CHEMICAL ENGINEEERING AND CHEMICAL PROCESS TECHNOLOGY – Vol. II - Distillation or Rectification - J. G.

Stichlmair

DISTILLATION OR RECTIFICATION

J. G. Stichlmair
Department of Chemical Engineering, Technische Universität München, Germany

Keywords: Separation technology, separating fluid mixtures, vapor liquid equilibrium,

azeotrope, tray columns, packed columns, batch distillation, reactive distillation,
azeotropic distillation, extractive distillation, sea water desalination, air separation,
crude oil refinery, production of absolute alcohol.

Contents

1. Introduction

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2. Fundamentals

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2.1. Vapor Liquid Equilibrium
2.1.1. Binary Mixtures

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2.1.2. Ternary Mixtures
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2.1.3. Multicomponent Mixtures
2.2. Continuous Distillation Processes
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2.2.1. Binary Mixtures
2.2.2. Ternary Mixtures
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2.2.3. Multicomponent Mixtures

2.3. Batch Distillation
2.4. Reactive Distillation
3. Equipment
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3.1. Tray Columns

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3.2. Packed Columns

4. Separation Processes
4.1. Processes for Separating Zeotropic Mixtures
4.2. Processes for Separating Azeotropic Mixtures
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Glossary
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Bibliography
Biographical Sketch

Summary

Distillation (or rectification) is the most important technique for separating fluid
mixtures into pure substances. Distillation is extensively used in chemical,
petrochemical, pharmaceutical and food industries. This article presents a concise
description of the state of the art and of novel developments. The first section deals with
the basic principles of distillation processes, for instance, vapor liquid equilibrium and
separation mechanisms in countercurrent columns. In the focus are binary as well as
multicomponent systems. The second section deals with the equipment of industrial
distillation. The design principles of tray columns and packed columns are explained,
and typical operational data are given, for instance, capacity, pressure drop and
separation efficiency. The last section deals with the conceptual design of complete

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CHEMICAL ENGINEEERING AND CHEMICAL PROCESS TECHNOLOGY – Vol. II - Distillation or Rectification - J. G.
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separation processes such as: batch distillation, reactive distillation, azeotropic

distillation, and extractive distillation. Some examples of important industrial
distillation processes are also presented, i.e. sea water desalination, air separation, crude
oil refinery and production of absolute alcohol.

1. Introduction

Distillation, in Europe often called rectification, is by far the most important technique
for separating fluid mixtures in the process industries, and consensus is that it will
remain so for years to come. Approximately 95 % of all liquid separations are carried
out by distillation processes. This exceptional role played by distillation is founded on
the fact that distillation is the only separation technique that is capable to fractionate a
fluid mixture into its pure constituents. The disadvantages of distillation are a risk of

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thermal degradation of the species and a high energy demand.

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Distillation uses a very simple principle that consists of three steps. Firstly, generation

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of a two phase system, secondly, mass transfer across the interface and thirdly,

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separation of the two phases. This principle is very effective and, therefore, it is also
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applied to other separation processes. However, in most alternative separation
processes, e.g. absorption, adsorption, and extraction, the two phase system is created
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by the addition of an external substance (entrainer or solvent) that has to be removed
later on in an additional separation process. In distillation however, the two phase
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system (vapor-liquid) is generated by a supply of heat which can easily be removed later
on.

Distillation (lat. destillare = dripping down) is a very old technique dating back to the
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first century A.D. Today, distillation is highly developed in all respects, i.e.
fundamentals (thermodynamics, vapor liquid equilibrium), process design as well as
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equipment (packed columns, tray columns). Distillation columns up to 10 m in diameter

and 100 m in height can be safely designed, constructed and operated. They dominate
the image of many industrial sites, e.g. chemical plants or oil refineries, see Figure 1.
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Figure 1: Chemical plant with distillation columns.
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2. Fundamentals

The basic principle of distillation is to bring a liquid into intimate contact with a vapor
so that mass transfer between the two coexistent phases takes place. The driving force
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for the interfacial mass transfer is the endeavor of each system to reach a state of
equilibrium. Therefore, a good knowledge of vapor liquid equilibrium is of essential
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importance for the design of distillation processes. In distillation, the concentrations of

the vapor ( y ) and the liquid ( x ) must be different.
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In a distillation unit, the liquid is at the boiling point and the vapor at the dew point. A
liquid mixture is at its boiling point if the sum of the partial pressures of all components
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is equal to the total pressure of the system. According to this condition, a liquid mixture
approaches the boiling point either by rising the temperature or by decreasing the
pressure. Analogously, a vapor mixture reaches the dew point either by decreasing the
temperature or by increasing the pressure. The region between the boiling and the dew
points is used in distillation processes.

