CHEN3011

Petroleum Field and Refinery Processes

Lecture 13
Distillation - Part 1

Dr. Arash Arami-Niya

[email protected]

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Recommended reading
 McCabe et al., Unit Operations of Chemical Engineering,
Chapter 21
 Treybal, R. E. Mass Transfer Operations, 3rd Edn.
McGraw-Hill 1955, Chapter 9
 BENÍTEZ, J. (2009). Principles and Modern Applications of
Mass Transfer Operations, Hoboken, USA, John Wiley
and Sons. Chapter 6
 COULSON, J. M. and RICHARDSON, J. F. Chemical
Engineering, Volume 6: Particle Technology and
Separation Processes, 5th Edn. Butterworth-Heinemann
2002
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Distillation learning objectives
1. Define concepts of flash vaporization and partial
condensation, and continuous distillation.
2. Relate operating temperature and pressure during flash
vaporization to the concentrations of the liquid and
vapour phases (material and energy balances).
3. Apply the McCabe-Thiele graphical method to determine
number equilibrium stages required for a given
separation and the optimal feed tray location.
4. Calculation height of random packing required for a
distillation separation using the HETP method.

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Distillation topics covered in this unit
Vapour

1. Single stage flash vaporization (or

condensation)
Flash
Feed tank

Heat exchanger

Liquid

2. Continuous distillation
Vapour Total condenser

3. Tray efficiencies
Distillate
reflux

Feed

Heat exchanger

Partial reboiler
Liquid

Bottoms

4. Distillation in packed columns

Could also have batch distillation processes; not covered in these lectures.

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Distillation defined
Phase 1

Feed
Phase
Phase 2
creation

Energy input

 Creating a second phase through vaporisation and condensation

 Requires energy input (heat/cool; shaft-work)
 Most common separation technique
 Fractionation of crude oil
 Rectification of alcohol

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Advantages of distillation
In comparison to absorption or desorption processes, distillation offers the
following advantages:
• Heat can usually be readily added or removed from process stream

• Possible to obtain at least two high-purity product streams from 1

column.

• Absorption operations produce a new solution which in turn may need

to be separated (eg. regeneration of spent amine in an acid gas
treating unit).

The drawback…
Distillation is a very energy intensive operation, especially when the
relative volatility of the components to be separated is low.
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Distillation mechanism
BENÍTEZ (2009) page 321:

“Distillation is a method of separating components of a solution

which depends upon the distribution of the substances between a
liquid and gas phase, applied to cases where all components are
present in both phases.”

The second phase is created from the feed solution by:

(i) vaporization
(ii) condensation

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Distillation Process Equipment
Most frequently distillation is carried
out in multi-tray columns.
www.sulzerchem.com

Can do distillation with packed

columns, for example if ΔP is critical.

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Equilibrium concept

 An approach to model heat and mass transfer

processes
 Assumes that V and L streams are in complete
equilibrium
 Efficiency defined to relate equilibrium stages to
actual tray performance
 Real trays = ideal trays(equilibrium)/efficiency

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Equilibrium concept - issues

 V and L phases not in equilibrium actually

 Instead, there is transport of material between
phases
 Difficult to actually achieve thermal equilibrium
Infinitely large phase interface
Large transfer co-efficient
 Difficult to find an efficiency factor to represent
thermal equilibrium

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Equilibrium concept - Approach

 Divides the distillation column design process

into three steps
 Thermodynamic data assembled

 Equilibrium (ideal) stages calculated

 Converted to actual number of trays using

efficiency information

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CHEN3011
Petroleum Field and Refinery Processes

Lecture 13-1
VLE Basics

Dr. Arash Arami-Niya

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Volatility and vapour pressure

 Tendency of a component to vaporise

 Determines how easily a solution boils
 Boiling: vapour pressure = external pressure
 High vapour pressure = high volatility = low Tbp
 Energy input raises vapour pressure
 Distillation possible due to differences in the volatility

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Relative Volatility Vapour-liquid equilibrium (VLE) relationships
The relative volatility for two components A and B, αAB , is defined as:

KA, KB here are

Henry’s law
y A xA pA x A KA
 AB    constants
y B xB pB x B KB

Usually written defined so that αAB ≥ 1

This means A is the more volatile component (MVC), then drop the
subscripts A & B, then substitute with

xB  1  x A ; y B  1  y A

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Thermodynamic data (VLE data)
 P, T set the composition
 Range of T’s and comps (for one substance) at fixed pressure OR range of P’s
and comps at fixed T
 Binary mixtures – Txy plot

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 Binary Mixture (Ideal)
Temperature - Composition (Tx) diagram at constant Pressure

Dew point curve –

Temperature Treybal p344+ discusses VLE data in a little
If vapour is cooled,
more detail than McCabe et al. or Benitiz.
droplets of liquid form.

