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Separation Process Engineering

CHEN 312
Instructor: Yousef Salameh, PhD,
Chemical Engineering, FS1 402, ext 3602,
Wankat, Phillip C. Separation Process
Engineering, Third Edition, Pearson
Education, Inc., New Jersey, 2011.
ISBN: 0-13-279021-1

Separations are crucial in chemical engineering. A typical
chemical plant is a chemical reactor surrounded by separators,
where raw materials are prepurified in separation devices and fed
to the reactor; unreacted feed is separated from the reaction
products and recycled back to the reactor.
Chemical plants commonly have from 40% to 70% of both capital
and operating costs in separations.
Separation processes can involve two phases (gas and liquid,
liquid and solid, gas and solid or two immiscible liquids)
Relatively easy to separate two phases due to density difference.
Difficult to separate components from a single phase.

Aim of most processes designed to separate a mixture of

components is to get the components into different phases
and then to separate the phases.

Functions of separation processes

Purification: undesired components in the feed mixture are
removed from the desired species.
Concentration: higher concentration of the
components, which are initially dilute, are obtained.


Fractionation: two or more components are segregated into

product streams of different composition.

Factors that influence the selection of feasible

separation operations:
Feed conditions
Composition, particularly concentration of species to be recovered
or separated
Flow rate
Phase state (solid, liquid and/or gas)
Product conditions
Required purities of products
Phase states

Characteristics of the separation operation

Ease of scale-up
Ease of staging
Temperature, pressure and phase state requirements
Physical size limitations
Energy requirements
For a separation to occur there must be a difference in either a
chemical or physical property between the various components of
the feed stream. This difference is the driving force basis for the
If two phases are at equilibrium, the temperatures, pressures and
fractions of them cease to change. Although molecules keep
moving from one phase to another, but in the same rate.

The equilibrium stage concept is applicable when the process

can be constructed as a series of discrete stages in which the two
phases are contacted and then separated. The two separated
phases are assumed to be in equilibrium with each other.
This simplifies the design and analysis of chemical engineering
separations and unifies the basic design principles and methods for
a given separation method (unit operation).
Unit Operations is a method of analysis and design of chemical
engineering processes in terms of individual tasks/operations.
- It is a way of organizing chemical engineering knowledge into
groups of individual tasks/operations.

Equilibrium conditions can be subdivided into:

Thermal: heat transfer stops and the temperature of the two
phases are equal.
Tliquid = T vapor (at equilibrium)
Mechanical: the forces (usually pressure) between two phases
Pliquid = pvapor (at equilibrium)
Phase equilibrium: the rate at which each species is vaporizing
is just equal to the rate at which it is condensing. Thus there is
no change in composition.
(chemical potential i)liquid = (chemical potential i)vapor

The basic mass transfer equation is:

Mass transfer rate = area X mass transfer coefficient X driving force
Rate/ volume = Ky a (yA* - yA)
Rate/ volume = Kx a (xA xA*)
Ky and Kx are overall gas and liquid mass transfer coefficients.
yA is the actual bulk gas of mole fraction.
xA is the actual bulk liquid of mole fraction.
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.
At equilibrium, y * = y and x * = x

Degrees of freedom: the number of variables that we can

arbitrarily specify. For nonreacting systems (Gibbs phase rule):
where: F = degrees of freedom, C = number of components,
P = number of phases.
For a binary system, C = 2 (2 components), P = 2 (vapor and
liquid). Thus F = 2
When pressure and temperature are set, all the degrees of
freedom are used.
This rules refers to intensive variables which do not depend on
the total amount of material present such as pressure, temperature
or mole fraction.
The extensive variables such as number of moles, flow rate and
variable are not included in the degrees of freedom. So a mixture
in equilibrium must follow the equilibrium data no matter how many
moles are present.

Graphical representation of binary VLE

y-x graph

y vs. x diagram for ethanol-water

Typically, the mole fraction of the more volatile component is

plotted. It is also called McCabe-Thiele diagram.
Pressure is constant, but the temperature is different at each
point on the equilibrium curve.
Points on the curve represents two phases in equilibrium.
Any point not on the equilibrium curve represents a system that
may have both liquid and vapor, but they are not in equilibrium.
Minimum boiling azeotrope: where the liquid and vapor are of
exactly the same composition.
It can be found by drawing the y = x line and finding the
intersection with the equilibrium curve.
Below the azeotrope composition, ethanol is the more volatile
component; above it, ethanol is the less volatile component.

