University of Tripoli

Chemical Engineering Department

Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Chapter Three
Multicomponent Distillation
A) Flash or Equilibrium Distillation

Flash distillation consists of vaporizing a definite fraction of liquid in such a way that the
evolved vapour is in equilibrium with the residue liquid, separating the vapour from the liquid
and condensing the vapour if desired as a product.
Vapor
V, yi

Heater
Feed
F, zi Valve
reduce P
Q
Liquid
L, xi

when we fed the feed in the flash drum should be two phases saturated liquid and saturated
vapor. we have to check feed are two phases by using bubble point calculation and dew point
calculation.

1. Bubble point calculations

𝑥𝑖 are known, find the set of K-values that satisfies
∑ 𝐾𝑖 𝑥𝑖 = 1.0 (3.1)

It can be doing by two ways Bubble point T , P is known

or Bubble point P , T is known

2. Dew point calculations

𝑦𝑖 are known, find the set of K-values that satisfies

𝑦𝑖
∑ = 1.0 (3.2)
𝐾𝑖

It can be doing by two ways Dew point T , P is known

or Dew point P , T is known

Flash calculations 𝑇𝑑𝑒𝑤 > 𝑇𝑓𝑒𝑒𝑑 > 𝑇𝑏𝑢𝑏𝑏𝑙𝑒 at constant P

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Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

OR 𝑃𝑑𝑒𝑤 > 𝑃𝑓𝑒𝑒𝑑 > 𝑃𝑏𝑢𝑏𝑏𝑙𝑒 at constant T

Material balance 𝐹 =𝑉+𝐿 (3.3)

Component balance 𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿𝑥𝑖 (3.4)

𝐿 =𝐹−𝑉 (3.5)

𝐹𝑧𝑖 = 𝑉𝑦𝑖 + (𝐹 − 𝑉 )𝑥𝑖 (3.6)

𝑦𝑖 𝑦𝑖
But 𝐾𝑖 = , 𝑥𝑖 =
𝑥𝑖 𝐾𝑖

𝑦𝑖
𝐹𝑧𝑖 = 𝑉𝑦𝑖 + (𝐹 − 𝑉 ) (3.7)
𝐾𝑖

For 1.0 lbmole or kgmole of feed ∴ 𝐹 = 1.0

𝐾𝑖 𝑧𝑖 = 𝑉𝑦𝑖 𝐾𝑖 + 𝑦𝑖 + 𝑉𝑦𝑖

𝐾𝑖 𝑧𝑖 = 𝑉𝑦𝑖 (𝐾𝑖 − 1) + 𝑦𝑖

𝐾𝑖 𝑧𝑖 = 𝑦𝑖 [𝑉 (𝐾𝑖 − 1) + 1]

𝐾𝑖 𝑧𝑖 𝐾𝑖 𝑧𝑖
𝑦𝑖 = , ∑ 𝑦𝑖 = 1.0 = ∑ (3.8)
[𝑉 (𝐾𝑖 − 1) + 1] [𝑉 (𝐾𝑖 − 1) + 1]

i) For Binary systems

Vapor

D, yD

Feed

F, xF

Liquid

W, xW

F = total moles of feed (A+B)

D = total vapour produced (A+B)
W = total liquid produced (A+B)
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Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

𝑥𝐹 composition of the more volatile component in the feed, mole fraction

𝑦𝐷 composition of the more volatile component in the top product (vapor), mole fraction
𝑥𝑊 composition of the more volatile component in bottom (liquid), mole fraction

Total material balance 𝐹 =𝐷+𝑊

Component material balance 𝐹𝑥𝐹 = 𝐷𝑦𝐷 + 𝑊𝑥𝑊

𝐷𝑦𝐷 = 𝐹𝑥𝐹 − 𝑊𝑥𝑊

𝐹 𝑊
𝑦𝐷 = 𝑥𝐹 − 𝑥𝑊
𝐷 𝐷

On the basis of 1 mole of feed 𝐹 = 1.0.

