University of Leeds

School of Chemical and Process Engineering

Separation Processes (CAPE 3301)

Part 2: Distillation

Dr Xiaoan Mao
[email protected]
Introduction

2
Objectives and Learning Outcomes
Objectives
After completion of the module, students should understand the following:
• basic concepts related to separation processes;
• fundamentals theories related to the separation processes;
• methodologies for designing simple separation devices.

Learning outcomes
On completion of the module students will be familiar with essential aspects of
gas-liquid separation by absorption/desorption and distillation.
They will understand the underlying physics associated with separation
processes, including analogies between mass, momentum and heat transfers
and be able to design absorption and distillation columns, falling film column
using established theoretical approaches.

3
Main contents

• Vapour-liquid equilibria

• Differential/simple, distillation

• Single-stage operation – flash/partial vaporization

• Continuous rectification – binary systems
• Multistage tray towers
– McCabe and Thiele Method
• Non-ideal continuous distillation
• Multi-component mixture

• Azeotropic and extractive distillation

• Practical consideration of distillation column design

4
What you will learn

1) Theories of distillation processes

2) Methods of distillation calculations
– Equilibrium
– Binary systems
• Batch
• Flash
• Rectification
– Multi-component systems
3) Design methods and consideration

5
Useful reading

• Mass transfer operation, Robert E. Treybal (3rd ed), Chapter 9 Distillation

• Transport processes and separation process principles (includes unit

operations), Christie John Geankoplis (5th ed), Chapter 26 Distillation
• Separation process principles, J. D. Seader et al (3rd ed), Chapter 7 Distillation
of binary mixtures (& Chap 4 Single Equilibrium Stages and Flash
Calculations, Chap 9 Multicomponent, Multistage Separations, Chap 13)

• Coulson and Richardson's Chemical Engineering

Volume 2 (5th ed), Chapter 11 Distillation (Knovel)
Volume 6 (4th ed), Chapter 11 Distillation (Knovel) - Design

6
Methods of teaching

• 20 hours’ worth of lecture content

– Schedule (Mondays 0900-1100)
– Mech Eng LT B 2.37
– Q/A – before and after the lectures

• Supporting materials and means

– Lectures slides, additional notes
– 20 worked examples
– 16 self-study questions as quiz (model solutions come later)
– Email for appointments

Past Examination and Assessment Papers - Doc

uments - All Documents (sharepoint.com)

7
Assessment

• Form of assessments

CAPE3301
Mid-term – in person test on Minerva 15%
(10-15 short questions, 1 hour) Week 20
Exam – Numeric questions 35%
(~3 long questions, formula sheet provided) End of May or beginning of June

8
9
 Basic separation techniques

Main focus on separation by phase creation and phase addition

10
 Need for separation processes

• A significant number of chemical engineering unit operations are concerned with the
problem of changing the compositions of solutions and mixtures through methods NOT
necessarily involving chemical reactions. Separations, including enrichment,
concentration, purification, refining and isolation, are important to chemical engineers.
• The mixing of chemicals to form a mixture is a spontaneous, natural process that is
accompanied by an increase in entropy and randomness. The inverse process, the
separation of that mixture into its constituent chemical species, is not a spontaneous
process; it requires an expenditure of energy.
• A general separation process is shown below. The feed mixture can be vapour, liquid or
solid, while the two products may differ in composition and phase state from each other,
as well as from the feed.

11
 Basic separation techniques

12
J. D. Seader et al, Separation process principles: chemical and biochemical operations, 2011, 3rd edition, John Wiley & Sons, Inc.
Basic separation techniques

Separation by phase addition or phase creation

If the feed mixture is homogeneous, single phase solution (gas, liquid), a second
immiscible phase must often be created or added before separation of chemical
species can be achieved.
This second phase is created by an energy-separating agent (ESA) and/or added as a
mass-separating agent (MSA).
Application of an energy-separating agent involves heat transfer to or from the
mixture to be separated. Alternatively, vapour may be created from a liquid phase by
reducing the pressure.
A mass-separating agent may be partially immiscible with one or more mixture
components and frequently is the constituent of highest concentration in the added
phase. Alternatively, the mass-separating agent may be miscible with a liquid feed
mixture, but may selectively alter partitioning of species between liquid and vapour
phases.

13
Basic separation techniques
Separation by phase addition or phase creation

When the feed mixture includes species that differ widely in volatility, expressed as
vapour-liquid equilibrium ratios (K – values), partial condensation or partial vaporization
may be adequate to achieve the desired separation.
Two phases are created when a vapour feed is partially condensed, by removing heat, or
a liquid feed is partially vaporized, by adding heat.
Alternatively, partial vaporization can be initiated by flash vaporization, by reducing the
feed pressure, with a valve or a turbine.
In both operations, after partitioning of species has occurred by interphase mass transfer,
the resulting vapour phase is enriched with respect to the species that are more easily
vaporized (MVCs), while the liquid phase is enriched with respect to the less-volatile
species (LVCs).

14
Basic separation techniques

15
Basic separation techniques

16
 Basic separation techniques
Distillation is the most widely utilised industrial separation method. It is a very versatile
process that is used throughout a wide variety of industries to separate mixtures of different
chemical species.

Some applications include:

1. Oil and gas production, which requires the separation of oil, gas, and water.
2. The petroleum industry to separate different fuels and chemical feed stocks.
3. The chemical and pharmaceutical industries to separate products from by-products and
raw materials and to recover solvents.

Distillation accomplishes separation by exploiting boiling point differences between different

chemical species.
For example, at atmospheric pressure acetone (nail polish remover) boils at 56.02°C while
water boils at 100°C. This simply means that the vapour pressure of acetone is higher than
the vapour pressure of water at temperatures between 56.02 and 100°C (actually at all
temperatures).

17
 Basic separation techniques

Consider a 50-50 mol % mixture of acetone and water placed in a

flask at atmospheric pressure.
There will be a range of temperatures (between 60.23 and
82.15°C), at which both vapour and liquid mixtures of acetone
and water exist. The lower temperature, 60.23°C, is called the
bubble point temperature (when the first bubble of vapour
appears on heating). The upper temperature, 80.15°C, is called
the dew point temperature because it is the temperature at Controlled mass under a
which the first drop of liquid appears on cooling. constant pressure (e.g. 1 atm.)

Suppose we were to measure the composition of the vapour and liquid at any temperature
between 60.23 and 82.15°C. The vapour phase would have more than 50 mol % acetone and
the liquid would have less than 50 mol % acetone.
Thus by simply bringing a mixture of acetone and water to a temperature in the range of
60.23 and 82.15°C, we are able to place more acetone in the vapour and more water in the
liquid. In other words, we can effectively separate the original 50-50 mixture of acetone and
water to some degree.

18
Basic separation techniques
Liquid-liquid extraction
Using one or two solvents respectively, it is widely used when distillation is impractical,
especially when the mixture to be separated is temperature-sensitive or more than
100 distillation stages would be required. When one solvent is used, it selectively
dissolves only one or a fraction of the components of the feed mixture. Additional
separation operations are generally required to recover, for recycling, solvent from
streams leaving the extraction operation.

Evapouration – is defined as the transfer of volatile components of a liquid into a gas

by heat transfer. Applications include humidification, air conditioning, and
concentration of aqueous solutions.

Crystallization – is carried out in some organic, and in almost all inorganic, chemical
plants where the desired product is a finely divided solid. Crystallization is a
purification step, so the conditions must be such that impurities do no precipitate with
the product. In solution crystallization the mixture, which includes a solvent, is cooled
and there is mass transfer of a solute from the liquid solution to a pure solid crystalline
phase.

19
Basic separation techniques
Liquid-solid extraction
Leaching is used in the metallurgical, natural product, and food industries. The major
problem in leaching is to promote diffusion of the solute out of the solid and into the
liquid solvent. The most effective way of doing this is to reduce the dimensions of the
solid to the smallest feasible particle size. For large scale applications, large open tanks
are used in counter-current operation. The major difference between solid-liquid and
liquid-liquid extractions centres around the difficulty in transporting the solid, or the solid
slurry from stage to stage.

20
 Basic separation techniques

21
J. D. Seader et al, Separation process principles: chemical and biochemical operations, 2011, 3rd edition, John Wiley & Sons, Inc.
Basic separation techniques
Separation by barriers
The use of micro-porous and non-porous membranes as semi-permeable barriers is
rapidly gaining popularity in industrial separation processes for application to difficult
and highly selective separations. Membranes are usually fabricated from natural
fibres, synthetic polymers, ceramics or metals, but they may also consist of liquid films.
Solid membranes are fabricated into flat sheets, tubes, hollow fibres or spiral-wound
sheets.
Osmosis involves the transfer, by a concentration gradient, of a solvent through a
membrane into a mixture of solute and solvent. The membrane is almost non-
permeable to the solute. In reverse osmosis, transport of solvent in the opposite
direction is effected by imposing a pressure, higher than the osmotic pressure, on the
feed side. Using a non-porous membrane, reverse osmosis successfully desalts water.
Microporous membranes can be used in a manner similar to reverse osmosis to
selectively allow small solute molecules and/or solvents to pass through the
membrane and prevent large dissolved molecules and suspended solids from passing
through.
Microfiltration refers to the retention of molecules typically in the size range from
0.05 to 10 µm. Ultrafiltration refers to the range from 1 to 100 nm.