Vapour Composition (y)

At equilibrium & temperature T1:
Tboil, B
 Composition of A in the
Tie line liquid phase = C1
T1 Liquid is richer in B

Bubble point curve –  Composition of A in the

If liquid is heated,
bubbles of vapour Tboil, A vapour phase = C2
form. Liquid Composition (x) Vapour is richer in A.
C1 C2
Pure B Pure A
Mole fraction A
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 Binary Mixture (Ideal)
Temperature - Composition (Tx) diagram at constant Pressure

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 One component more One component more One component more
Volatile than the other volatile than the other volatile than the other
over the entire range up to xg after that up to xg after that
of compositions volatilities reversed. volatilities reversed.
AZEOTROPES AZEOTROPES

Separated by simple
distillation
Extractive distillation

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Can also show this data as a distribution diagram (x vs y*)?

y* = mole 0.75
fraction A in
vapour

0.5

0.25

0
0 0.25 0.5 0.75 1

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x = mole fraction A in liquid
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 Why is the eq. curve above the 45°line?
1

y* = mole 0.75

fraction A
in vapour
0.5

0.25

0
0 0.25 0.5 0.75 1

x = mole fraction A in liquid

The vapour is richer in the more volatile component.

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Constant Relative Volatility

 For binary systems that form ideal solutions such as:

benzene + toluene (methyl-benzene)
heptane + octane,

 that also have a ratio of vapour pressures that are

constant then the relative volatility αAB is constant (not
affected by T or {xi}).

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Constant Relative Volatility

 For a constant relative volatility the vapour composition, y

can be written as a function of α and x, for the binary
system:

12 
 y1 x1 
 y2 x2 

y1 
12 x1 x
or y 
1  12  1 x1 1    1 x

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 “45°” line
i.e. yi = xi

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Relative volatilities

Useful because for many substances  is constant over a

reasonable range of T & P

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CHEN3011
Petroleum Field and Refinery Processes

Lecture 13-2
Flash distillation

Dr. Arash Arami-Niya

[email protected]

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Flash distillation “equilibrium distillation”

 Partial vaporisation in one equilibrium stage

 Creates two phases, L and V, in equilibrium with

each other

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Flash distillation plant

• Sometimes used as preliminary

process before a distillation

• Flash calcs done to:

– Determine condition of feed into a

distillation column

– Determine V from a reboiler or a

condenser if latter a partial condenser

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 Vapour

D mole/s (D for distillate)

yD - mole frac. MVC
Flash HD enthaply (kJ/mol)
Feed tank

F mole/s
xF - mole frac. MVC
Q(in)
HF enthaply (kJ/mol) B mole/s (L for liquid)
xB - mole frac. MVC
Liquid
HB enthaply (kJ/mol)

Material and energy balances for a single-stage flash tank:

Overall: F  DB
MVComp: xF F  yD D  xB B
Energy: FH F  Q  DH D  BH B
** HF, HD and HB are the enthalpies of the feed, vapour & liquid products respectively.
Q is an amount of heat added (Q > 0) or removed (Q < 0) from the process.

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Flash separation - Binary component mixture

TF has to be between the Tbp and Tdp of the feed in order to create two
phases.

The above puts limits on the maximum vapour concentration achievable (yD)
and the minimum liquid concentration achievable (xB)

What does this mean? See next slide.

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Limits on Tflash

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Material balance on single stage flash
If we define the fraction f of feed vaporized in the flash process,
we could write the MVC balances using:

f: vaporization fraction f  D F ; and B  1  f  F

MVComp: xF  yD f  xB 1  f 
𝑓−1 𝑥𝐹
Rearrange: 𝑦𝐷 = 𝑥𝐵 +
𝑓 𝑓

A straight line through point (xF, xF) with a slope of (f – 1)/f

There are 2 unknowns in the MVComp balance yD and xB, so to use

this equation we need the second relationship between the
vapour and liquid concentrations of the MVC:
 the VLE data or relative volatility
y A xA x
 AB  or y 
1    1 x
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y B xB
Flash separation – diagram with equilibrium curve and working
line

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Some questions….