Let 𝑓 be the molal fraction of the feed that is vaporized (1 − 𝑓) molal fraction of the liquid
left.
𝐹 = 1, 𝐷 = 𝑓 , and 𝑊 = (1 − 𝑓 )

𝑥𝐹 (1 − 𝑓)
𝑦𝐷 = − 𝑥𝑊 (3.9)
𝑓 𝑓

(1−𝑓) 𝑥𝐹
𝑦𝐷 = − 𝑥𝑊 + (straight line equation)
𝑓 𝑓
Vapor
f

Feed
F = 1 mole

Liquid
(1-f)
(1−𝑓)
Slope is −
𝑓
𝑥𝐹
Intercept of equation is
𝑓
(1−𝑓)
The equation a straight line with a slope of − and can be plotted on the equilibrium
𝑓
diagram, the coordinates the inter section of the line and the equilibrium curve are at 𝑥 = 𝑥𝑊
and 𝑦 = 𝑦𝐷 .

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Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Equilibrium curve

yD

y Slope = - [(1-f)/f]

xW xF
x
The intersection of the material balance line and the diagonal 𝑦 = 𝑥 can be used as a point on
the line.

ii) For Multicomponent systems

Equation (3.9) can be written for each component as

𝑥𝐹𝑖 (1 − 𝑓)
𝑦𝐷𝑖 = − 𝑥𝑊𝑖 (3.10)
𝑓 𝑓
For 𝑖 = 1, 2, 3, … … … , 𝑛 where n = the number of components

Since the distillate and the bottom product are at equilibrium

1) If the system is ideal (Roualt’s law)

𝑃𝑡 𝑦𝑖 = 𝑥𝑖 𝑃𝑖∗ (3.11)

2) If the system is vapor ideal & liquid non ideal (modified Roualt’s law)
𝑃𝑡 𝑦𝑖 = 𝛾𝑖 𝑥𝑖 𝑃𝑖∗ (3.12)

3) If the system is vapor non ideal & liquid non ideal (Real system)
𝑃𝑡 𝑦𝑖 𝜙𝑖𝑣 = 𝛾𝑖 𝑥𝑖 𝜙𝑖𝑙 (3.13)
𝑦
Distribution coefficient 𝐾𝑖 = 𝑥𝑖
𝑖

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 University of Tripoli
Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

1) ideal system (Roualt’s law)

𝑦𝑖 𝑃𝑖∗
𝐾𝑖 = = (3.14)
𝑥𝑖 𝑃𝑡

2) Non ideal liquid and ideal vapor (Modified Roualt’s law)

𝑦𝑖 𝛾𝑖 𝑃𝑖∗
𝐾𝑖 = = (3.15)
𝑥𝑖 𝑃𝑡

3) Non ideal liquid and vapor (Real system)

𝑦𝑖 𝛾𝑖 𝜙𝑖𝑙
𝐾𝑖 = = (3.16)
𝑥𝑖 𝑃𝑡 𝜙𝑖𝑣

The use of relative volatility

𝐾𝑖 = 𝑘𝑏 𝛼𝑖𝑏 (3.17)

𝑦𝑖 ⁄𝑥𝑖 𝑦𝑖 𝑥𝑏
𝛼𝑖𝑏 = = (3.18)
𝑦𝑏 ⁄𝑥𝑏 𝑥𝑖 𝑦𝑏

𝑘𝑏 = is a base component chosen usually as the least volatile component in the system

Equation (3.9) can be written as

1
𝑦𝐷𝑖 = [𝑥 − (1 − 𝑓)𝑥𝑊𝑖 ] (3.19)
𝑓 𝐹𝑖

Divide Equation (3.19) by 𝑥𝑤𝑖 gives

𝑦𝐷𝑖 1 𝑥𝐹𝑖
= [ − (1 − 𝑓 ) ] (3.20)
𝑥𝑤𝑖 𝑓 𝑥𝑤𝑖

1 𝑥𝐹𝑖
𝐾𝑖 = [ − (1 − 𝑓 ) ] (3.21)
𝑓 𝑥𝑤𝑖

1 𝑥𝐹𝑖
𝐾𝑖 = 𝑘𝑏 𝛼𝑖𝑏 = [ − (1 − 𝑓 ) ] (3.22)
𝑓 𝑥𝑤𝑖
Equation (3.22) can be solved for 𝑥𝑤𝑖
𝑥𝐹𝑖
𝐾𝑖 𝑓 + (1 − 𝑓) = (3.23)
𝑥𝑤𝑖