22
Basic separation techniques
Separation by solid agents
The solid, usually in the form of a granular material or packing, acts as an inert support
for a thin layer of absorbent, or alternatively, enters directly into the separation
operation by selective adsorption of, or chemical reaction with, certain species in the
feed mixture. The active separating agent eventually becomes saturated with solute
and must be regenerated or replaced periodically.
Adsorption is used to remove components present in low concentrations in non-
adsorbing solvents or gases and to separate the components in gas and liquid mixtures
by selective adsorption on solids, followed by desorption to regenerate the adsorbent.

Chromatography is a method for separating components of a feed gas or liquid

mixture by passing the feed through a bed of packing. The feed may be volatilized into
a carrier gas, and the bed may be a solid adsorbent (gas or liquid-solid
chromatography). Because of selective adsorption on the solid adsorbent surface (or
absorption into the liquid absorbent), followed by desorption, the different
components of the feed mixture move through the bed at different rates, thus
effecting the separation.
Ion exchange resembles adsorption in that solid particles are used and regenerated.
However, a chemical reaction is involved. In water softening, an organic or inorganic
polymer in its sodium form removes calcium ions by a calcium-sodium exchange.
23
Basic separation techniques
Separation by force field
Pressure wave
Static electric field
Centrifugal force
…

Any other separation technique you can think of?

24
Quiz
For each of the following binary mixtures, a separation operation is suggested.
Explain why the operation will or will not be successful.

a) Separation of air into oxygen-rich and nitrogen-rich products by distillation.

b) Separation of m-xylene from p-xylene by distillation.
c) Separation of benzene and cyclohexane by distillation.

25
26
 An overview of distillation

Overall scheme of distillation unit

Cascade (multi-stage) distillation column, with rectifying and stripping sections
Material balance equations and energy (heat) balance equation

27
An introduction to distillation
Throughout the 20th century, multistage distillation has been by far the most widely used
method for separating liquid mixtures of chemical components. Unfortunately, distillation
is a very energy intensive technique, especially when the relative volatility of the
components being separated is low (<1.5). The energy consumption for distillation alone
in the US for 1976 totalled nearly 3% of the entire national energy consumption.
Approximately two-thirds of the distillation energy was consumed by petroleum refining,
where distillation is widely used to separate crude oil into petroleum fractions, light
hydrocarbons and aromatic chemicals.

 Key operation in oil refining for large scale pure product production (can exceed 1 M
bbl/day, one thousand barrels per day). The world’s largest refinery complex is in
India with a production capacity of 1.24 M bbl/day.
 Column diameters and height typically in the range of 0.3 –10 m and 3 –75 m,
respectively.
 Capable of providing constant product purity with variation in feed composition.
 Coupled with control systems and other separation units.

28
Distillation column

Chemical Boiling Point (°C) Melting Point (°C)

Benzene 80.1 5.5
Toluene 110.6 -95.0
29
Distillation column - P&ID for Benzene Distillation

30
 Continuous Distillation
Continuous distillation involves multiple contacts between counter-currently flowing liquid
and vapour phases. Each contact consists of mixing the two phases to promote rapid
partitioning of species by mass transfer, followed by phase separation. The contacts are
often made on horizontal trays (referred to as stages) arranged in a vertical column.

Vapour, while flowing up the column, is increasingly enriched with respect to the more
volatile species. Correspondingly, liquid flowing down the column is increasingly enriched
with respect to the less volatile species.

Feed to the distillation column enters on a tray somewhere between the top and bottom
trays, most often near the middle of the column. The portion of the column above the feed
entry is called the enriching or rectifying section; and that below is the stripping section.

Feed vapour will move up the column; feed liquid will move down. Liquid is required for
making contacts with vapour above the feed tray, and vapour is required for making contacts
with liquid below the feed tray. Normally, vapour from the top of the column is condensed in
a condenser by cooling water or a refrigerant to provide contacting liquid, called reflux.
Similarly, liquid at the bottom of the column passes through a reboiler, where it is heated by
condensing steam or some other heating medium to provide contacting vapour, called boil-
up.

31
 Continuous Distillation
The feed mixture of two or more components is separated into two or more products,
including, and often limited to, an overhead distillate and a bottom product, whose
compositions differ from that of the feed. Most often, the feed is a liquid or a vapour-liquid
mixture. The bottom product is always a liquid, but the distillate may be a liquid or a
vapour or both.

The separation requires that:

(1) a second phase be formed, so that both liquid
and vapour phases are present and can contact
each other;
(2) the components have different volatilities so that
they will partition between the two phases to
different extents, and
(3) the two phases can be separated by gravity or
other mechanical means.

32
Equilibrium-stage processes
A large class of mass transfer devices consists of
assemblies of individual units, or stages, that
are interconnected so that the materials being
processed pass through each stage in turn.
The two streams move through the assembly
either counter-currently, co-currently, or cross-
currently.
In each stage, they are brought into contact,
mixed and then separated. Such multistage
systems are called cascades.
The counter-current arrangement is normally
preferred, because it generally results in a
higher degree of separation than the other two.

33
 Equilibrium-stage processes

For mass transfer to take place, the streams entering each stage must not be equilibrium
with each other, for it is the deviation from equilibrium conditions that provides the driving
force for transfer. The leaving streams are usually not in equilibrium either but are much
closer to being so than the entering streams are.

To simplify the calculations for a cascade, the streams leaving each stage are often assumed
to be in equilibrium, which, by definitions, makes each stage ideal.

A correction factor, or efficiency factor, is applied later to account for any actual departures
from equilibrium.

Note –mass transfer separations are governed by transport (mass transfer limits the rate of
separation) and by equilibrium (thermodynamics limit the extent of separation).

34
 Cascades
The cascade shown consists of a series of single sections or stages with streams entering
and leaving only from the ends. Such cascades are used to recover components from a feed
stream but are not generally useful for making a sharp separation between two selected
feed components.

To do this, it is best to provide a cascade consisting

of two sections and the counter-current cascade is
often used. It consists of one section above the feed
and one below.

35
 Material and energy balance for stages
When considering multistage systems as a whole, attention is focused on the streams
passing between the individual stages. An individual unit in a cascade normally receives two
streams from the two units adjacent to it (e.g. one from the stage above and the other from
the stage below, brings them into close contact, and delivers two streams respectively (e.g.
one to the stage above and one to the stage below).
The individual contact units in a cascade are numbered sequentially, starting from one end.
If we consider the stages are numbered from the bottom and up. A general stage in the
system is the nth stage, which is number n counting from the bottom. The stage
immediately ahead of stage n in the sequence is stage n-1 and that immediately following it
is stage n+1.
To designate the streams pertaining to any one stage, all streams originating in that stage
carry the number of the unit as a subscript. Thus, for a two-component system, yn-1 is the
mole fraction of the lightest component (i.e. the one with the lowest boiling point) in the
vapour phase leaving stage n-1, and Ln is the molar flow rate of the L phase leaving the nth
stage.

36
Material and energy balance for stages

The total input of material to stage n is + units (mass or moles) per time and the total
output is + units per time. Since, under steady flow, there is neither accumulation nor
depletion, the input and the output are equal and the material balance can be written
as:

This equation is the total material balance for the stage.

Another balance can be written by equating input to output for component i giving the
component i balance:

Obviously, if all the component balances for a system were added up, the sum would be
equal to the total material balance.

37
Material and energy balance for stages

In most equilibrium stage processes, the general energy balance can be simplified by
neglecting potential energy and kinetic energy. If, in addition, the process is workless
and adiabatic, a simple enthalpy balance applies:

where and are the enthalpies per unit (mass or moles) of the L phase and V phase,
respectively, and is the heat added.

38
 Worked example 1

Material balance

A mixture of methanol and water containing 40 mol% of methanol is to be separated to give

a product of 90 mol% of methanol at the top, and a bottom product with 10 mol% of
methanol. The feed flow rate is 100 kmol/hr and the feed is heated so that it enters the
column at its bubble point.
Find the top and bottom product flow rates.

39
A mixture of methanol and water containing 40 mol% of methanol is to be separated to give
a product of 90 mol% of methanol at the top, and a bottom product with 10 mol% of
methanol. The feed flow rate is 100 kmol/hr and the feed is heated so that it enters the
column at its bubble point.
Find the top and bottom product flow rates.

40
Vapour-Liquid Equilibria

41
 Vapour-Liquid Equilibria

The chemical potential of liquids: To discuss the equilibrium properties of liquid mixtures we
need to know how the chemical potential of a liquid varies with its composition. To calculate
its value, we use the fact that, at equilibrium, the chemical potential of a substance present as
a vapour must be equal to its chemical potential in the liquid.
Phase boundaries: The phase diagram of a substance shows the regions of pressure and
temperature at which its various phases are thermodynamically stable. The lines separating
the regions, which are called phase boundaries, show the values of P and T at which two
phases co-exist in equilibrium

42
 Vapour-Liquid Equilibria

Consider a liquid sample of a pure substance in a closed vessel. The pressure of a vapour in
equilibrium with the liquid is called the vapour pressure of the substance. Therefore, the
liquid-vapour phase boundary in a phase diagram shows how the vapour pressure of the
liquid varies with temperature.

where
= total pressure
= vapour pressure of component A

Recall Dalton’s law:

The pressure exerted by a mixture of perfect gases (intermolecular forces are neglected) is
the sum of the partial pressures of the gases.
That is, if a certain amount of H2 exerts 25 kPa when present alone in a container, and an
amount of N2 exerts 80 kPa when present alone in the same container at the same
temperature, then the total pressure when both gases are present is the sum of these two
partial pressures, or 105 kPa.
𝑃 𝑡 =𝑝 𝐴 +𝑝 𝐵 ⋯⋯ 43
 Vapour-Liquid Equilibria

Next, we define the partial pressure, , for a mixture of vapours A and B (a two-fluid mixture):

The partial pressure, , for a mixture of liquids A and B, are

using Raoult’s Law.