2.1. Vapor Liquid Equilibrium

At equilibrium, the two coexistent phases have the same temperature T , the same total
pressure p , and the same partial pressures pi of all components i . The partial pressure
in the vapor phase is determined by Dalton’s law:

pi = yi ⋅ p (1)

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The partial pressure in the liquid phase is described by Raoult’s law, and under
supercritical temperatures by Henry’s law:

Raoult pi = γ i ⋅ xi ⋅ pi0 or Henry pi = γ i ⋅ xi ⋅ H i , j (2)

In these equations, γ i denotes the activity coefficient of component i , which is unity for
ideal mixtures. For non-ideal mixtures, it can be either larger or smaller than unity. The
values of the activity coefficients depend on all components in the mixture at hand.
According to the present state of the art, the values of the activity coefficients are
calculated from the free excess enthalpy g E . The free excess enthalpy is a
thermodynamic quantity which describes the non-ideal behavior of a liquid mixture.
There are several well known g E functions e.g. van Laar, Margules, Wilson, NRTL,

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UNIQUAC etc. The parameters in these empirical equations are determined from

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experimental equilibrium data. Thus, the excess enthalpy only provides a

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thermodynamically consistent interpolation of the phase equilibrium. A more rigorous

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method is based on equations of state (e.g. Van-der-Waals, Soave-Redlich-Kwong,
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Peng-Robinson, Virial equation etc.). However, the use of these equations of state is
presently restricted to special applications, for instance, to the processing of natural gas.
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2.1.1. Binary Mixtures
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The vapor liquid equilibrium of binary mixtures is shown in Figure 2 for the cases A:
ideal mixtures, B: mixtures with total mixing gap in the liquid, and C: mixtures with an
irreversible instantaneous reaction in the liquid.
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Figure 2: Vapor liquid equilibrium of three binary mixtures. A: ideal system, B: system
with a mixing gap in the liquid phase, C: system with irreversible chemical reaction in
the liquid phase.

The partial pressures pi and the total pressure p versus the molar concentration x of
the liquid phase at constant temperature are plotted in the upper row. Ideal mixtures
show a linear dependence of the pressures on liquid concentration. System B, with a
total mixing gap, exhibits an increase of total pressure p . System C, with chemical

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CHEMICAL ENGINEEERING AND CHEMICAL PROCESS TECHNOLOGY – Vol. II - Distillation or Rectification - J. G.
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reaction, is characterized by a decrease of the total pressure p .

The second row shows the boiling and dew point temperatures versus the concentration
at constant pressure. In ideal systems, both temperatures monotonously decrease with
rising concentrations x of the low boiler a. System B shows a boiling and a dew point
minimum which is caused by the rise of the total pressure of the mixture. Analogously,
system C shows a maximum of the boiling and dew point temperatures.

In the third row of Figure 2, the concentration y* of the vapor is plotted versus the
concentration x of the liquid at constant pressure. For ideal systems, the following
equation holds:

α ⋅x

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y* = (3)
1 + (α − 1) ⋅ x

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Here, α denotes the relative volatility, defined as: α ≡ pa0 / pb0 .

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In the two non-ideal mixtures (systems B and C) the equilibrium curves intersect the
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diagonal of the diagram. At the point of intersection, vapor and liquid have the same
concentration ( y* = x ). This point is of great importance for distillation. It is called
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azeotrope.

The fourth row of Figure 2 shows the dependence of the activity coefficients on the
liquid concentration x . System B is characterized by strong intermolecular repulsion
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forces; hence both activity coefficients γ a and γ b are larger than unity. In system C
with a chemical reaction (i.e. intermolecular attraction forces), both activity coefficients
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are smaller than unity. The smaller the concentration of a component i, the bigger
(system B) or smaller (system C) is its activity coefficient γ i .
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Figure 2 shows the three extreme cases of vapor liquid equilibrium. The behavior of real
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systems, shown in Figure 3, lies in between. The system benzene/toluene is nearly ideal.
Here, the intermolecular forces are the same for all molecules. In the systems at the left
hand side of Figure 3, the intermolecular forces are increasingly repulsive. In those
shown at the right hand side, the intermolecular forces are increasingly attractive.

Azeotropes

The existence of azeotropes is of primary importance for distillation because at this

point, the vapor and the liquid phases have the same concentration, i.e. yi* = xi . A
maximum azeotrope is characterized by a boiling point maximum, and a minimum
azeotrope by a boiling point minimum. In multicomponent mixtures, saddle point
azeotropes with an intermediate boiling point can exist. At the azeotrope, the mixture
behaves like a pure substance. Azeotropes are a barrier to distillation; therefore, the
knowledge of azeotropic concentrations is essential for the design of distillation
processes. However, alternative separation processes, e.g. absorption, adsorption,

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CHEMICAL ENGINEEERING AND CHEMICAL PROCESS TECHNOLOGY – Vol. II - Distillation or Rectification - J. G.
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extraction etc., can overcome azeotropes.