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Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

𝑥𝐹𝑖
𝑥𝑤𝑖 = (3.24)
𝐾𝑖 𝑓 + (1 − 𝑓)
𝑥𝐹𝑖
𝑥𝑤𝑖 = (3.25)
[𝑘𝑏 𝛼𝑖𝑏 𝑓 + (1 − 𝑓)]

Summering overall components gives

𝑛

∑ 𝑥𝑤𝑖 = 1.0
𝑖=1
𝑛
𝑥𝐹𝑖
1.0 = ∑ { } (3.26)
[𝐾𝑖 𝑓 + (1 − 𝑓)]
𝑖=1

𝑛
𝑧𝑖 (𝐾𝑖 − 1)
𝐹 (𝑣 ) = ∑ { }=0 (3.27)
[1 + 𝑣 (𝐾𝑖 − 1)]
𝑖=1
B) Differential Distillation

In this process the vapour formed on boiling the liquid is removed at once from the system.
Since this vapour is richer in the more volatile component than the liquid it follows that the
liquid remaining becomes steady weaker in the more volatile component (m.v.c.) with the
result that the composition of the product is progressively alters. while the vapour formed
over a short period is in equilibrium with the liquid the total vapour produced is not in
equilibrium with the residue liquid. At the end of the process the liquid which has not been
vaporized is removed as a bottom product
Let:
𝑆 = moles of the material in the still.
𝑥 = mole fraction of the component 𝐴 (mole volatile component) m.v.c.
Suppose an amount 𝑑𝑆 containing a mole fraction y of 𝐴 be vaporized.
Amount left in the liquid = 𝑆 − 𝑑𝑆.

Still Q (heat)

Original amount = amount left in the liquid + amount in the vapour

𝑆 𝑥 = (𝑆 − 𝑑𝑆)(𝑥 − 𝑑𝑥) + 𝑑𝑆 𝑦

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Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

𝑆 𝑥 = 𝑆𝑥 − 𝑑𝑆 𝑥 − 𝑆𝑑𝑥 + 𝑑𝑆 𝑑𝑥 + 𝑑𝑆 𝑦

𝑆 𝑥 = 𝑆𝑥 − 𝑑𝑆 𝑥 − 𝑆𝑑𝑥 + 𝑑𝑆 𝑑𝑥 + 𝑑𝑆 𝑦

Neglect 𝑑𝑆 × 𝑑𝑥 ≅ 0
𝑑𝑆 𝑥 + 𝑆𝑑𝑥 = 𝑑𝑆 𝑦

𝑆𝑑𝑥 = 𝑑𝑆 (𝑦 − 𝑥)

𝑑𝑥 𝑑𝑆
= (3.27)
(𝑦 − 𝑥 ) 𝑆

i) For Binary systems

Integrate:
𝑆1 𝑥1
𝑑𝑆 𝑑𝑥
∫ =∫ (3.28)
𝑆2 𝑆 𝑥2 (𝑦 − 𝑥 )

1/(y-x)
1/(y-x)

𝑥1
𝑆1 𝑑𝑥
𝑙𝑛 = ∫
𝑆2 𝑥2 (𝑦 − 𝑥 )

x2 x1
x

S1: original total moles.

S2: total moles of residue liquid.
x1: original composition of the (m.v.c.) in the original liquid.
x2: composition of the (m.v.c.) in the residue.

𝑆1 𝑥1 𝑆1 (1 − 𝑥1 )
𝑙𝑛 ( ) = 𝛼𝑎𝑏 𝑙𝑛 [ ] (3.29)
𝑆2 𝑥2 𝑆2 (1 − 𝑥2 )

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 University of Tripoli
Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

ii) For Multicomponent systems

You have to choose a base component and you apply the above Equation (3.29) for any two
components

𝑆1 𝑥𝑖1 𝑆1 (𝑥𝑏𝑖 )
𝑙𝑛 ( ) = 𝛼𝑖𝑏 𝑙𝑛 [ ] (3.29)
𝑆2 𝑥𝑖2 𝑆2 (𝑥𝑏2 )