: total pressure
: vapour pressure of pure component A
: vapour pressure of pure component B
: partial pressure of A
: partial pressure of B
: mole fraction of A in liquid phase
: mole fraction of B in liquid phase
: mole fraction of A in vapour phase
: mole fraction of B in vapour phase 44
 Vapour-Liquid Equilibria

Raoult’s Law
For an ideal solution, the equilibrium partial pressure of a constituent at a fixed temperature
equals the product of its vapour pressure when pure at this temperature and its mole fraction
in the liquid.

In a two-fluid mixture (a binary mixture),

If the vapour phase is also ideal, Dalton’s law is applicable:

and

And the total as well as the partial pressures are linear in at a fixed temperature!
45
Vapour-Liquid Equilibria

46
 Vapour-Liquid Equilibria

Henry’s law (Ideal-dilute solutions): William Henry found experimentally that, for real
solutions at low concentrations (low solubility), although the partial pressure of the solute is
proportional to its mole fraction, the constant of proportionality is not the vapour pressure of
the pure substance.

In this expression, is the mole fraction of the solute.

And is the proportionality factor (with the dimensions of pressure) determined so that the
plot of the partial pressure of A against its mole fraction is tangent to the experimental curve
at = 0.
Failure to follow Henry’s law over wide concentration ranges may be the result of chemical
interaction with the liquid or electrolytic dissociation, as is the case with water-ammonia, or
non-ideality in the gas phase.

47
Vapour-Liquid Equilibria

48
 Vapour-Liquid Equilibria

Summary:
,

𝑉 𝑉
𝑃 𝑡 =𝑝 𝐴 +𝑝 𝐵 =𝑃 𝐴 𝑥 𝐴 + 𝑃 𝐵 (1− 𝑥 𝐴 )

49
 Worked example 2 - Raoult’s Law

Calculate the vapour-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

• Calculate the liquid and vapour mole fractions for the more volatile component at 110 °C
• Calculate the relative volatility

50
51
 Worked example 2a - Raoult’s Law

Calculate the vapour-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

T (°C) (mmHg) (mmHg)

98.4 760 333
105 940 417
110 1050 484
115 1200 561
120 1350 650
125.6 1540 760

52
53
 Worked example 2a - Raoult’s Law

Calculate the vapour-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

T (°C) (mmHg) (mmHg)

98.4 760 333 1.000 1.000 -
105 940 417 0.656 0.811 2.254
110 1050 484 0.488 0.674 2.169
115 1200 561 0.311 0.492 2.139
120 1350 650 0.157 0.279 2.077
125.6 1540 760 0.000 0.000 -

54
 Worked example 2a - Raoult’s Law

Calculate the vapour-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

130

125 Bubble point

Dew point
120
Temperature (°C)

115

110

105

100

95
0.0 0.2 0.4 0.6 0.8 1.0
Mole fraction (x, y)

55
 Constant-Pressure Equilibria
The upper curve provides the temperature-vapour composition (t-y) relationship, the lower
that of the temperature-liquid composition (t-x). Liquid and vapour mixtures at equilibrium are
at the same temperature and pressure throughout, so that horizontal tie lines such as line DF
join equilibrium mixtures at D and F. There are an infinite number of such tie lines for this
diagram. A mixture on the lower curve, as at point D, is a saturated liquid; a mixture on the
upper curve, as at F, is a saturated vapour. A mixture at E is a two-phase mixture, consisting of
a liquid phase composition at D and a vapour phase composition at F in such proportions that
the average composition of the entire mixture is represented by E. The relative amounts of the
equilibrium phases are related to the segments of the tie line,

𝑀𝑜𝑙𝑒𝑠𝑜𝑓 𝐷 𝑙𝑖𝑛𝑒 𝐸𝐹
=
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐹 𝑙𝑖𝑛𝑒 𝐷𝐸

56
 Constant-Pressure Equilibria

Consider a solution at G at constant pressure. The solution is entirely liquid. If it is heated, the
first bubble of vapour forms at H and has the composition at J, richer in the more volatile
substance, and hence the lower curve is called the bubble-point-temperature curve. As more
of the mixture is vaporized, more of the vapour forms at the expense of the liquid, giving rise,
for example, to liquid L and its equilibrium vapour K, although the composition of the entire
mass is still the original as at G. The last drop of liquid vapourizes at M and has the composition
of N. Superheating the mixture follows the path MO. The mixture has vaporized over a
temperature range from H to M.

57
 Constant-Pressure Equilibria

The vapour-liquid equilibrium compositions can also be shown on a distribution diagram (x vs

y). Point P on the diagram represents the tie line DF, for example. Since the vapour is richer in
the more volatile substance, the curve lies above the 45° diagonal line.

58
 Constant-Pressure Equilibria

Relative Volatility: The greater the distance between the equilibrium curve and the diagonal
line, the greater the difference in liquid and vapour compositions and the easier the separation

the case of distillation, the relative volatility (𝛼). This is the ratio of the concentration ratio of A
by distillation. One numerical measure of this is called the separation factor or, particularly in

and B in one phase to that in the other and is a measure of separability.

If (except at x = 0 or 1), = 1.0 and no separation is possible. The large the value of above
unity, the greater the degree of separability.

Recall

59
 Constant-Pressure Equilibria

For narrow-boiling binary mixtures that exhibit ideal or nearly ideal behaviour, the relative
volatility, , varies little with pressure. If is constant over the entire composition range, the y-x
phase-equilibrium curve can be determined and plotted from:

Note the assumption!

60
 Constant-Pressure Equilibria

Thus, from the knowledge of just the vapour pressures of the two components at a given
temperature, a y-x phase equilibrium curve can be approximated using only one value of .
Families of curves can be used for preliminary calculations in the absence of detailed
experimental data.

When the area enclosed by the

equilibrium curve and the 45° line is
large, separation of the mixture by
distillation will be easier.

61
 Constant-Pressure Equilibria

K-Values: A phase equilibrium ratio is the ratio of mole fractions of a species in two phases
(vapour and liquid) at equilibrium. For vapour-liquid systems, the constant is referred to as the
K-value or vapour-liquid equilibrium ratio:

If Raoult’s law and Dalton’s law hold, values of can be calculated from the vapour pressure and
the total pressure of the system.
and

62
 Constant-Pressure Equilibria

K-Values: The K factors are strongly temperature-dependent because of the change in vapour
pressure, but the relative values of K for two components change only moderately with
temperature. The ratio of K factors is the same as the relative volatility of the components:

𝑦𝑖
𝐾 𝑖=
𝑥𝑖
When Raoult’s law applies:

63
 Binary Vapour-Liquid Systems

Experimental vapour-liquid equilibrium data for binary systems are widely available. Because
and , the data are presented in terms of just four intensive variables: , , and .

Both phases become richer in the less-volatile

component, B, as temperature increases. For
= 1, the temperature is the boiling point of A
at 1 atm; for = 0, the temperature is the
normal boiling point of B.
For the water-glycerol system, the difference in
boiling points is 190 °C. Therefore, relative
volatility values are very high, making it possible
to achieve good separation in a single
equilibrium stage. Industrially, the separation is
often conducted in an evaporator, which
produces a nearly pure water vapour and a
glycerol-rich liquid. For example, at 207 °C, a
vapour of 98 mol% water is in equilibrium with a
liquid containing more than 90 mol% glycerol.

64
 Binary Vapour-Liquid Systems

Consider the system n-hexane (H) and n-Octane (O) at 101.3 kPa. The upper curve, labelled
“Saturated vapour”, gives the dependency of vapour mole faction on the dew-point
temperature; the lower curve, labelled “Saturated liquid”, shows the bubble-point temperature
as a function of liquid-phase mole fraction. The two curves converge at = 0, the normal boiling
point of n-Octane (258.2 °F = 125.7 °C), and at = 1, the boiling point of n-hexane (155.7 °F =
68.7 °C). For two phases to exist, a point representing the overall composition of the binary
mixture at a given temperature must be located in the two-phase region between the two
curves.
If the point lies above the saturated-vapour
curve, a superheated vapour exists; if the point
lies below the saturated-vapour curve, a
subcooled liquid exists.

