B40EA Unit Operations A

Advanced Distillation
Topic 1 – Binary Distillation Review
Semester 1 2018-19

1 © Heriot-Watt University 2018 B40EA Units Operations A: Advanced Distillation

Binary Distillation Review
 Material for this topic was covered in B49CA Separations
A and B49CE Multiphase Thermodynamics.

 In this review, the focus will be on the nomenclature and

terms used.

 More specifically, we’ll look at:

 Should we be distilling this mixture?
 Flash stages – using K values
 McCabe-Thiele method
 Feed stage considerations
 Analysing binary columns – Rmin, Nmin

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Distillable Mixtures
 Distillation is often the first operation proposed to separate
mixtures.
THIS IS WRONG!!!
 Before we select a separation method, we need to fully
understand:
 Basic chemistry of the mixture components
 Thermodynamics
 Costs (capital and operating)
 And then evaluate the different methods available to us.

 Selecting distillation when another method is more suitable is

a common problem in design projects and will be penalised.
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Distillable Mixtures
Mixture Type Can/Cannot? Should?
1 Alkanes C1 to C5
2 Benzene,Toluene, Xylene
3 Ethanol,Water
4 Salts (NaCl, KCl) and water
5 Limonene, water
6 Styrene monomer and butane
7 Sulphuric Acid and water
8 Acetic acid and water
9 95% Acetic Acid and water
10 25% Acetic Acid and water

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Distillable Mixtures
 However:
 Even though some mixtures are difficult to separate
by distillation, we often have no other choice.
 Some mixtures that can be distilled may contain
that much of one of the other components that
distillation would be not be economic.
 Some easy distillations require high pressures or
very low temperatures that increase the cost of the
utilities needed.

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Thermodynamics Review
Vapour-Liquid Equilibrium
 In dealing the equilibrium situations, we need
to find out the relation between composition
in the vapour and liquid phases.
 Under ideal conditions, we can assume the two
phase system obeys Raoult’s Law:

∗ ∗
𝑃𝑖 = 𝑃𝑖 𝑥𝑖  𝑃𝑇 𝑦𝑖 = 𝑃𝑖 𝑥𝑖

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Thermodynamics Review
Vapour-Liquid Equilibrium
 Using vapour-pressure data, a T-x-y diagram then a x-y
diagram can be constructed using Antoine’s Equation:

𝐵𝑖
= 𝐴𝑖 − 𝑙𝑛𝑃𝑖∗
𝑇 + 𝐶𝑖
 And the mole fraction of one component in a binary
mixture in a saturated liquid can be found from the
vapour pressure:

𝑃𝑇 − 𝑃𝐵
𝑥𝐴 =
𝑃𝐴 − 𝑃𝐵

© Heriot-Watt University 2018 B40EA Units Operations A: Advanced Distillation 7

Thermodynamics Review
De Preister Charts and K-Values
 The composition of a liquid and vapour at equilibrium
is normally expressed in terms of an equilibrium
constant, Ki
 For simple, binary distillation and as a first pass
assumption for multicomponent distillation, we
assume that system is ideal and hence the activity
constant, gi, is equal to 1.

𝑃𝐴 𝑃𝐴
𝑦𝐴 = 𝑥𝐴 = 𝑥𝐴 𝛾𝐴 = 𝐾𝐴 𝑥𝐴
𝑃𝑇 𝑃𝑇

© Heriot-Watt University 2018 B40EA Units Operations A: Advanced Distillation 8

Thermodynamics Review
De Preister Charts and K-Values
 For a given system within
the component,
temperature and
pressure range of the
chart, equilibrium
constants, Ki, can be read
from a De Preister Chart

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Thermodynamics Review
K-Values from Correlations
 De Preister Charts are limited by the range of components,
temperatures and pressure available.
 A number of correlations are available that calculate Ki over a
wider, and more useful range.
 One of the more commonly used correlations and which can
easily be used in spreadsheets or computer programs is the
Wilson Correlation:

𝑃𝑐𝑖 𝑇𝑐𝑖
𝐾𝑖 = exp 5.37 1 + 𝜔𝑖 1−
𝑃 𝑇
where
 Pci = critical pressure of component i
 Tci = critical temperature of component i
 wi = acentric factor of component i

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Binary Distillation Review
Stage Nomenclature
 The molar balance around a stage is:

𝑉𝑛 𝑦𝑛 + 𝐿𝑛 𝑥𝑛 = 𝑉𝑛+1 𝑦𝑛+1 + 𝐿𝑛−1 𝑥𝑛−1

n-1
Vn Ln-1
𝑉𝑛 𝐾𝑥𝑛 + 𝐿𝑛 𝑥𝑛 = 𝑉𝑛+1 𝑦𝑛+1 + 𝐿𝑛−1 𝑥𝑛−1
yn xn-1
n 𝑉𝑛+1 𝑦𝑛+1 + 𝐿𝑛−1 𝑥𝑛−1 = 𝐾𝑉𝑛 + 𝐿𝑛 𝑥𝑛

Ln 𝐾𝑉𝑛 + 𝐿𝑛 𝐿𝑛−1
Vn+1
𝑦𝑛+1 = 𝑥𝑛 − 𝑥𝑛−1
xn 𝑉𝑛+1 𝑉𝑛+1
yn+1 n+1

which is the equation of a straight line and

can be solved in a step-by-step manner.
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Binary Distillation Review
Column Configuration

Pressure Temperature
Increasing Increasing
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Binary Distillation Review
McCabe-Thiele Method
 The McCabe-Thiele Method is one of the most
widely used graphical methods for binary distillation
calculations.
 The main assumptions for use of the method are:
 Column has a total condenser and partial reboiler.
 Only two components.
 System is ideal, or close to ideal.
 Constant Molal Overflow

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Binary Distillation Review
McCabe-Thiele Method – Constant Molal Overflow
 For Constant Molal Overflow, we assume that:
 The two components have equal and constant enthalpies of
vaporisation.
 The heat capacity changes are negligible compared to the heat
of vaporisation.
 The column is well insulated so heat loss is negligible.
 The pressure in the column is uniform.

 For this condition, it is assumed that the amount of

vapour transferred to the liquid stream in each stage is
equal to the amount of liquid transferred to the vapour
stream.
 Therefore the liquid and vapour stream flow rates are
constant in the entire section.

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 Binary Distillation Review
McCabe-Thiele Method – Construction Lines

q-Line
𝑞 1 Rectifying Section
𝑦= 𝑥− 𝑥
𝑞−1 𝑞−1 𝐹 𝐿 𝑅
Slope = = <1
𝑉 𝑅+1
𝐿 𝐷
𝑦 = 𝑥 + 𝑥𝐷
𝑉 𝑉

Stripping Section
𝐿′ 𝑉𝐵 + 1
Slope = ′ = >1
𝑉 𝑉𝐵
𝐿′ 𝐵
𝑦 = ′ 𝑥 − ′ 𝑥𝐵
𝑉 𝑉

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Binary Distillation Review
McCabe-Thiele Method – Minimum Reflux
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 If the reflux rate is reduced, the slope
of the rectifying operating line
decreases, with the intercept on the
y-axis increasing.
 This goes on until the two operating
lines join where the q-line joins the
equilibrium line.
 At this point, the number of stages in
both sections reach infinity and the
reflux ratio is at its minimum, Rmin
 By returning no exiting vapour as
reflux and no exiting liquid as boilup,
the operating line intersection is as
far to the left as equilibrium allows.
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Binary Distillation Review
McCabe-Thiele Method – Minimum Number of Stages
 The minimum number of stages, Nmin,
for any separation occurs when total
reflux occurs.
 By returning all the exiting vapour as
reflux (i.e. there is no distillate) and
all the exiting liquid as boilup, the
operating lines have slope of one.
 As no product is produced, the feed
must therefore also be zero.
 Although not a practical operating
condition, columns are often operate
at total reflux at start-up until steady
state conditions are reached.

© Heriot-Watt University 2018 B40EA Units Operations A: Advanced Distillation 17