𝑃𝑖∗
𝛼𝑖𝑏 = ∗
𝑃𝑏

Example 3.1
A mixture of 33% n-haxane 33% n-heptane, and 34% n-Octane is to be subjected to a flash
distillation at 1 atm 60% of the feed is vaporized find the temperature of the flash and the
composition of the products
‫في البداية يجب معرفة درجتان الحرارة التي يكون فيها الخليط في حالة تشبع طورين وعليه يجب حساب درجة التشبع لطور السائل‬
‫ودرجة التشبع لطور البخاري حتى نقترب من الحل الصحيح‬
a) Bubble point temperature calculation (saturated liquid)
b) Dew point temperature calculation (saturated vapor)
‫باستخدام قانون رولتز لحساب التراكيب ومعرفة درجة الحرارة التي تم فيها الفصل حسب معطيات المساله سنحتاج حساب الضغط‬
‫البخاري للمركبات باستخدام معادلة انطوني‬
𝐵
𝑙𝑛𝑃∗ = 𝐴 + 𝑃∗ , 𝑘𝑃𝑎 𝑎𝑛𝑑 𝑇, 𝐶 𝑜
𝑇, 𝐶 𝑜 + 𝐶
A B C
n-hexane 13.8193 2696.04 224.317
n-heptane 13.8622 2910.26 216.432
n-octane 13.9346 3123.13 209.635

From Equation (3.14)

𝑛 𝑛
𝑥𝑖 𝑃𝑖∗
∑ 𝑦𝑖 = 1.0 = ∑ 𝐵𝑢𝑏𝑏𝑙𝑒 𝑝𝑜𝑖𝑛𝑡
𝑃𝑡
𝑖=1 𝑖=1
𝑛 𝑛
𝑦𝑖 𝑃𝑡
∑ 𝑥𝑖 = 1.0 = ∑ 𝐷𝑒𝑤 𝑝𝑜𝑖𝑛𝑡
𝑃𝑖∗
𝑖=1 𝑖=1

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 University of Tripoli
Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

𝑇𝐵𝑢𝑏𝑏𝑙𝑒 = 90.5𝑜 𝐶
} 𝑎𝑡 𝑃𝑡 = 1 𝑎𝑡𝑚
𝑇𝐷𝑒𝑤 = 105.5𝑜 𝐶
Using the flash Equation

𝑛=3
𝑥𝐹𝑖
1.0 = ∑
𝑓 (𝑘𝑏 𝛼𝑖𝑏 − 1) + 1
𝑖=1

𝑓 = 0.6, Let base component is n-Octane (least volatile)

Assume 𝑻 = 𝟗𝟓𝒐 𝑪
∗ ∗ ∗
𝑃𝐶6 = 216.189 𝑘𝑃𝑎 , 𝑃𝐶7 = 91.6 𝑘𝑃𝑎 , 𝑃𝐶8 = 39.748 𝑘𝑃𝑎

𝑃1∗ 216.189 𝑃2∗ 91.6 𝑃𝑏∗ 39.748

𝐾1 = = = 2.1402, 𝐾2 = = = 0.9081 , 𝐾𝑏 = = = 0.3935
𝑃𝑡 101.013 𝑃𝑡 101.013 𝑃𝑡 101.013

𝐾1 2.1402 𝐾2 0.9081 𝐾𝑏 0.3935

∝1𝑏 = = = 5.4389, ∝2𝑏 = = = 2.3045 , ∝𝑏 = = = 1.0
𝐾𝑏 0.3935 𝐾𝑏 0.3935 𝐾𝑏 0.3935
3
0.33 0.33
∑ 𝑥𝑤𝑖 = +
0.6[(0.3935 × 2.3045 − 1) + 1] 0.6[(0.3935 × 5.439 − 1) + 1]
𝑖=1
0.34
+ = 1.08
0.6[(0.3935 × 1 − 1) + 1]
This trial is not correct

By using solver software in Excel sheet it can be obtained Temperature (99.89oC)

𝑥𝑊1 = 0.1775 , 𝑥𝑊1 = 0.3207 , 𝑥𝑊1 = 0.5017
𝑦𝑖 = 𝐾𝑏 𝛼𝑖𝑏 𝑥𝑖
𝑦1 = 0.4316 , 𝑦2 = 0.3361 , 𝑦3 = 0.2322