65
 Binary Vapour-Liquid Systems

Consider a mixture of 30 mol% H (n-hexane) at 150 °F. Point A is a subcooled liquid with = 0.3.
When this mixture is heated at 1 atm, it remains liquid until a temperature of 210 °F, point B is
reached. This is the bubble point where the first bubble vapour appears. This bubble is a
saturated vapour in equilibrium with the liquid at the same temperature. Its composition is
determined by following a tie line, which is BC, from = 0.3 to = 0.7. This tie line is horizontal
because the phase temperatures are equal.
As the temperature of the two-phase mixture
is increased to point E, on the horizontal tie
line DEF at 225 °F, the mole fraction of H in the
liquid phase decreases to = 0.17 (because it is
more volatile than O (n-octane) and
preferentially vapourizes, and the mole
fraction of H in the vapour decreases to =
0.55.

66
 Binary Vapour-Liquid Systems

Throughout the two-phase region, the vapour is at its dew point, and the liquid at its bubble
point. The overall composition of the two phases remains at a mole fraction of 0.30 for hexane.
At point E, the relative phase amounts are determined by the inverse-lever-arm rule using the
lengths of the line segments DE and EF.

𝑉 𝐷𝐸
The vapour/liquid ratio, =
𝐿 𝐸𝐹

When the temperature is increased to 245 °F,

point G, the dew point = 0.3, is reached,
where only a differential amount of liquid
remains. An increase in temperature to point H
at 275 °F gives a superheated vapour with =
0.3.

67
 Binary Azeotropic Systems

Departure from Raoult’s law commonly manifest themselves in the formation of azeotropes.

Azeotropic-forming mixtures exhibit either maximum-or minimum-boiling points at some

composition, corresponding, respectively, to negative and positive deviations from Raoult’s
law.
Vapour and liquid compositions are identical for an azeotrope; thus, all K-values are 1, = 1,
and no separation can take place.
If only one liquid phase exists, it is a homogenous azeotrope;
If more than one liquid phase is present, the azeotrope is heterogeneous.
When there are strong physical or chemical interactions between components, azeotropes
may form. As a critical composition where the liquid and vapour compositions are identical,
separation cannot continue without changing pressure.

68
 Binary Azeotropic Systems

A mixture whose total pressure is greater than that computed for ideality is said to show
positive deviations from Raoult’s law. In these cases the partial pressures of each component
are larger than the ideal. The liquid-and vapour-composition curves are tangent at point L,
the point of azeotropism at this pressure, which represents the minimum-boiling
temperature for this system. For all mixtures of composition less than L, such as those at C,
the equilibrium vapour (E) is richer in the more volatile component than the liquid (D).
For all mixtures richer than L, however, such as
at F, the equilibrium vapour (G) is less rich in
the more volatile substance than the liquid (H).
A mixture of composition L gives rise to a
vapour of composition identical with the
liquid, and it consequently boils at constant
temperature without change in composition.

A well-known example of an azeotrope is

95.6% ethanol and 4.4% water (by weight).
Ethanol boils at 78.4 °C, water boils at 100 °C,
but the azeotrope boils at 78.1 °C, which is
lower than either of its constituents.
69
 Binary Azeotropic Systems

The most common by far is the minimum-boiling homogenous azeotrope, e.g. isopropyl
ether-isopropyl alcohol. At a temperature of 70 °C, the maximum total pressure is greater
than the vapour pressure of either pure component, as shown in (a), because activity
coefficients are greater than 1. The y-x diagram in (b) shows that for a pressure of 1 atm, the
azeotropic mixture is at 78 mol% ether. Figure (c) is a T-x diagram at 1 atm, where the
azeotrope is seen to boil at 66 °C. In Figure (a), for 70 °C, the azeotrope occurs at 123 kPa, for
72 mol% ether. Thus, the azeotropic composition and temperature shift with pressure. In
distillation, minimum-boiling azeotropic mixtures are approached in the overhead product.

70
 Binary Azeotropic Systems

When the total pressure of a system at equilibrium is less than the ideal value, the system is
said to deviate negatively from Raoult’s law. This gives rise to a maximum in the boiling
temperatures, as at point L, and a condition of azeotropism. The equilibrium vapour is leaner
in the more volatile substance for liquid whose x is less than the azeotropic composition and
greater if x is larger.

An example is hydrochloric acid at a

concentration of 20.2% hydrogen chloride and
79.8% water (by weight). Hydrogen chloride
boils at -84 °C and water at 100 °C, but the
azeotrope boils at 110 °C, which is higher than
either of its constituents.
110 °C is the maximum temperature at which
any hydrochloric acid solution can boil.

71
 Binary Azeotropic Systems

For maximum-boiling homogenous azeotropic acetone-chloroform system in (a), the

minimum total pressure at 60 °C is below the vapour pressures of the pure components
because activity coefficients are less than 1. The azeotrope is approached in the bottom
product in a distillation operation. Phase compositions at 1 atm are shown in Figures (b) and
(c).

72
 Worked example 3 - Raoult’s Law

Use Raoult’s Law to calculate the vapour and liquid compositions in equilibrium (in mole
fractions, y and x) for the benzene-toluene system at a pressure of 101.32 kPa, using vapour
pressure data measured as shown in the table.

Vapour pressure
Temperature Benzene (A) Toluene (B)
°K °C kPa mmHg kPa mmHg
353.3 80.1 101.32 760 - -
358.2 85.0 116.9 877 46.0 345
363.2 90.0 135.5 1016 54.0 405
368.2 95.0 155.7 1168 63.3 475
373.2 100.0 179.2 1344 74.3 557
378.2 105.0 204.2 1532 86.0 645
383.3 110.6 240.0 1800 101.32 760

73
 Worked example 3 - Raoult’s Law

Use Raoult’s Law to calculate the vapour and liquid compositions in equilibrium (in mole
fractions, y and x) for the benzene-toluene system at a pressure of 101.32 kPa, using vapour
pressure data measured as shown in the table.

T, °C
80.1
85.0
90.0
95.0
100.0
105.0
110.6

𝑦𝐴 𝑦𝐴
𝑉 𝑉 𝑉
𝑃𝑡 − 𝑃 𝐵 𝑃 𝑥𝐴
𝐴 𝑥𝐴 𝑦 𝐴 𝑥𝐵 𝑥𝐴 𝑦𝐴 𝑃𝐴
𝑥 𝐴= 𝑉 𝑉 𝑦 𝐴= 𝛼 𝐴𝐵=
𝑦𝐵
=
𝑦 𝐵 𝑥𝐴
= 𝐾 𝐴= =
𝑃𝐴−𝑃 𝐵 𝑃𝑡 (1 − 𝑦 𝐴) 𝑥𝐴 𝑃𝑡
𝑥𝐵 ( 1− 𝑥 𝐴 )
74
 Worked example 3 - Raoult’s Law

Use Raoult’s Law to calculate the vapour and liquid compositions in equilibrium (in mole
fractions, y and x) for the benzene-toluene system at a pressure of 101.32 kPa, using vapour
pressure data measured as shown in the table.

T, °C
80.1 1 1 0 0 1 - -
85.0 0.780 0.900 0.220 0.100 1.154 0.454 2.541
90.0 0.581 0.776 0.419 0.224 1.337 0.533 2.509
95.0 0.411 0.632 0.589 0.368 1.537 0.625 2.460
100.0 0.258 0.456 0.742 0.544 1.769 0.733 2.412
105.0 0.130 0.261 0.870 0.739 2.015 0.849 2.374
110.6 0 0 1 1 - 1 -

𝑦𝐴 𝑦𝐴
𝑉 𝑉 𝑉
𝑃𝑡 − 𝑃 𝐵 𝑃 𝑥𝐴
𝐴 𝑥𝐴 𝑦 𝐴 𝑥𝐵 𝑥𝐴 𝑦𝐴 𝑃𝐴
𝑥 𝐴= 𝑉 𝑉 𝑦 𝐴= 𝛼 𝐴𝐵=
𝑦𝐵
=
𝑦 𝐵 𝑥𝐴
= 𝐾 𝐴= =
𝑃𝐴−𝑃 𝐵 𝑃𝑡 (1 − 𝑦 𝐴) 𝑥𝐴 𝑃𝑡
𝑥𝐵 ( 1− 𝑥 𝐴 )
75
76
Self study questions 1-4

2021-22 exam paper (S2) Q1

77
 Batch Distillation
Flash Distillation
and
Cascade Configuration

78
 Batch Distillation

A familiar example of a batch distillation is the laboratory distillation, where a liquid mixture
is charged to a still-pot and heated to boiling. The vapour formed is continuously removed
and condensed to produce a distillate. The compositions of the initial charge and distillate
change with time; there is no steady state. The still temperature increases and the amount of
lower-boiling components in the still-pot decreases as distillation proceeds.

1. Vapour is condensed and collected in

a receiver;
2. Liquid remaining in the still-pot is
called the residue;
3. The composition of the material
collected in the receiver varies with
time;
4. Often, the receiver will be emptied
several times to collect separate cuts
of product.

79
Batch Distillation

1. Heat source
2. Still-pot
3. Still head
4. Thermometer/Boiling point temperature
5. Condenser
6. Cooling water in
7. Cooling water out
8. Distillate/receiving flask
9. Vacuum/gas inlet
10. Still receiver
11. Heat control
12. Stirrer speed control
13. Stirrer/heat plate
14. Heating (Oil/sand) bath
15. Stirring means e.g. magnetic follower
16. Cooling bath

80
 Batch Distillation

Batch operations can be used to advantage when:

1. The capacity of a facility is too small to permit continuous operation at a practical rate.
2. Seasonal or customer demands require distillation in one unit of different feedstocks to
produce different products.
3. Several new products are to be produced with one distillation unit for evaluation by
potential buyers.
4. Upstream process operations are batch-wise and the compositions of feedstocks for
distillation vary with time or from batch to batch.
5. The feed contains solids or materials that form solids, tars, or resin that can plug or foul a
continuous distillation column.

