝑉𝑉𝑉𝑖𝑖 + 𝐿𝐿𝑥𝑥𝑖𝑖
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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
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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
𝑃𝑃 = 105.2847 kPa
Since the operating pressure lies between the calculated bubble and dew
pressures, we have confirmed the system is in the two phase region.
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Solution
Determine Ki for each species at 110 kPa and 80°C
K1 K2 K3
1.958826 0.889473 0.474453
Use the mass balance equation for flash calculation to obtain L, V, xi and yi
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Solution
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