COLLEGE OF ENGINEERING

Department of Mechanical and Industrial

Engineering

UNIT OPERATIONS- II (EME10318)

SPRING SEMESTER (2022-23)

CHAPTER 1: DISTILLATION
(Part 4)
 What’s Inside?
1 Introduction to multi-component distillation

2 Introduction to azeotropic distillation

3 Extractive Distillation

4 Numerical Problem Solving

Spring Semester (2022-23) EME10318 Unit Operations – II (BEng Chemical Engineering)

 Multi-component Distillation
⮚ Multicomponent (3 or more components) distillation is a chemical
process in which a mixture of volatile compounds separates based on
their boiling points.
⮚ The process occurs in a distillation column, a vertical stacking of trays or
stages upon which components in their liquid and vapor phases coexist.
⮚ For many systems, particularly those consisting of chemically similar
substances, the relative volatilities of the components remain constant
over a wide range of temperature and composition
⮚ With a ternary system (4 components system) the conditions of
equilibrium are more complex
⮚ the mole fraction yA in the vapour depends not only on xA in the liquid,
but also on the relative proportions of the other two components.
 Muticomponent distillation
➢In a distillation column with a single feed, single distillate, and single
bottoms, a multicomponent mixture is split into two fractions
➢Lighter (more volatile) components go to the top of the column
➢Heavier (less volatile) constituents go to the bottom of the column
Example: for refining
Propane (C3) - Light Key
gasoline
Butane (C4)- Heavy Key
➢Very volatile components
like propane, etc. are to be
removed as distillate
➢Heavier constituents like
butane and above are to
be retained in the bottoms
 Terms defined
Key components - those components that are being separated; appear in both the top and
bottom of a column ; distillate and bottoms fractional recoveries usually specified
(1) light key (LK) - the most volatile of the keys; appears mostly in the top and slightly in the bottom, i.e. it is
the lightest component in the bottom,
(2) heavy key (HK) - ; the least volatile of the keys; appears primarily in the bottom and is the heaviest
component in the top

Non-keys (NK) - the other components

(3) Light non-key (LNK) - is referred when non-key is more volatile than the light key, any components lighter
than the light key
(4) heavy non-key (HNK) - is less volatile than the heavy key, those components heavier than the heavy key

Several short-cut methods are used for carrying out calculations in multicomponent systems.

These involve:
1. an estimation of the minimum number of trays,
2. the estimation of minimum reflux rate and
3. number of stages at finite reflux for simple fractionators
 Theoretical Concept
⮚ In the fractionation of multicomponent mixtures, the essential requirement is often
the separation of two components called the key components
⮚ If a four-component mixture A–B–C–D (ternary system) is to be separated then,
the main purpose of the fractionation is the separation of B from C.

A is the most volatile B is the lightest component

Key components appearing in the bottoms and is
termed the light key component
D the least volatile

C is the heaviest component appearing in the distillate and is

called the heavy key component.
 Processing Sequence
Major Categories Objective

1. Stripping ⮚ remove light material from a heavy product

(L from H)

2. Rectification ⮚ remove heavy material from a light product

(H from L)

3. Fractionation ⮚ remove a light material from a heavy

product and a heavy material from a light
product at the same time
⮚ making two products
4. Complex fractionation ⮚ makes multiple products from either a
single tower or a complex of towers
combined with recycle streams between
them
⮚ making more than two products

7
 Basic Equations
Material Balance equations:
Total Balance: Component Balance
F=D+ B F xf = D xd + B xb
Where:
F = Feed rate xf= mole fraction of Feed
D = Distillate xd= mole fraction of Distillate
B = Bottoms xb= mole fraction of Bottoms
FRACTIONAL RECOVERY (FR)
(FR) = (D*xd) x 100 (FR) = (B*xb) x 100
(F*xf) (F*xf)

Where:
F = Feed rate (moles) (F*xf) = moles of each component in the Feed
D = Distillate (moles (D*xd) = moles of each component in the Distillate
B = Bottoms (moles) (B*xb) = moles of each component in the Bottoms

Amount of Distillate (D),moles = sum of all components in the Distillate = (Ʃ) (D*xd)i
Amount of Bottoms (B),moles = sum of all components in the Bottoms = (Ʃ) (B*xb)i
 Total Reflux Condition & Fenske equation