81
 Batch Distillation

The simple, batch distillation was first quantified by Lord Rayleigh and is often referred to as
differential distillation. There is no reflux; at any instant, vapour leaving the still-pot with
composition is assumed to be in equilibrium with liquid (residue) in the still-pot, which is
assumed to be perfectly mixed.
For total condensation, . The still pot is assumed to be the only equilibrium stage because
there are no trays above the still-pot.
The following nomenclature is used for variables that are a function of time, t, assuming that
all compositions refer to a particular species in the multi-component feed.

D = instantaneous distillate rate (mol/hr)

y = (more volatile component in the vapour) Overall mass balance:
= (more volatile component in product)
= mole fraction in instantaneous distillate leaving the still-pot
W = moles of liquid (residue) left in still-pot
x = = mole fraction of more volatile component
in liquid (residue)
0 = subscript referring to t = 0
82
 Batch Distillation

For any component in the mixture: instantaneous rate of output =

Also, the instantaneous rate of depletion in the still is

Chain rule

Distillate rate and, therefore, liquid-depletion rate in the still-pot, depend on the heat-input
rate, , to the still-pot.

By component material balance at any instant:

From the total material balance

or, when is assumed constant

83
 Batch Distillation

The component material balance can also be written:

Multiplying by , and separating variables and integrating from the initial charge condition of
and

This is the well-known Rayleigh equation, which was first applied to batch distillation of
wide-boiling mixtures such as HCl-H2O, H2SO4-H2O, and NH3-H2O, where one stage is sufficient
to get the desired separation.

84
 Batch Distillation

Without reflux, and are assumed to be in equilibrium, and hence

Rayleigh equation
where is replaced by .

Simple case 1:
This equation is easily integrated when pressure is constant, temperature change in the still-
pot is relatively small, and K-values are composition independent. Then , where is
approximately constant.

85
 Batch Distillation

Simple case 2:
For a binary mixture, if the relative volatility , instead of , is assumed constant then:

followed by integration and simplification gives:

From these equations, the amount of liquid to be distilled in order to obtain a liquid of given
concentration in the still-pot may be obtained.

86
 Worked example 4

A batch still-pot is loaded with 100 kmol of a binary mixture of 50 mol% benzene and
toluene. As a function of time, make plots of:
(a) still-pot temperature,
(b) instantaneous vapour composition,
(c) still-pot composition, and
(d) average total-distillate composition.
Assume a constant boil-up rate, and therefore, constant D of 10 kmol/hr, and a constant of
2.41 at a pressure of 101.3 kPa (1 atm).
T, °C
105.3 0.10 0.208
101.5 0.20 0.372
Vapour-Liquid equilibrium data for 98.0 0.30 0.507
Benzene (B) and Toluene (T) at 101.3 kPa. 95.1 0.40 0.612
92.3 0.50 0.713
89.7 0.60 0.791
87.3 0.70 0.857
85.0 0.80 0.912
82.7 0.90 0.959
81.4 0.95 0.980 87
88
 Worked example 4a

Repeat the previous example, except that instead of using = 2.41, use the vapour-liquid
equilibrium data for benzene-toluene at 101.3 kPa to solve the problem graphically.

T, °C
105.3 0.10 0.208
101.5 0.20 0.372
Vapour-Liquid equilibrium data for 98.0 0.30 0.507
Benzene (B) and Toluene (T) at 101.3 kPa. 95.1 0.40 0.612
92.3 0.50 0.713
89.7 0.60 0.791
87.3 0.70 0.857
85.0 0.80 0.912
82.7 0.90 0.959
81.4 0.95 0.980 89
90
 Batch Distillation

Graphical methods:
1. Plot the y-x equilibrium curve
2. At a series of x values, find y-x
3. Plot 1/(y-x) vs. x
4. Graphically integrate from x0 to x
5. The final charge of material W in
the still-pot is:

91
 Worked example 5

A 100 g/mol liquid mixture containing 50 mole% n-heptane and 50 mole% n-octane at 30 °C
is subjected to a differential distillation at atmospheric pressure. The process is stopped
when the mole fraction of the most volatile component in the still-pot reaches 0.33.
Determine the amount of composited distillate collected and its mole fractions (i.e. ).

0.655 0.810
0.510 0.698
Equilibrium data for n-heptane and n- 0.487 0.674
octane is (in mole fractions n-heptane in 0.312 0.492
vapour and liquid). 0.284 0.459
0.157 0.279
0.097 0.184
0.039 0.078
0.012 0.025
0.00 0.00 92
93
 Flash Distillation

A flash is a single-equilibrium-stage distillation in which a feed is partially vaporized to give a

vapour richer than the feed in the more volatile components.
In (a):
1) a pressurized liquid feed is heated and flashed adiabatically across a valve to a lower
pressure, resulting in creation of a vapour phase that is separated from the remaining
liquid in a flash drum;
2) if the valve is omitted, a liquid can be partially vaporized in a heater and then separated
into two phases.
Alternatively, a vapour feed can be cooled and partially condensed (b) to give, after phase
separation, a liquid richer in the less volatile components. For properly designed systems, the
streams leaving the drum will be in phase equilibrium.

94
 Flash Distillation

Flash distillation is used extensively in petroleum refining, in which petroleum fractions are
heated in pipes stills and the heated fluid is flashed into vapour and residual liquid streams,
each containing many components. Liquid from an absorber is often flashed to recover some
of the solute; liquid from a high-pressure reactor may be flashed to a lower pressure, causing
some vapour to be vaporized.

95
 Flash Distillation

Usually there are six degrees of freedom (DOF) to work with for the design of a binary flash
distillation. The original feed specifications often take up four of these DOF:
1. Feed flow rate,
2. Feed composition,
3. Temperature,
4. Pressure,
Of the remaining, the designer will usually select first:
5. Drum pressure,
The pressures must be chosen so that at the feed pressure, , the feed is below its bubble point
and remains liquid. While at the pressure of the flash drum, , the feed is above its bubble
point and some of it vaporizes. The drum pressure must be below the critical pressure for the
mixture so that a liquid phase can exist.

96
Flash Distillation
We will assume that the flash drum acts as an equilibrium stage, so vapour and liquid are
in equilibrium.
The phase equilibrium of the mixture, which can be represented by , or , can be the sixth
DOF.
For a binary system, the mole fraction of the more volatile component in the vapour, y, and
its mole fraction in the liquid, x, and can be determined from the equilibrium expressions:

Mass and energy balances are written for the balance around the flash drum.
For a binary system there are two independent mass balances.
The overall mass balance is given by:

and the component balance for the most volatile component is:

97
 Flash Distillation

The energy balance is:

where , , and are the enthalpies of the feed, vapour(distillate) and liquid streams. Usually, ,
since the flash drum is insulated, and the flash is considered to be adiabatic.

To use the energy balance equations, we need to know the enthalpies. Their general form is:

For ideal mixtures, the enthalpies can be calculated from heat capacities and latent heats.
Then;

where and are mole fractions of component A in liquid and vapour, respectively. is the molar
heat capacity, is the chosen reference temperature, and is the latent heat of vaporization at .

98
 Flash Distillation

To solve these equations we first combine the mass balances and solve for y:
𝑦 =𝑚𝑥 +𝑏
This is the operating equation, which for a single-stage system relates the compositions of the
two streams leaving the stage (i.e. and ).

The equation can be rewritten in terms of either the fraction vaporized, (or the fraction
remaining liquid, ).
From the overall mass balance, the liquid-vapour split is given as:

Then the operating equation becomes:

99
 Flash Distillation

Now the equilibrium and the operating equation must be solved simultaneously. The exact
way to do this depends on the form of the equilibrium data.

For binary systems, a graphical solution is convenient. A single straight line, call the operating
line, can be plotted on a graph of y versus x.

• The straight line will have:

• And y intercept ()

100
 Flash Distillation

The equilibrium data at Pdrum can also plotted on the y-x diagram. The intersection of the
equilibrium curve and the operating line is the simultaneous solution of the mass balances
and equilibrium.
This plot of y versus x showing both equilibrium and operating lines is called a McCabe-Thiele
diagram and is shown below for ethanol-water separation.

101
 Flash Distillation

We can also solve the mass balance to yield :

or as shown in the operating equation:

We can also solve the mass and energy balance simultaneously to yield:

102
 Worked example 6

A liquid mixture containing 50 mol% n-heptane (A), 50 mol% n-octane (B), at 30 °C, is to be
continuously flash-vaporized at 1 std atm pressure to vaporize 60 mol% of the feed. What will
be the composition of the vapour and liquid at the temperature in the separator for an
equilibrium stage?

Solution basis: F = 100 mol, xF= 0.5, D = 60 mol, L = 40 mol.