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 University of Tripoli
Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Example 3.2
A liquid containing 50% benzene, 25% toluene, and 25% o-xylene is differentially distilled at 1 atm
32.5% by mole of the total feed is distilled compute the distillate and residue composition.
Basis: 100 of feed
𝑆1 = 100 𝑚𝑜𝑙𝑒𝑠 , 𝐷 = 32.5 𝑚𝑜𝑙𝑒𝑠
𝑆2 = 𝑆1 − 𝐷 = 100 − 32.5 = 67.5 𝑚𝑜𝑙𝑒𝑠
𝑆1 𝑥𝑖1 𝑆1 (𝑥𝑏𝑖 )
𝑙𝑛 ( ) = 𝛼𝑖𝑏 𝑙𝑛 [ ]
𝑆2 𝑥𝑖2 𝑆2 (𝑥𝑏2 )

‫ لمعرفة ماذا نفرض من درجة الحرارة‬Bubble point Temperature ‫الغرض من معرفة‬

Bubble point Temperature calculation: By using Roualt’s law and Antoine’s Equation

𝑦𝑖 𝑃𝑖∗
𝐾𝑖 = = 𝑓𝑜𝑟 𝑖𝑑𝑒𝑎𝑙 𝑠𝑦𝑠𝑡𝑒𝑚
𝑥𝑖 𝑃𝑡
𝐵
𝑙𝑛𝑃 ∗ = 𝐴 + 𝑃∗ , 𝑚𝑚𝐻𝑔 𝑎𝑛𝑑 𝑇, 𝐾 𝑜
𝑇, 𝐾 𝑜 + 𝐶
A B C
BENZENE 15.9008 2788.51 -52.36
TOLUENE 16.0137 3096.52 -53.67
O-XYLENE 16.1156 3395.57 -59.46

𝑛 𝑛
𝑥𝑖 𝑃𝑖∗
∑ 𝑦𝑖 = 1.0 = ∑ 𝐵𝑢𝑏𝑏𝑙𝑒 𝑝𝑜𝑖𝑛𝑡
𝑃𝑡
𝑖=1 𝑖=1

𝑇𝐵𝑢𝑏𝑏𝑙𝑒 = 95.5𝑜 𝐶 , 𝑎𝑡 𝑃𝑡 = 1 𝑎𝑡𝑚

Assume the temperature 100𝑜 𝐶 as average

T, C T, K P*, mmHg αib = ki/kb xi yi Equations

100 373.15 1350.414 2.42744994 0.382035 0.745 3E-07
556.3096 1 0.281951 0.18364 1.86E-08
198.5411 0.3568896 0.336014 0.07135
1 1

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

zi Ki P*i αib
BENZENE 0.5 1.77686 1350.4136 2.42744994
TOLUENE 0.25 0.73199 556.30955 1
O-XYLENE 0.25 0.26124 198.54109 0.3568896

Apply Equation
100 × 0.5 100 × 0.25
𝑙𝑛 ( ) = 2.42745 𝑙𝑛 [ ] ( 3.30)
67.5 𝑥1 67.5 𝑥𝑏

100 × 0.25 100 × 0.25

𝑙𝑛 ( ) = 0.356889 𝑙𝑛 [ ] ( 3.31)
67.5 𝑥3 67.5 𝑥𝑏

𝑥1 + 𝑥𝑏 + 𝑥3 = 1.0 (3.32)

Solving simultaneously the Equations (3.30), (3.31), and (3.32) by assuming values if 𝑥𝑏 computing
𝑥1 and 𝑥3 checking the sum until it equals unity by using solver software in Excel.
From component balance you can get 𝑦𝑖
𝑆1 𝑧1 = 𝐷𝑦1 + 𝑆2 𝑥1 (3.33)

zi xi yi
BENZENE 0.5 0.382035 0.745
TOLUENE 0.25 0.281951 0.18364
O-XYLENE 0.25 0.336014 0.07135

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 University of Tripoli
Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