 Which statement is true?

In order for two phases to be created in flash distillation,

1. TF must be equal to the bubble point of the feed.

2. TF must be between the bubble point and due point of the feed.
3. TF must be equal to the dew point of the feed.

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Some questions….

 In an x-y plot when the equilibrium line coincides with the

45 degree line, this means

1. The relative volatility is high

2. The relative volatility is low

3. The separation is possible but will be difficult

4. The separation will be impossible

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 Example

n-heptane boiling point at 1 atm is 98.4 degC and n-

octane boiling point is 125.6 degC. Which is the
more volatile component?

1. n-octane
2. n-heptane

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Example single stage flash.

Illustration 9.4 Treybal. A liquid mixture containing 50% mol

n-heptane and 50 mol% n-octane (ideal solution) at 30°C
is to be flash-vaporized at 1 std atm pressure to vaporize
60 mol % of the feed.
Main question: (1) Plot the bubble point curve and the dew
point curve. (2) What will be the composition of the vapour
and liquid and the temperature in the separator for an
equilibrium stage?
Equilibrium data for this problem is provided in Illustration
9.1 of Treybal.

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n-heptane and n-octane at 1 std atm
Tbp, degC n-heptane 98.4 n-octane 125.6

T pA
PA* pB
PB* x y* alpha
deg C mmHg mmHg
98.4 760 333 1 1 2.28
105 940 417 0.655 0.81 2.25
110 1050 484 0.487 0.674 2.17
115 1200 561 0.312 0.492 2.14
120 1350 650 0.1571 0.279 2.08
125.6 1540 760 0 0 2.03
Using Raoult’s Law:
PA = PA* x, PB = PB* (1- x),
x = xA = (P - PB*)/(PA*- PB*)
P = PA + PB
y* = yA* = PA*x/P

e.g. at 105 degC, x = (760-417)/(940-417) = 0.655,

and y* = 940 x 0.655/760 =0.81,
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and α = (0.81/0.655)/((1-0.81)/(1-0.655)) = 2.25

Plot the bubble point curve and the dew point curve

130

125

120

115
T, deg C

110

105

100

95

90
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

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Plot the bubble point curve and the dew point curve

Dew point curve

Bubble point curve

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Equilibrium data - Illustration 9.4 Treybal.

1 140

0.9 T curve
120
0.8

0.7 100
y* = mole fraction
heptane in vapour 0.6
y* 80
0.5 zf=0.5 T, degC
60
0.4

0.3 40

0.2
20
0.1

0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x = mole fraction heptane in liquid
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Equilibrium data - Illustration 9.4 Treybal.
Vapour
Basis F=100 mol/s feed;
Want to vaporize 60% of the feed.
Flash
So, the vaporization fraction f = 0.6 tank
Feed

So, vapour flow D = 0.6F = 60 mol/s and liquid flow

B = 40 mol/s
Liquid

Like gas-liquid absorption column could write an operating line

Slope : (f – 1)/f = (0.6-1) / 0.6 = -0.667

Or from a material balance:

B 40
slope -  -  0.667
D 60
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Equilibrium data - Illustration 9.4 Treybal.

1 140

0.9
Bubble point curve
120
0.8
T flash  113 C
0.7 100
y* = mole fraction
Slope =
heptane in vapour 0.6 -0.667
80
0.5 T, degC
60
0.4
y D*  0.575 0.3 40
x B  0.387 0.2
20
0.1

0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x = mole fraction heptane in liquid
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Which stream is at 113 degC?

1. The vapour
2. The liquid
3. The liquid and the vapour

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CHEN3011
Petroleum Field and Refinery Processes

Lecture 13-3
Continues distillation

Dr. Arash Arami-Niya

[email protected]

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Achieving separation by distillation

The process of distillation is achieved by promotion of mass

transfer of more volatile material from the liquid to the
vapour phase

Mass transfer is achieved by controlled gas/liquid contacting

usually in a distillation column or tower

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Multistage/ Equilibrium stage continuous separation processes

Applies to distillation and other separation processes such

as:
Liquid-liquid extraction
Gas Adsorption
Scrubbing

Essence is that for each stage equilibrium is achieved

for distillation this means that the vapour ({yi}) and the liquid ({xi})
compositions are in equilibrium.