T, °C
98.4 1.0 1.0
105.0 0.655 0.81
110.0 0.487 0.674
115.0 0.312 0.492
120.0 0.1571 0.279
125.6 0.0 0.0

103
104
 Worked example 7

An equimolar mixture of benzene and toluene in subjected to flash distillation at a pressure of

1 bar in the separator. Determine the compositions (in mole fraction benzene) of the liquid
and vapour leaving the separator when the feed is 25% vaporized.
1) Estimate the temperature in the separator.
2) What are the concentrations in the vapour and liquid, and the separator temperature
when the feed is: a) 0% vaporized, b) 50% vaporized, c) 75% vaporized and d) 100%
vaporized.
Plot the operating lines for each of these cases and discuss how the operating lines change as
f changes.

T, °C
80.1 1.0 1.0
Equilibrium data for
85.0 0.780 0.900
benzene-toluene
90.0 0.581 0.777
system at 1 bar:
95.0 0.411 0.632
100.0 0.258 0.456
105.0 0.130 0.261
110.6 0.0 0.0

105
106
Self study questions 5-8

107
108
 Cascade
One separation stage is rarely sufficient to produce pure commercial products. Cascades,
which are aggregates of stages, are needed to:
1) Accomplish separations that cannot be achieved in a single stage;
2) Reduce amounts of mass-or energy-separating agents required;
3) Make efficient use of raw materials.

Counter-current cascade is prevalent in unit

operations such as distillation, absorption,
stripping, and liquid-liquid extraction. Two or more
process streams of different phase states and
compositions are intimately contacted to promote
rapid mass and heat transfer so that the separated
phases leaving the stage approach physical
equilibrium. Although equilibrium conditions may
not be achieved in each stage, it is common to
design and analyze cascades using equilibrium-
stage models.

109
 Cascade configurations

Shown below are possible cascade configurations in both horizontal and vertical layouts.
Stages are represented by either boxes [as shown in (a)], or as horizontal lines [as shown in
(d)].
Symbols:
is the feed;
is the mass-separating agent, if used, and
are products.

110
 Cascade configurations

The linear counter-current cascade, shown in (a), is very efficient and widely used. The linear
cross-current cascade, shown in (b), is not as efficient as the counter-current cascade, but it is
convenient for batchwise configurations in that the solvent is divided into portions fed
individually to each stage.
Figure (c) depicts a two-dimensional diamond configuration rather than a linear cascade. In
batch crystallization, feed F is separated in stage 1 into crystals, which pass to stage 2, and
mother liquor, which passes to stage 4. In other stages, partial crystallization or
recrystallization occurs by processing crystals, mother liquor, or combinations thereof with
solvent S. Final products are purified crystals and impurity-bearing mother liquors.

111
 Cascade configurations

The cascade shown in the figure (LHS) consists of single sections of stages with streams
entering and leaving only from the ends. Such cascades are used to recover components from
a feed stream, but are not useful for making a sharp separation between two selected feed
components, called key components. To do this, a cascade of two sections of stages is used,
e.g., the counter-current cascade of (d), which consists of one section above the feed and one
below. If S2 is boiling vapour produced by steam or partial vaporization of P2 by a boiler, and S1
is liquid reflux produced by partial condensation of P1, this is a simple distillation column. If
two solvents are used, where S1 selectively dissolves certain components of the feed while S 2
is more selective for the other components, the process is fractional liquid-liquid extraction.

112
 Cascade configurations

Figure (e) is an interlinked system of two distillation columns containing six counter-current
cascade sections. Reflux and boil-up for the first column are provided by the second column.
This system can take a three-component feed, F, and produce three almost pure products, P 1,
P2, and P3.

113
 Cascade configurations

The cascade shown has a decreasing

vapour flow rate as we go from the feed
stage to the top stage and a decreasing
liquid flow rate as we go from the feed
stage to the bottom stage. The cascade is
the usual form in which distillation is done.
Because of the repeated vaporizations and
condensations as we go up the column,
the top product (distillate) can be highly
concentrated in the most volatile
component. The section of the column
above the feed stage is known as the
enriching or rectifying section. The
bottom product is highly concentrated in
the less volatile component, since the
most volatile component has been
stripped out by the rising vapours. This
section is called the stripping section.

114
Continuous distillation with reflux
(Equimolar overflow)

115
Key points

• Material balances in plate columns

• McCabe-Thiele assumptions
• Operating line equations
• Feed line
• Total reflux
• Minimum reflux
• McCabe-Thiele method
• Lewis-Sorel method

116
 Continuous Distillation with Reflux

Action on an ideal plate: On an ideal plate, by definition, the

liquid and vapour leaving the plate are brought into
equilibrium. Consider a single plate in an ideal cascade, such
as plate n in the figure. Assume that the plates are numbered
in series from the top down and that the plate under
consideration is the nth plate from the top. Then the plate
immediately above plate n is plate n-1, and that immediately
below it is plate n+1. Subscripts are used on all quantities to
show the point of origin of the quantity.

Two fluid streams enter plate n, and two leave it. A stream of
liquid Ln-1 mol/h from plate n-1 and a stream of vapour Vn+1
mol/h from plate n+1 are brought into intimate contact. A
stream of vapour Vn mol/h rises to plate n-1, and a stream of
liquid Ln mole/h descends to plate n+1. Since the vapour
streams are the V phase, their concentrations are denoted by
y. The liquid streams are the L phase, and their
concentrations are denoted by x.

117
 Continuous Distillation with Reflux

To produce nearly pure products at both the top and bottom of a continuous distillation
column, the feed is admitted to a plate in the central portion of the column. If the feed is
liquid, it flows down the column to the reboiler and is stripped of component A by the vapour
rising from the reboiler. By this means a bottom product can be produced which is nearly pure
B.

A typical continuous distillation column

equipped with the necessary auxiliaries and
containing rectifying and stripping sections are
shown opposite. Column A is fed near its
center with a steady flow of feed of definite
concentration. Assume that the feed is a liquid
at its boiling point. The plate on which the feed
enters is called the feed plate. All plates above
the feed plate constitute the rectifying section,
and all plates below the feed, including the
feed plate, constitute the stripping section.

118
 Continuous Distillation with Reflux

The concentrations of the streams entering and

leaving the nth plate are:
vapour leaving plate
Liquid leaving plate
vapour entering plate
Liquid entering plate

The boiling point diagram for the mixture being

treated is shown. By definition of an ideal plate,
the vapour and liquid leaving plate n are in
equilibrium, so and represent equilibrium
concentrations. The vapour is enriched in more
volatile component A as it travels up the
column, and the liquid is depleted of A as it
flows downward.
Thus the concentration of A in both phases increases with the height of the column; is
greater than , and is greater than .

119
 Continuous Distillation with Reflux

The feed flows down the stripping section to the bottom of the column, in which a definite
level of liquid is maintained. Liquid flows by gravity to reboiler B. This is a steam-heated
vaporizer that generates vapour and returns it to the bottom of the column. The vapour passes
up the entire column.
At one end of the reboiler is a weir. The bottom
product is withdrawn from the pool of liquid on the
downstream side of the weir and flows through the
cooler G.

120
 Continuous Distillation with Reflux

The vapours rising through the rectifying section are completely condensed in condenser C,
and the condensate is collected in accumulator D, in which a definite liquid level is maintained.
Reflux pump F takes liquid from the accumulator and delivers it to the top plate of the tower.
This liquid stream is called the reflux.

It provides the downflowing liquid in the rectifying

section that is needed to act on the upflowing
vapour.
Without reflux, no rectification would occur in the
rectifying section, and the concentration of the
overhead product would be no greater than that of
the vapour rising from the feed plate.
Condensate not picked up by the reflux pump is
cooled in heat exchanger E, called the product
cooler, and withdrawn as the overhead product.

121
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
The material-balance diagram for a typical
continuous distillation plant is shown.

The column is fed with F mol/h of

concentration and delivers D mol/h of
overhead product of concentration and B
mol/h of bottom product of concentration .

Two independent overall material balances

can be written:
Total-material balance:

Component A balance

122
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Eliminating B from these equations gives:

Eliminating D gives:

Eliminating F gives:

These equations are true for all values of the flows of vapour and liquid within the column.

123
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
Quantity D is the difference between the flow rates of the streams entering and leaving the
top of the column. A material balance around the condenser and accumulator is given by:

The difference between the flow rates of vapour and liquid anywhere in the upper section of
the column is also equal to D, as shown by considering the part of the plant enclosed by
Control Surface I. This part includes the condenser and all plates above n+1.

A total material balance around this Control

Surface I gives:

Thus quantity D is the net flow rate of material

upward in the upper section of the column.
Regardless of changes in V and L, their
difference is constant and equal to D.

124
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
Similar material balances for component A give the equations:

Quantity is the net flow rate of component A upward in the upper section of the column. It,
too, is constant throughout this part of the equipment. A material balance for the most
volatile component over the envelope for the total condenser and stages 1 to n is as follows:

Solving for yn+1 gives the equation for the rectifying-section operating line:

This equation relates the most volatile component compositions yn+1 and xn of passing streams
and , respectively.