NOTE: Under total reflux condition, D = 0, thus, V2 = L1. The component material balance
for the light key component around the first plate and the top of the column i

reboiler

NOTE: This is a form of the Fenske Equation. In Equation (1), Nmin is the number of equilibrium trays
required at total reflux including the partial reboiler, (2) Nmin is the number of equilibrium trays required at
total reflux excluding the partial reboiler

The vapor-liquid quilibria for a mixture are described by distribution coefficients or K factor, where K for
each component is the ratio of mole fractions in the vapor and liquid phases at equilibrium.
Ki = yi/ xi
 Derived equations
For binary system(A-B system)

useful in the calculation of

plate enrichment and finds
wide application in
multicomponent distillation

Separation of multicomponent mixtures of hydrocarbons, is to use the simple relation:

yA = KxA K = y /x
α - the relative volatility is
the ratio of the K at a specific
condition of temperature and
pressure for a component to
the K value for the heavy key
component.

∝ (ij) = y(i) / x (i) ∝ (ij) = K (j)

Ki = yi/ xi y(j) / x(j) K (j)
NOTE: (i) light key (LK) (j) – heavy key (HK)
10
 Example# 5 (Multicomponent
Distillation)
Illustration 5.18 p236 by A. Suryanarayana (with modification)
A mixture having the following composition below is to be separated by distillation
so that 95% of propane charged is removed into distillate and 99 % of butane
charged is removed into bottoms. The column is operating at 465 psi.
Sl. No Component Feed , kg-moles
1 ethane 10
2 propane 30
3 n-butane 40
4 n-pentane 20

❖Calculate the complete product compositions and the minimum number of ideal
plates at infinite reflux ratio.
❖ Data: K1 = 2.5 K2 = 1.1 K3 = 0.6 K4= 0.3
 Problem Analysis
GIVEN:

D= ?
xD = ?
Composition Fractional Recovery (FR)
LNK C2H6 (assumed) 100% 1
LK C3H8 95% 0.95
HK C4H10 (100-99%) = 1% 0.01
HNK C5H12 (assumed) 0 0
F = 100 kmoles
Composition (F*xf),kmoles K
LNK C2H6 10 2.5
LK C3H8 30 1.1
HK C4H10 40 0.60 B=?
HNK C5H12 20 0.32
Total(Ʃ) = 100 kmoles
xB = ?
Composition Fractional Recovery (FR)
LNK C2H6 (assumed) 0% 0
LK C3H8 (100-95%) = 5% 0.05
HK C4H10 99% 0.99
REQUIRED: HNK C5H12 (assumed) 100% 1

a) Calculate the complete product compositions NOTE: total moles (D, B) and composition( xB and xD)
b) Minimum number of ideal plates at infinite reflux.
 Part (a): Complete Product Compositions

STEPS FOR METHOD 1

1. List the feed components and arrange in order of their relative
volatility
2. Determine the fractional recovery (FR) of each component in
the Distillate and Bottoms products
3. Determine the amount (or moles) of each component in the
Distillate product using the Fractional Recovery (FR) data
4. Determine the composition (or mole fraction) of each
component in the Distillate product using the calculated
amount
5. Determine the amount (or moles) of each component in the
Bottoms product using the Fractional Recovery (FR) data
6. Determine the composition (or mole fraction) of each
component in the Distillate product using the calculated
amount
 Step 1
List the feed components and arrange in order of their relative volatility

Feed (F) = 100 kmoles

Composition (F*xf),moles
LNK C2H6 10
Key components because
distillate and bottoms
fractional recoveries
LK C3H8 30
specified in the problem
HK C4H10 40
HNK C5H12 20
Total (Ʃ)
relative volatility in C2H6 ˃=C3H8 ˃ C4H10 ˃ C5H12 100
terms of K values
K = 2.5 K = 1.1 K = 0.6 K = 0.32
 Step 2
Determine the fractional recovery (FR) of each component
A. Distillate product

Composition FR
LNK C2H6 (assumed)100% 1 Totally vaporized, lightest component
LK C3H8 95% 0.95 Removed into distillate
HK C4H10 (100-99%) = 1% 0.01
HNK C5H12 (assumed) 0 0 no vaporization, heaviest component