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Figure 3: Vapor liquid equilibrium of some real mixtures.

2.1.2. Ternary Mixtures

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In ternary systems, the vapor liquid equilibrium is also calculated from Dalton’s and
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Raoult’s laws. With the definitions α ac ≡ pa0 / pc0 and α bc ≡ pb0 / pc0 , equation (3) can be
written for ideal systems:
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α ac ⋅ xa α bc ⋅ xb
ya* = and yb* = (4)
1 + (α ac − 1) ⋅ xa + (α bc − 1) ⋅ xb 1 + (α ac − 1) ⋅ xa + (α bc − 1) ⋅ xb
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For non-ideal systems, the values of the activity coefficients have to be calculated from
g E functions. The ternary coefficients can be determined from experimental data of all
binary systems in the mixture.

In ternary mixtures, the vapor liquid equilibrium is graphically represented by

distillation lines in a triangular diagram. Distillations lines are given by a sequence of
equilibrium stages calculated via the following recursion formula:

x0 → y0* = x1 → y1* = x2 → y2* = x3 → y3* = ... (5)

Starting from a liquid concentration x0 , the equilibrium concentration y0* of the

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coexistent vapor is determined. This vapor is totally condensed, resulting in a liquid

with the same concentration, x1 = y0* , etc. A sequence of such equilibrium stages
constitutes a distillation line. Distillation lines follow the course of a ball rolling down
the boiling point surface shown in Figure 4. Thus, distillation lines always start at a
local temperature maximum and end at a local temperature minimum. In azeotropic
mixtures, there may exist several start and end points of distillation lines. The regions
with different start or end points are separated from each other by boundary distillation
lines that always run between local temperature extremes of the same type (either
maxima or minima). Boundary distillation lines are barriers to ternary distillation,
similar to azeotropes in binary mixtures.

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Figure 4: Boiling point surface and distillation lines of the system octane/2-ethoxy-
ethanol/ethylbenzene. o azeotropes.
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Bibliography
Doherty, M.F.; Malone, M.F.(2001): Conceptual Design of Distillation Systems, McGraw-Hill, New
York. [A modern description of distillation thermodynamics and of conceptual design of distillation
processes including reactive distillation].

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Gmehling, J.; Menke, J.: Krafczyk, J.; Fischer, K.(1994): Azeotropic Data I and II, VCH
Verlagsgesellschaft, Weinheim [This represents an extensive two-volume compilation of azeotropic data
of more than 18 000 systems].
Gmehling, J.; Onken, U.(1977): Vapor-Liquid Equilibrium Data Collection, Chemistry Data Series, Vol. I
ff, Dechema, Frankfurt. [This represents the most extensive (more than 20 volumes) collection of vapor-
liquid equilibria of binary and higher systems].
Kister, H.Z.(1989): Distillation Operation, McGraw-Hill, New York, Distillation Design, McGraw-Hill,
New York 1992. [These two books focus on the practical problems of industrial distillation].
Perry, R.H.; Green, D.W.; Maloney, J.D.: Perry’s Chemical Engineers’ Handbook, McGraw-Hill, New
York 1997. [A standard work on chemical engineering with some chapters on distillation].
Seider, W.D.; Seader, J.D.; Lewin, D.R.(1999): Process Design Principles, John Wiley&Sons, Inc., New
York. [Description of strategies for the design of chemical processes. The book contains several sections
on distillation].
Smith, R.: Chemical Process Design, McGraw-Hill, New York 1995

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Stichlmair, J.G.; Fair, J.R.: Distillation - Principles and Practice, Wiley-VCH, New York 1998. [This
presents an up-to-date description of thermodynamics, equipment, industrial applications, and control of

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distillation processes].

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Biographical Sketch
Johann G. Stichlmair is Professor of Chemical Engineering at the Technical University of Munich,
Germany. A graduate of the Technical University of Munich, he holds a master’s (Dipl.-Ing.) and a
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doctoral (Dr.-Ing.) degree of the same university. He worked several years in industry (Linde, QVF)
before he became a full professor at the University of Essen (1980) and Munich (1993). Besides winning
several professional awards (Arnold Eucken Award, Kirschbaum Medal), he served nine years as
chairman of the German Working Party on Absorption, Distillation and Extraction. From 1995 to 1998 he
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was vice president of the German Society of Chemical Engineers. He is author of more than 130 papers in
scientific journals and of four books.
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