125
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
For the equation to be plotted as a straight line, , which is the locus of compositions of all
passing streams in the rectifying section, L and V must not vary from stage to stage in the
rectifying section. This is the case if:
1) The two components have equal and constant molar enthalpies of vapourization (latent
heats);
2) Component sensible-enthalpy changes (), and heat of mixing, are negligible compared to
latent heat changes;
3) The column is insulated, so heat loss is negligible;
4) Column pressure is uniform.
These are the McCabe-Thiele assumptions leading to the condition of constant molar
overflow in the rectifying section, where the molar flow rates remain constant as the liquid
overflows each weir from one stage to the next. Since a total material balance for the
rectifying-section envelope gives , if L is constant, then V is also constant for a fixed D. Hence,

126
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
In designing columns, the concept
of constant molar overflow is
often used, which means

𝐿and 𝑉may be dropped.

Thus, the slope of the operating line in the rectifying subscript n, n+1, m, and m+1on
section:
1) is a constant ,
2) with ,
3) and .

For constant molar overflow in either the rectifying or the stripping section, only material
balances and an equilibrium curve are required. Energy balances are needed only to
determine condenser and reboiler duties.
Liquid entering Stage 1 at the top is the external reflux rate, , and its ratio to the distillate
rate, , is the reflux ratio . Because of constant molar overflow, is a constant in the rectifying
section.

127
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
Since , the slope of the operating line is readily related to the reflux ratio:

Similarly

Combining with

This is the equation for the operating line of the rectifying section. The y intercept is set by ,
and , the reflux ratio, is an operating variable that can be controlled at will by adjusting the
split between reflux and overhead product, or by changing the amount of vapour formed in
the reboiler for a given flow rate of the overhead product.

128
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
If and are specified, then plots as a straight line, with an intersection at on the 45° line (y =
x); a slope of ; and an intersection at for x = 0.

𝑦 1= 𝑥 𝐷

𝑦1 𝑥 0= 𝑥 𝐷
1
𝑥1
𝑦2
2
𝑥2
3
𝐿 and 𝑉 refer to flows in the
upper part of the column.

129
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
The McCabe-Thiele construction for the top plate does depend on the action of the
condenser. The figure below shows material-balance diagrams for the top plate and the
condenser. The concentration of the vapour from the top plate is , and that for the reflux to
the top plate is . In accordance with the general properties of operating lines, the upper
terminus of the line is at the point ().

130
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
The simplest arrangement for obtaining reflux and liquid product, and one that is frequently
used, is the single total condenser, which condenses all the vapour from the column and
supplies both reflux and product. When such a single total condenser is used, concentrations
of the vapour from the top plate, of the reflux to the top plate, and of the overhead product
are equal and can all be denoted by . The operating terminus of the operating line becomes
point (), which is the intersection of the operating line with the diagonal. Triangle a, b, c
represents the top plate in the column.

131
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Upper Section and Condenser
When a partial condenser is used, the liquid reflux does not have the same composition as
the overhead product; that is, . Sometimes two condensers are used in series, first a partial
condenser to provide reflux, then a final condenser to provide liquid product. vapour leaving
the partial condenser has a composition, , which is the same as . The operating line passes
through the point () on the diagonal, but as far as the column is concerned, the operating line
ends at point a’, which of course has coordinates (). Triangle a’, b’, c’ represents the top plate
of the column. Since the vapour leaving a partial condenser is normally in equilibrium with
the liquid condensate, the vapour composition, is the ordinate value of the equilibrium curve
where the abscissa is . The partial condenser, represented by the dotted triangle a, b, a’, is
therefore equivalent to an additional theoretical stage in the distillation column.

132
 Continuous Distillation with Reflux
Feed-Stage consideration – the q-line
Consider the five feed conditions, where the feed has been flashed adiabatically to the feed-
stage pressure. If the feed is a bubble-point liquid, it adds to the reflux, , from the stage
above, to give . If the feed is a dew-point vapour, it adds to the boilup, , coming from the
stage below to give . For partially vaporized feed, , , and . If the feed is a superheated
vapour, it will cause a portion of the reflux, , to vaporize, giving and . If the feed is subcooled
liquid, it will cause some of the boilup, , to condense, giving and .

a) subcooled-liquid feed
b) bubble-point liquid feed
c) partially vaporized feed
d) dew-point vapour feed
e) superheated-vapour feed

133
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Lower Section and Reboiler
In the lower section of the column, the net flow rates are also constant but are in a downward
direction. The net flow rate of total material equals ; that of component A is . The following
equations apply:

Subscript m is used in place of n to designate a general plate in the stripping section.

Solving for , which is the equation for the
operating line in the stripping section:

and are in equilibrium.

134
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Lower Section and Reboiler

where and are total molar flows.

The slope of this operating line for the compositions of passing streams in the stripping
section is . Because ; .

vapour leaving the partial reboiler is assumed to be in equilibrium with the liquid bottom
product, B, making the partial reboiler an equilibrium stage. The vapour rate leaving it is
the boil-up, (), and its ratio to the bottoms product rate, , is the boil-up rate. With the
constant-molar-overflow assumption, is constant in the stripping section.

Eliminating gives:

135
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Lower Section and Reboiler

Since

Similarly

Combining with

136
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Lower Section and Reboiler
If values and are known, can be plotted as a straight line with an intersection at on the 45°
line and a slope of .

and refer to flows in

the lower part of the
column.

137
 Continuous Distillation with Reflux –
Material Balances in Plate Columns
Lower Section and Reboiler
If x is set equal to , y is also equal to , so the operating line for the stripping section crosses the
diagonal at point (). The lower operating line could then be constructed using the point () and
the slope . In the common type of reboiler, the vapour leaving the reboiler is in equilibrium
with the liquid leaving as bottom product. Then and are coordinates of a point on the
equilibrium curve, and the reboiler acts as an ideal plate. The figure shows the graphical
construction for the reboiler (triangle c, d, e) and the bottom plate (triangle a, b, c). Such a
reboiler is called a partial reboiler.

𝑚 −1 𝑥𝑚− 1
𝑦𝑚
𝑚 𝑥𝑚
𝑦𝑚
𝑦𝑏

𝑦𝑏

𝑥𝑚 = 𝑥 𝑏 𝑥𝑚− 1
138
 Continuous Distillation with Reflux – Condition of Feed
At the plate where the feed is admitted, the liquid rate or the vapour rate or both may
change, depending on the thermal condition of the feed.
Feed-Stage consideration – the q-line
Consider the five feed conditions, where the feed has been flashed adiabatically to the feed-
stage pressure. If the feed is a bubble-point liquid, it adds to the reflux, , from the stage
above, to give . If the feed is a dew-point vapour, it adds to the boil-up, , coming from the
stage below to give . For partially vaporized feed, , , and . If the feed is a superheated
vapour, it will cause a portion of the reflux, , to vaporize, giving and . If the feed is subcooled
liquid, it will cause some of the boil-up, , to condense, giving and .

a) subcooled-liquid feed
b) bubble-point liquid feed
c) partially vapourized feed
d) dew-point vapour feed
e) superheated-vapourfeed
139
 Continuous Distillation with Reflux – Condition of Feed

Feed –Stage considerations – the q-Line:

All five of the feed types can be characterized by , which is the

ratio of the increase in molar reflux rate (liquid flow) across
the feed stage to the molar feed rate,

𝐿− 𝐿
𝑞=
𝐹

Also, from the material balance around the feed stage,

(Material entering = Material leaving)

So, can be also written as

140
 Continuous Distillation with Reflux – Condition of Feed

Feed –Stage considerations – the q-Line:

Values of for the five feed conditions:

𝐿− 𝐿
𝑞=
𝐹

141
 Continuous Distillation with Reflux –Condition of Feed

Feed –Stage considerations – the q-Line:

is also defined as the ratio of heat to vaporise one mole of
feed to the molar latent heat of the feed.

• For a subcooled liquid feed (>1),

• For a superheated vapour feed (<0),

where
and are molar heat capacities,
is the molar enthalpy change from the bubble point to the dew point (enthalpy
of vaporization),
, , and are, respectively, feed, dew-point, and bubble-point temperatures at
column operating pressure.

142
 Continuous Distillation with Reflux – Feed line

Feed –Stage considerations – the q-Line:

Most columns operate with the feed as liquid at or near its boiling point. The feed is often
preheated by heat exchange with the bottoms product or other hot liquids, or by the use of
steam.
The value of , e.g. those obtained from or , can be used with the material balances to find the
locus for all points of intersection of the operating lines. The equation for this line of
intersections can be found as follows.

The contribution of the feed stream to the internal flow of liquid is , so the total flow rate of
reflux in the stripping section is
and
Likewise, the contribution of the feed stream to the internal flow of vapour is , and so the
total flow rate of vapour in the rectifying section is
and

143
 Continuous Distillation with Reflux – Feed line

Feed –Stage considerations – the q-Line:

For constant molar overflow, the material-balance equations for two sections are

To locate the point where the operating lines intersect, let and and subtract from .

However, overall,

So

144
 Continuous Distillation with Reflux – Feed line

Feed –Stage considerations – the q-Line:

And substituting and ,

then

𝑞 𝑥𝐹
𝑦= 𝑥−
𝑞 −1 𝑞−1

This equation is called the feed line (or q-line) equation, on which all intersections of the
operating lines must fall.
The position of the line depends only on and .
The slope of the feed line is The feed line crosses (, ).