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Define: Purity and Recovery
 Purity – refers to the actual composition of the product, i.e.
the distillate composition
xD = 0.99, so the purity is 99 %
 Recovery – refers to the percentage of a component in the
feed which appears in the product.
Distillate Recovery of A
45 mol of A = 45/60 = 75%
? mol of B
(indpt. of recovery of B)
Feed
60 mol of A
40 mol of B

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Continuous Distillation

Video
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51
Multiple Equilibrium Stages

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Learning objectives

1. Define concepts of flash vaporization and partial

condensation, and continuous distillation. Done
2. Relate operating temperature and pressure during flash
vaporization to the concentrations of the liquid and
vapour phases (material and energy balances).
Done
3. Apply the McCabe-Thiele graphical method to determine
number equilibrium stages required for a given
separation and the optimal feed tray location.
4. Calculation height of random packing required for a
distillation separation using the Height Equivalent a
Theoretical Plate (HETP) method.
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 Rectification in the lower
section of the column,
including the feed plate itself,
Feed Section is called stripping. Since the
liquid reaching the reboiler is
stripped of
component A, the bottom
product can be nearly pure B.
RECTIFYING SECTION
Stripping
Section
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 Tray columns or Plate columns
What does the U-shaped
tube mean in this diagram?
Downcomer
The flow of vapour
through the holes and the
liquid on the plate requires
a difference in pressure.

Low vapour velocity →

weeping

The upper limit of the

velocity → flooding

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Stable operation of a tray tower

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Tray openings for vapour

Perforation Valve Cap Bubble Cap

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Trays

Trays with valve caps

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An ideal plate/stage

Ideal plate: vapour / liquid leaving the plate are at equilibrium

– with respect to composition, temperature and pressure
For column design a stage efficiency is applied
For example if the # ideal plates = 12,
& if know from experience, stage efficiency = 80%,
then # actual plates = 12 / (80%) = 15

In HYSYS and other process simulation tools the default is

typically for an ideal stage, i.e. default efficiency = 100%

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Binary multistage continuous distillation

For simplicity we will consider a binary system of

components.

x = mole fraction of the most volatile component (MVC)

in the liquid.

y = mole fraction of the MVC in the vapour.

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Single Equilibrium Stage (MESH equations)
Material, Equilibrium, Summation, Heat
Vn, yn Ln-1, xn-1

Fn , Zn n Sn, xn

qn (heat added / lost)

Vn+1, yn+1 Ln, xn

Material balance: Vn+1 yn+1 + Ln-1 xn-1 + FnZn = Vn yn + Ln Xn + Sn xn

Equilibrium condition: yi = Ki xi

Summation condition: ∑ yi,n = ∑ xi,n = 1.0

Heat balance: vapour / liquid heat in + Qin= vapour / liquid heat out
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Heat and mass balances on an ideal plate
Vn-1
V = vapour rate (mol·s-1)
y n-1
n-1 L = liquid rate (mol·s-1)
L n-1 Vn
x n-1 yn n, n+1 etc – refer to plate number
(subscripts)
n
Ln
V n+1 x = liquid mol. fr. MVC
xn
y n+1
n+1 y = vapour mol. fr. MVC
L n+1
x n+1

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Material balance

For plate n can write two material balances:

For the total material:

Vn 1  Ln 1  Vn  Ln

and for the more volatile component (MVC)

yn 1Vn 1  xn 1 Ln 1  ynVn  xn Ln

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Assumptions applied in a classical stage by stage analysis of a
distillation column

1. Each plate (stage) behaves like an ideal plate.

2. Heat losses are negligible.
3. Heat of mixing are negligible.
4. Sensible heat changes from plate to plate are small.
5. Molar latent heats (Enthalpies of vaporisation) are
constant.