C) Multicomponent Rectification Distillation - Shortcut Methods

While we can graphically solve a binary component distillation system using the McCabe-
Thiele method or Ponchon Savarit Method, it is also possible to do a complete analytical
solution using mass and energy balances with the equilibrium relationship.
However, for multi-component systems, C > 2, one would find that the number of equations
obtained from mass and energy balances with the equilibrium relationship will always be one
less than the number of unknowns.
‫ قد تجد أن عدد المعادالت التي تم الحصول عليها‬، 2 ‫ بالنسبة لألنظمة متعددة المكونات اي عدد المركبات أكثر من‬، ‫ومع ذلك‬
.‫من موازين الكتلة والطاقة مع عالقة التوازن سيكون دائ ًما أقل من عدد المجاهيل‬
Consequently, one cannot do a complete analytical solution for multi-component distillation –
it requires a trial-and-error solution with the additional unknown assumed to be known, as
well as special considerations as to enhancing convergence of the solution.
‫ فهو يتطلب حالً بستخدام محاوالت الصح والخطأ‬- ‫ ال يمكن أن يقوم بحل تحليلي كامل للتقطير متعدد المكونات‬، ‫وبالتالي‬
‫ باإلضافة إلى اعتبارات خاصة لتعزيز تقارب الحل‬، ‫مع افتراض أن المجهول اإلضافي معروف‬

MCD – Practical calculation methods

Fortunately, numerical design packages, such as Aspen Plus, and Aspen Hysys have been
developed to perform the rigorous solution of multi-component distillation systems.
However, as a design engineer, one always needs to know the underlying theory and methods
of calculation to enable one to make decisions about the validity of these “off–the– shelf”
packages and to verify the results.

MCD – Additional Terminologies

Introducing some new terminology in addition to the terms used in binary distillation:
❖ Fractional recoveries
❖ Key components
❖ Non-key components
❖ Splits – distributing and non-distributing systems
Note that binary systems can be handled in the same terms.

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MCD – Fractional Recoveries

A fractional recovery, FRi, is the amount or flow rate of component i in the distillate or
bottoms stream with respect to the amount or flow rate of component i in the feed stream:
(𝐷𝑥𝑖 )𝐷 𝐷𝑥𝐷,𝑖
(𝐹𝑅𝑖 )𝐷 = = (3.34)
𝐹𝑧𝐹,𝑖 𝐹𝑧𝐹,𝑖
(𝐷𝑥𝑖 )𝑊 𝑊𝑥𝑊,𝑖
(𝐹𝑅𝑖 )𝑊 = = (3.35)
𝐹𝑧𝐹,𝑖 𝐹𝑧𝐹,𝑖
(𝐹𝑅𝑖 )𝐷 = 1 − (𝐹𝑅𝑖 )𝑊 (3.36)
(𝐹𝑅𝑖 )𝑊 = 1 − (𝐹𝑅𝑖 )𝐷 (3.37)
It is the simple relationships expressed by the right-hand-side equations that make the use of
fractional recoveries useful.
These are also often specified simply as % recovery.

MCD – Key Components

❖ The components that have their distillate and bottoms composition specified are known as the
key components.
❖ The most volatile of the key components is termed the light key (LK).
❖ The least volatile of the key components is termed the heavy key (HK).
❖ All other components not specified in the distillate or bottoms are termed non-key components
(NK’s).

The light key:

It is the lightest component that will appear in the bottom stream in any appreciable quantity. It
should have enough information to specify its recovery in the distillate product.

The heavy key:

It is the heaviest component appearing in the distillate in any appreciable quantity. It should have
enough information to be specifying its recovery in the bottom product.
The main purpose of the fractionation is the separation of the light key from the heavy key.

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Multicomponent Distillation

Relative volatility:
It is always computed with expect to the heavy key
𝐾𝑖
∝𝑖−ℎ𝑘 = (3.38)
𝐾ℎ𝑘
If the system is ideal
𝑃𝑖∗
∝𝑖−ℎ𝑘 = ∗ (3.39)
𝑃ℎ𝑘
∝ℎ𝑘−ℎ𝑘 = 1, ∝ ′𝑠 for components lighter than the heavy key > 1.0 and for heavier than the heavy
key < 1.0.

Fenske-Underwood-Gilliland Method (FUG)

❑ Approximate methods are used in various purposes
o Preliminary design.
o Parametric studies to establish optimum design conditions.
o To determine optimal separation sequences
❑ Most widely method is commonly referred to as Fenske-Underwood-Gilliland (FUG)
method.