Temperature-composition diagram

Temperature-composition diagram for ethanol-water

Two curves: liquid temperature vs. x, and vapor temperature vs. y

The curves are called saturated liquid and saturated vapor lines.
They represent all possible liquid and vapor systems that can be
in equilibrium at a constant pressure.
Any point below the saturated liquid curve represents a subcooled liquid (liquid below its boiling point).
Any point above the saturated vapor curve would be a
superheated vapor (vapor above its boiling point).
Points between the two curves represents streams consisting of
both liquid and vapor.
These streams will give a vapor and liquid in equilibrium if
allowed to separate, which will be at the same temperature.
Therefore they can be connected by a horizontal isotherm.
Azeotropic point is located where the saturated liquid and vapor
curve touch.

Enthalpy-composition diagram

Its also called Ponchon-Savarit diagram.

Two plots: one for liquid and one for vapor.
Points between the saturated vapor and liquid curves represents two
phase systems.
Liquid and vapor in equilibrium are connected by an isotherm since
they are at the same temperature.
The isotherms show the change in enthalpy at constant temperature as
weight fraction varies.
The azeotrope is located where the isotherm becomes vertical.

Use of auxiliary line

Drawing isotherms on the enthalpy-composition diagram (A) from the

temperature-composition diagram; (B) from the y-x diagram

Ideal Solution & Raoult's Law

Raoult's Law states that, for an ideal solution, the equilibrium partial
pressure of a component at a fixed temperature T equals the product
of its vapor pressure (when it is pure) and its mole fraction in the
pA = POA xA
pA = equilibrium partial pressure of component-A in the gas at
temperature T
POA = vapor pressure of pure liquid A at temperature T
xA = liquid-phase mole fraction of component-A at temperature T
Note: The vapor pressure is a constant at constant temperature.
Hence, from the equation, we see that Raoult's Law predicts a linear


The constant-temperature phase

diagram for an ideal solution is
For a binary mixture of A and B;
pA = POAxA; pB = POBxB = POB (1 - xA)


The partial pressures vary linearly

with xA. This is shown as pA vs. xA
and pB vs. xB
For an ideal gas mixture, the total
pressure is the sum of the partial
Total pressure PT = pA + pB.

PT = pA + pBTotal pressure,
= POA xA + POB xB
POA xA + POB (1 - xA)=
:If the vapor may be taken as an ideal gas then

=yA* = pA/PT P x P x

= yB* = pB/PT


P OB x B


Relative Volatility
Distillation processes require a difference in volatilities of the components.
The greater the difference, the easier it is to separate the components. A
measure for this is termed the relative volatility.
Volatility of component-i is: partial pressure of component-i divided by mole
fraction component-i in liquid
For a binary mixture of A and B, therefore:
Volatility of A = pA / xA

Volatility of B = pB / xB

where p is the partial pressure of the component and x is the liquid mole
Relative volatility is the ratio of volatility of A (More Volatile Component MVC)
over volatility of B (Lower Volatile Component LVC):

Relative volatility is therefore a measure of separability of A and B.

Since xB = 1 - xA , we have:

Replace with pA = yAPT ; pB = ( 1 - yA )PT so as to express everything in

terms of the MVC:

Dropping subscript 'A' for more volatile component, and simplifying:

we obtain the equation for relative volatility:

The larger the value of above 1.0, the

greater the degree of separability, i.e.
the easier the separation. Recall that
when a system has reached equilibrium,
no further separation can take place.
The net transfer rate from vapor to
liquid is exactly balanced by the
transfer rate from liquid to vapor.
Separation by distillation is only feasible
within the region bounded by the
equilibrium curve and the 45o diagonal

From the equilibrium curves, we see that the greater the distance between the
equilibrium curve and the diagonal line (where y = x), the greater the difference
in liquid and vapor compositions and therefore the easier the separation by