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Constant Molal Overflow

Assumptions 2-5 are the conditions for what is called

“Constant Molal Overflow”
Refers to one mole of vapour condensing liberates just
sufficient heat to vaporise one mole of liquid
In Practice this simply mean that “liquid and vapour molar
flow rates” in each section are constant, respectively:

rectifying Vn 1  Vn  Vn 1 Ln1  Ln  Ln1

stripping Vm1  Vm  Vm1 Lm1  Lm  Lm1

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 An Idealized
Ln-2 Vn-1
Illustration
Ln-2= Ln-1 = 14
n-1 Vn-1 = Vn = 10

Vn
Mole

MVC
Ln-1
Ln-1 = Ln = 14
n Vn+1=Vn = 10

Vn+1
Mole

Less
Ln Volatile
Ln+1 = Ln = 14 cmpnt
n+1 Vn+2=Vn+1 = 10

Vn+2 One mole of vapour condensing

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liberates just sufficient heat to
vaporise one mole of liquid
 Rectifying
Section
n-1
n
n+1
Vn 1  Vn  Vn 1 Ln1  Ln  Ln1

Feed Section
m-1
m
m+1
Vm1  Vm  Vm1 Lm1  Lm  Lm1
Stripping
Vn = or ≠ Vm, Ln = or ≠ Lm
Section Case by case, depending on
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Rectification
Rectifying (or absorbing or enriching)
section of a column is the section above
the feed point. Rectifying
rising vapour is washed with liquid section

The vapour at the top of the column is

condensed
some returned to column as “reflux”.
material permanently removed is “distillate” OR “top
product”.

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Rectifying section balances
total
condenser
Vapour

Liquid

D, x D Distillate

Ln+1 xn+1 n -1
Material
Vn yn
Balance
n Boundary

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Rectifying section balances

Total material balance:

Vn  Ln 1  D (1)
In Out
Most volatile component:
Vn yn  Ln 1 xn 1  DxD (2)

For constant molal overflow

→ (1) becomes:
Vn  Ln  D (3)
and (2) becomes:
Vn yn  Ln xn 1  DxD (4)
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Operating line – Rectifying section

Equation (4) can be rearranged to:

 Ln   DxD 
yn    xn 1    (5)
 Vn   Vn 
Since Ln, Vn, D and xD are all constant, eqn (5) is a linear
relationship relating the compositions of the passing
streams within the column -
this is referred to as the operating line equation for the
rectifying section, or the top operating line (TOL)

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Reflux ratio, R

total Is defined at the top of the

Vn condenser column as the ratio of the
liquid rate returned to the
column to the distillate rate
i.e.:
Ln D
Reflux
R  Ln D

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Rectifying section operating line (TOL) as a function of the Reflux
Ratio

For constant molal overflow: R = Ln/D. LN= Ln VN= Vn

total
Vn condenser
Vn  Ln  D
Ln Ln
D so 
Ln
Vn Ln  D
Reflux
Ln Ln D R
 
Vn Ln D  D D R  1

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 Rectifying section operating line
(TOL) as a function of the Reflux Ratio
Vn  VN  Ln  D
D D
Also: 
Vn Ln  D
D D D 1
 
Vn Ln D  D D R  1
 Ln   DxD 
So: yn    xn 1    becomes:
slope  Vn   Vn 
Intercept

 R   xD  A straight line
yn    xn 1    though point (xD, xD)
 R  1   R  1 
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 Tutorial 1 Draw top operating line

A binary mixture containing 48.7% mol n-heptane and 51.3

mol% n-octane (ideal solution) is to be separated by a
continuous distillation tower at 1 atm pressure. It is
required to achieve at least 95% mol purity of n-heptane
in the distillate at the top of the column. The reflux ratio is
5.
Main question: (1) Plot the top operating line (TOL).
Equilibrium data for this problem is provided in Illustration
9.1 of Treybal and last lecture notes.

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Equilibrium data - Illustration 9.4 Treybal.
n-heptane and n-octane at 1 std atm
Tbp, degC n-heptane 98.4 n-octane 125.6

T pA
PA* pB
PB* x y* alpha
deg C mmHg mmHg
98.4 760 333 1 1 2.28
105 940 417 0.655 0.81 2.25
110 1050 484 0.487 0.674 2.17
115 1200 561 0.312 0.492 2.14
120 1350 650 0.1571 0.279 2.08
125.6 1540 760 0 0 2.03
Using Raoult’s Law:
PA = PA* x, PB = PB* (1- x),
x = xA = (P - PB*)/(PA*- PB*)
P = PA + PB
y* = yA* = PA*x/P

e.g. at 105 degC, x = (760-417)/(940-417) = 0.655,

and y* = 940 x 0.655/760 =0.81,
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and α = (0.81/0.655)/((1-0.81)/(1-0.655)) = 2.25

Procedure

(1)Using the equilibrium data to plot the equilibrium line (y* -

x) and the diagonal line y = x.
(2)Locate point a (xD, xD), i.e. (0.95,0.95).
(3)Determine the intercept of TOL for rectifying section, i.e.
xD/(R+1) = 0.95/(5+1) = 0.158. Then, locate the intercept at
point b (0, 0.158) in y axis.
(4)Connect ab, and get the TOL.