B. Bottoms product

Composition FR lightest component

Totally vaporized,
LNK C2H6 (assumed) 0% 0 removed as overhead product
LK C3H8 (100-95%) = 5% 0.05
HK C4H10 99% 0.99 Removed at the bottoms
HNK C5H12 (assumed) 100% 1 heaviest component
no vaporization,
Totally removed at the bottoms,
 Step 3
Determine the amount (or moles) of each component in the Distillate
product using the Fractional Recovery (FR) data

(FR) = (D*xd) x 100 (D*xd) = (FR)(F*xf) (D*xd) = (FR)(F*xf)

(F*xf) 100
in terms of fraction

Feed (F) = 100 kmoles Distillate(D) = ? = 38.9 kmoles

Composition (F*xf) FR (D*xd) = (FR)(F*xf)
LNK C2H6 10 1 (1)(10) = 10
LK C3H8 30 0.95 (0.95) (30) = 28.5
HK C4H10 40 0.01 (0.01) (40) = 0.4
HNK C5H12 20 0 (0) (20) = 0
Total (Ʃ) = 100 Total(Ʃ) = 38.9
 Step 4
Determine the composition (or mole fraction) of each component in
the Distillate product using the calculated amount

xd = (D*xd), kmoles (D*xd)i = kmoles of each component

Total(Ʃ)of D, Total(Ʃ)of D =total amount of Distillate in
in terms of fraction kmoles kmoles

Distillate(D) = ? = 38.9 kmoles

Components (D*xd) = (FR)(F*xf) xd= D*xd/Total(Ʃ)
C2H6 10 10/38.9 = 0.26
C3H8 28.5 28.5/38.9 = 0.73
C4H10 0.4 0.4/38.9 = 0.01
C5H12 0 0/38.9 = 0.00
Total(Ʃ) = 38.9 Total(Ʃ) = 1
 Step 5
Determine the amount (or moles) of each component in the Bottoms
product using the Fractional Recovery (FR) data

(FR) = (B*xb) x 100 (B*xb) = (FR)(F*xf) (B*xb) = (FR)(F*xf)

(F*xf) 100
in terms of fraction

Feed (F) = 100 kmoles Bottoms (B) = ? = 61.1 kmoles

Composition (F*xf) FR (B*xb) = (FR)(F*xf)
LNK C2H6 10 0 (0) (10) = 0

LK C3H8 30 0.05 (0.05) (30) = 1.5

HK C4H10 40 0.99 (0.99)(40) = 39.6
HNK C5H12 20 1 (1) (20) = 20
Total (Ʃ) = 100 Total(Ʃ) = 61.1
 Step 6
Determine the composition (or mole fraction) of each component in
the Bottoms product using the calculated amount

xb = (B*xb), kmoles (B*xb)i = kmoles of each component

Total(Ʃ)of B, Total(Ʃ)of B =total amount of Bottoms
in terms of fraction kmoles product in kmoles

Bottoms (B) = ? = 61.1 kmoles

Components (B*xb) = (FR)(F*xf) xb= B*xb/Total(Ʃ)
C2H6 0 0/61.1 = 0
C3H8 1.5 1.5/61.1 = 0.02
C4H10 39.6 39.60/61.1 = 0.65
C5H12 20 20/61.1 = 0.33
Total(Ʃ) = 61.1 Total(Ʃ) = 1
 (By TABULAR METHOD)

Feed (F) = 100 kmoles Distillate (D)=? = 38.9 kmoles Bottoms (B)=?= 61.1 kmoles

(F*xf), (D*xd), kmoles xd (B*xb),kmoles xb

Composition kmoles FR = (FR)(F*xf) = D*xd /Total(Ʃ) FR = (FR)(F*xf) = B*xb /Total(Ʃ)
LNK C2H6 10 1 (1) (10) = 10 10/38.90 = 0.26 0 (0) (10) = 0 0 /61.1 = 0