145
 Continuous Distillation with Reflux – Feed line
𝑞 𝑥𝐹
Feed –Stage considerations – the q-Line: 𝑦= 𝑥−
𝑞 −1 𝑞−1

𝑥𝐹
𝑦 =−(1− 𝑓
𝑓 ) 𝑥+
𝑓

146
 Continuous Distillation with Reflux

Construction of operating lines

The simplest method of plotting the operating lines is to:
1) Locate the feed line;
2) Calculate the y-axis intercept and plot that line through the intercept and the point ();
3) Draw the stripping line through point () and the intersection of the rectifying line with the
feed line.

147
 Continuous Distillation with Reflux – Feed plate location

After the operating lines have been plotted, the number of ideal plates is found by the usual
step-by-step construction. The construction can start either at the bottom of the stripping line
or at the top of the rectifying line.
In the following it is assumed that the construction begins at the top and that a total
condenser is used.
As the intersection of the operating lines is
approached, it must be decided when the steps
should transfer from the rectifying line to the
stripping line. The change should be made in such a
manner that the maximum enrichment per plate is
obtained, so that the number of plates is as small as
possible. The figure shows that this criterion is met if
the transfer is made immediately after a value of x is
reached that is less than the x coordinate of the
intersection of the two operating lines. The feed
plate is always represented by the triangle that has
one corner on the rectifying line and one corner on
the stripping line. At the optimum position, the
triangle representing the feed plate straddles the
intersection of the operating lines.
148
 Continuous Distillation with Reflux – Feed plate location

The transfer from one operating line to the other, and hence the feed plate location, can be
made at any location between points a and b; but if the feed plate is placed anywhere but at
the optimum point, an unnecessarily large number of plates are required.

For example, if the feed plate is number 7, the

smaller steps shown by the dashed lines make
the number of ideal plates needed about 8
plus a reboiler, instead of 7 plus a reboiler
when the feed is on plate number 5. Note that
the liquid on the feed plate does not have the
same composition as the feed except by
coincidence, even when the feed plate location
is optimum.

149
 Continuous Distillation with Reflux – Feed plate location

Normally the staircase is stepped off from the top and continued to the bottom, starting from
the point (y = xD, x = xD) on the 45° line as shown in the figure for a partially vaporized feed.
Point P is the intersection of the q-line with the two operating lines. The feed-stage location is
the transfer for stepping off stages between the rectifying-section operating line and the
equilibrium curve to stepping off stages between the stripping-section operating line and the
equilibrium curve. The smallest (optimal) number of total equilibrium stages occurs when the
transfer is made at the first opportunity after a horizontal line of the staircase passes over
point P, as in the figure where the feed stage is 3 from the top and the total number of stages
is exactly 5 (that is 4 plus a partial reboiler).

150
 Continuous Distillation with Reflux – Feed plate location

If the transfer is delayed and the feed stage is stage 5, the total number of stages is 6.4
(rounded up to 7). If the transfer is made early, at feed stage 2, resulting again in more stages
than the optimal number of 5.

151
Continuous Distillation with Reflux - Summary

152
 Continuous Distillation with Reflux

Total Reflux
In total reflux all overhead vapour is returned to the column as reflux, and all underflow liquid
is returned as boil-up; thus distillate and bottoms flow rates are zero. At steady state the feed
rate must also be zero. Total reflux is used for starting up columns, for keeping a column
operating when another part of the plant is shut down, and for testing column efficiency.

The analysis of total reflux is simple. Since all vapour is condensed and refluxed, . Also, . Thus
both operating lines become y = x line. Total reflux represents the maximum separation that
can be obtained with a given number of stages but zero throughput. Total reflux also gives
the minimum number of stages required for a given separation.

Neither the feed composition, , nor the q-line influences the staircase construction. When , ,
and the total condensed overhead is returned as reflux. Also, all liquid leaving the bottom
stage is vaporized in the reboiler and returned as boil-up.

153
 Continuous Distillation with Reflux

Total Reflux

154
 Continuous Distillation with Reflux

Minimum Reflux
At any reflux less than total, the number of plates needed for a given separation is larger than
at total reflux and increases continuously as the reflux ratio is decreased. As the ratio becomes
smaller, the number of plates becomes very large, and at a definite minimum, called the
minimum reflux ratio, the number of plates becomes infinite. All actual columns producing a
finite amount of desired top and bottom products must operate at a reflux ratio between the
minimum at which the number of plates is infinity, and infinity, at which the number of plates
is a minimum.

Minimum Reflux:
is defined as the external reflux ratio at which the desired separation could just be obtained
with an infinite number of stages. To have an infinite number of stages, the operating and
equilibrium lines must touch. The point where the operating line touches the equilibrium
curve is called the pinch point.

155
 Continuous Distillation with Reflux

Minimum Reflux

156
 Continuous Distillation with Reflux

Minimum Reflux
For binary systems the minimum reflux ratio is easily determined. The top operating line is
drawn to a pinch point. Then is equal to the slope of this operating line:

where ( and ) are the coordinates of the intersection of the feed line and the equilibrium
curve. Once is known

Note that the minimum reflux ratio depends on , , and can depend on .

More will be discussed later.

157
 Worked example 8

A distillation column operating at 1 atm is to be designed for separating an ethanol-water

mixture. The feed is 20 mole% ethanol and the feed flow rate is 1000 kmole/hr of saturated
liquid. A distillate composition of 80 mole% ethanol and a bottoms composition of not more
than 2 mole% ethanol are desired. The reflux ratio is 5/3

Determine:
1)Total number of equilibrium stages
2)Optimum feed plate location
3)Distillate and bottoms flow rates

 Analyse the graphical solution. What can you

conclude about the extent of separation in the
rectifying section and stripping section,
respectively?
 Obtain the mole fractions in liquid and vapour
each tray and plot a concentration profile for your
design (vertical-axis: number of trays, top -down,
horizontal-axis: mole fractions x and y).

158
159
160
 Worked example 9

A distillation column operating at 1 atm is to be designed for separating a binary mixture of A

and B. The feed is 50 mole% A and the feed flow rate is 200 mol/hr of saturated liquid. A
distillate composition of 95 mole% A and a bottoms composition of not more than 20 mole%
A are desired. The reflux ratio is 4.

Determine the total number of equilibrium stages required to provide this separation.

Equilibrium data for the

mixture at 1 atm pressure are
given in the table.

161
162
Worked example 9 EXTRA

Other scenarios:

9a) Set R = 0.75

9b) Set R = 0.75 and q = 1.75
9c) Set R = 0.75 and q = 0.75
9d) Set R = ∞ and q = 0.75
9e) Set R = Rmin and q = 1
9f) Set R = 0.75 and q = 1 : change feed location (non-optimum)

163
164
 Continuous Distillation with Reflux

Binary stage-by-stage method – Lewis-Sorel method

allow for variations in the 𝐿/𝑉 ratio with tray number by tray-to-tray enthalpy balances at the
This establishes the first estimate of the number of trays required. Although it is possible to

same time, since the products are not yet firmly established, it is best to omit this refinement.

If a unit is operating as shown, so that a

binary feed F is distilled to give a top
product D and a bottom product B, with ,
and as the corresponding mole fractions
of the more volatile component, and the
vapour () rising from the top plate is
condensed, and part is run back as liquid
at its boiling point to the column as
reflux, the remainder being withdrawn as
product, then a material balance above
plate n, indicated by the Loop I gives:

165
 Continuous Distillation with Reflux

Binary stage-by-stage method – Lewis-Sorel method

Expressing this balance for the more volatile component gives:

Thus:

This equation relates the composition of the vapour rising to the plate to the composition of
the liquid on any plate above the feed plate. Since the molar liquid overflow is constant, may
be replaced by and:

166
 Continuous Distillation with Reflux

Binary stage-by-stage method – Lewis-Sorel method

Similarly, taking a material balance for the total streams and for the more volatile component
from the bottom to above plate m, as indicated by the Loop II, and noting that gives:

and

Thus:

This equation gives the corresponding relation between the compositions of the vapour rising
to a plate and the liquid on the plate, for the section below the feed plate. These two
equations are the operating lines.

167
 Worked example 10

A mixture of benzene and toluene containing 40 mole% benzene is to be separated to give a

product containing 90 mole% benzene at the top, and a bottom product containing not more
than 10 mole% benzene. The feed enters the column at its boiling point, and the vapour
leaving the column which is condensed but not cooled, provides reflux and product. It is
proposed to operate the unit with a reflux ratio of 3 kmol/kmol product. It is required to find
the number of theoretical plates needed and the position entry for the feed. The equilibrium
diagram at 100 kN/m2 is shown.

168
169
Worked example 10

170
 Continuous Distillation with Reflux

Efficiencies
To compare the performance of an actual stage to an equilibrium stage, we use a measure of
efficiency. The overall efficiency, , is defined as the number of equilibrium stages required for
the separation divided by the actual number of stages required:

Partial condensers and partial reboilers are not included in the equilibrium number of stages
since they will not have the same efficiency as the stages in the column.

The variables that would affect column efficiency include the hydrodynamic flow properties,
such as viscosity and gas flow rate; the mass transfer rate, which is affected by the diffusivity.
Overall efficiency is usually smaller as the separation becomes easier ( increases).

171
172
Self study questions 9-12

173