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 Equilibrium data - Illustration 9.4 Treybal.
1

0.9
a (xD, xD)
y = xD = 0.95
0.8

0.7

0.6
y*

0.5

0.4

0.3
Intercept = 0.158

0.2 b

0.1

0
0 0.1 0.2 0.3
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xD = 0.95
x
Stripping
Stripping (or exhausting) section of
a column is the section below the
feed point.
Liquid is stripped of MVC by vapour
rising up the column

Liquid exiting column is reboiled

Partial vaporisation of the bottom
liquid is performed and returned to the Stripping
column
The material removed at bottom is
section
“residue” OR “bottom product”

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Stripping section balances

Lm-1
m+1 xm+1
xm-1 m -1
Vm ym
m

Vapour
Material
Total Balance
Liquid
Reboiler Boundary

Bottom
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product
B, xB
Stripping section balances

Total material balance:

Lm 1  Vm  B (6)
m-1 In Out
More volatile component:
Lm 1 xm 1  Vm ym  BxB (7)

For constant molal overflow

→ (6) becomes:
Lm  Vm  B (8)
and (7) becomes:

Lm xm 1  Vm ym  BxB (9)
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 Operating line – Stripping section

Equation (9) can be rearranged to:

slope Intercept

 Lm   BxB  A straight line

ym    xm 1    (10) through point (xB, xB)
 Vm   Vm 

Since Lm, Vm, B and xB are all constant, eqn (10) is a linear
relationship relating the compositions of the passing
streams within the column -
this is referred to as the operating line equation for the
stripping section, or bottom operating line (BOL)

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Tutorial 2 Draw bottom operating line

A binary mixture containing 48.7% mol n-heptane and 51.3

mol% n-octane (ideal solution) is to be separated by a
continuous distillation tower at 1 atm pressure. It is
required to achieve no more than 5% mol n-heptane in
the bottom product. It is also known at the bottom of the
column, 20% mol of the liquid is drawn as the bottom
product.
Main question: (1) Plot the bottom operating line (BOL)
Equilibrium data for this problem is provided in Illustration
9.1 of Treybal and Lecture 4.1.

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Procedure
(1)Using the equilibrium data to plot the equilibrium line (y* -
x) and the diagonal line y = x.
(2)Locate point c (xB, xB).
(3)Because mass balance : Lm  Vm  B (8)
and constant molal overflow Lm = L, Vm = V
for every one mole of liquid (L), 0.2 mole is drawn as
bottom product (B), and 0.8 mole is reboiled (V). Then,
determine the slope of BOL for stripping section, i.e. Lm/Vm=
1/(1-0.2) = 1.25.
(4) Then, draw a straight line though point c (0.05, 0.05) with
slope of 1.25 and get the BOL.
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Equilibrium data - Illustration 9.4 Treybal.
1

0.9

0.8

0.7

0.6
y*

0.5

0.4

0.3 Slope = 1.25

0.2

0.1
0.05 c
0
0 0.1 0.2 0.3
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85
x
Equation over load...

What is important?
The mass balances you should all be able to do/ understand at this level
Concept/definition of reflux and reflux ratio R
Concept of constant molal overflow and what it means in practical
terms
The concept of an ideal plate, should be/become obvious, how to correct
will be dealt with later

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The key equations we will use

 xi
Relationship between xi and yi yi 
1    1 xi

Operating line for Rectifying section  R   xD 

yn   
 n 1 
x 
 R 1   R  1 
Operating line for Stripping section
 Lm   BxB 
ym    xm 1   
 m
V  m 
V

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Azeotropes
Even if the operating lines
are along y = x:
• Infinite plates will achieve
no separation
• The vapour composition is
the same as the liquid
composition
• Hence relative volatility is
1 and no separation is
possible

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Azeotropes and distillation
Azeotrope point

Can add a third component to avoid azeotrope.

For ethanol-water system:
Classical: benzene
Salts also effect phase equilibria – non-volatile
Potassium acetate

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