LK C3H8 30 0.95 28.5 0.73 0.05 1.5 0.02

HK C4H10 40 0.01 0.4 0.01 0.99 39.6 0.65

HNK C5H12 20 0 0 0.00 1 20 0.33

Total(Ʃ) = 100 38.9 1 61.1 1

20
 Part(b): Minimum number of ideal plates at infinite reflux

DATA LK C3H8 xD(i) = 0.73 xB(i) = 0.02 K (i) = 1.10

: HK C4H10 xD(j) = 0.01 xB(j) = 0.65 K (j) = 0.60

∝ (C3,n-C4) = K (j)
(0.73/0.02)
ln (0.01/0.65) K (j)
Nmin = -1
∝ (C3,n-C4) = 1.10 = 1.83
ln 1.83
0.60
= 7.77 - 1
0.60
Nmin = 11.95 (excluding the reboiler) NOTE: Minimum number of stages at
total reflux (or infinite reflux ratio)
 Final Analysis
Minimum number of stages at total reflux
(Nmin) = 11.95 (excluding the reboiler)

Distillate(D)=? = 38.9 kmoles

(D*xd) = xd=
Composition FR (FR)(F*xf) D*xd/Total(Ʃ)
F=D+ B LNK C2H6 1 10 0.26
100 kmoles = (38.9 + 61.1) kmoles LK C3H8 0.95 28.5 0.73
100 kmoles =100kmoles HK C4H10 0.01 0.4 0.01
HNK C5H12 0 0 0.00
Total(Ʃ) 38.9 1.00

F = 100 kmoles

Composition (F*xf),kmoles K
LNK C2H6 10 2.5
LK C3H8 30 1.1
HK C4H10 40 0.6 Bottoms (B)=?= 61.1 kmoles
HNK C5H12 20 0.32 (B*xb) = xb=
Total(Ʃ) = 100 kmoles Composition FR (FR)(F*xf) B*xb/Total(Ʃ)
LNK C2H6 0 0 0.00
LK C3H8 0.05 1.5 0.02
HK C4H10 0.99 39.6 0.65
HNK C5H12 1 20 0.33
Total(Ʃ) 61.1 1.00

F xf = D xd + B xb (for LK) F xf = D xd + B xb (for HK)

30 kmoles =(28.50+ 1.50)kmoles 40 kmoles =(0.40+ 39.60)kmoles
30 kmoles =30kmoles 40 kmoles = 40 kmoles
 What is Azeotropic Distillation?
➢ Substances forming constant boiling mixtures or azeotropes,
on the other hand, cannot be separated by ordinary methods
of distillation since the compositions of liquid and vapour
become same at the point where azeotrope is formed.
➢ a third component is added to the binary mixture to make the
separation readily possible.
➢ When the added substance combines with the low boiling
component and is recovered from the distillate, the operation
is called azeotropic distillation.

Spring Semester (2021-22) EME10318 Unit Operations – II (BEng Chemical Engineering)

 Azeotropic Distillation

SOURCE: https://chemicalengineeringworld.com/azeotropic-distillation-process/

Spring Semester (2022-23) EME10318 Unit Operations – II (BEng Chemical Engineering)

 What is Extractive Distillation?
➢ In extractive distillation, the third component
known as the solvent is added to change the
relative volatility of the constituents to be
separated.
➢ The solvent is of low volatility and in contrast to
azeotropic distillation, remains mostly with the
bottom product without being appreciably
vaporised.

Spring Semester (2021-22) EME10318 Unit Operations – II (BEng Chemical Engineering)

 Extractive Distillation

SOURCE: https://www.processingmagazine.com/home/article/21241815/extractive-distillation-what-is-it-and-when-should-it-be-used
Spring Semester (2021-22) EME10318 Unit Operations – II (BEng Chemical Engineering)
 Self-Test
(1) What do you mean by an azeotrope and azeotropic distillation?
(2) In an azeotropic mixture, the equilibrium vapour composition
as compared with the liquid composition, is
(a) more (b) same (c) less (d) uncertain
(3) What should be the nature of volatility of solvents for use in
extractive distillation?
(4) Solvent used in extractive distillation:
(a) alters the relative volatility of the original components
(b) is of low volatility, (c) must not form any azeotrope with the
original substance, (d) all the above

Spring Semester (2021-22) EME10318 Unit Operations – II (BEng Chemical Engineering)

 Prepared by: Course Coordination Team
Spring Semester (2022-23) EME10318 Unit Operations – II (BEng Chemical Engineering)