Approximate methods – FUG method

Gilliland correlation
Underwood – determining
– Rmin number of stages at
Fenske – finite reflux
calculate Nmin

Estimating the
composition and product
flow rates

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Multicomponent Distillation

𝑵𝒎𝒊𝒏 – Fenske Equations

𝑥𝐷 ⁄𝑥𝑊
𝑙𝑛 ( 𝐿𝐾 ⁄ 𝐿𝐾 )
𝑥𝐷𝐻𝐾 𝑥𝑊𝐻𝐾
𝑁𝑚𝑖𝑛 = (3.40)
̅ 𝐿,𝑎𝑣𝑔
𝑙𝑛 ∝

̅ 𝐿,𝑎𝑣𝑔 = √∝𝐿𝐷 ∝𝐿𝑊

∝ (3.41)

𝐾 𝑃∗
∝𝐿𝐷 = relative volatility of light key at distillate temperature = 𝐾 𝐿𝐾,𝐷 = 𝑃𝐿𝐾,𝐷
∗
𝐻𝐾,𝐷 𝐻𝐾,𝐷

𝐾 𝑃∗𝐿𝐾,𝑊
∝𝐿𝑊 = relative volatility of light key at bottom temperature= 𝐾 𝐿𝐾,𝑊 =
𝐻𝐾,𝑊 𝑃∗𝐻𝐾,𝑊

𝐾𝐿𝐾,𝐷 = equilibrium constant (K-value) for light key component at distillate temperature.
𝐾𝐻𝐾,𝐷 = equilibrium constant (K-value) for heavy key component at distillate temperature.
𝐾𝐿𝐾,𝑊 = equilibrium constant (K-value) for light key component at bottom temperature.
𝐾𝐻𝐾,𝑊 = equilibrium constant (K-value) for heavy key component at bottom temperature.
𝑃∗𝐿𝐾,𝐷 = vapor pressure for light key component at distillate temperature.
𝑃∗𝐻𝐾,𝐷 = vapor pressure for heavy key component at distillate temperature.

̅𝑁
∝𝑘𝑗
𝑚𝑖𝑛

𝐹𝑅𝑘 = (3.42)
𝐹𝑅𝑗,𝑊
̅ 𝑁𝑚𝑖𝑛
1 − 𝐹𝑅𝑗,𝑊 +∝𝑘𝑗

𝐹𝑅𝑘 = fraction recovery of component k.

̅ 𝑘𝑗 =
∝ average relative volatility component k to heavy key at distilled, bottom and feed.
𝐹𝑅𝑗,𝑊 = fraction recovery of heavy key in the bottom.

̅ 𝑘𝑗 = 3√∝𝐷𝑘𝑗 ∝𝐹𝑘𝑗 ∝𝑊𝑘𝑗

∝ (3.43)

∝𝐷𝑘𝑗 = relative volatility component k to heavy key at distillate temperature

∝𝐹𝑘𝑗 = relative volatility component k to heavy key at feed temperature

∝𝑊𝑘𝑗 = relative volatility component k to heavy key at bottom temperature

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Example 3.3
A distillation column with a total condenser is being used to separate a mixture of benzene, toluene,
and 1,2,3-trimethylbenzene. The feed, 40 mol% benzene, 30 mol% toluene, and 30 mol% 1,2,3-
trimethylbenzene enters the column as saturated vapor. We desire to 95% recovery of the toluene in
the distillate and 95% recovery of 1,2,3-trimethylbenzene in the bottom. The reflux is returned as a
saturated liquid, and constant molar overflow can be assumed. The column operates at a pressure of 1
atm. Find the number of equilibrium stages required at total reflux, and the recovery fraction of
benzene in the distillate. Solutions of benzene, toluene, and 1,2,3-trimethylbenzene are ideal

D
D×xB = ?
D×xT = √
D×xTMB = √

xB = 0.4 F
xT = 0.3
xTMB = 0.3

W W×xB = ?
W×xT = √
W×xTMB = √

Component mass balance to obtain the product compositions and flow rates

Guess #1: assuming all of the LNK to be recovered in the distillate

Component %recovery classifications xF F×xF D×xD W×xW xD xW
B 100 LNK 0.4 40 40 0 0.57 0
T 95 LK 0.3 30 28.5 1.5 0.41 0.05
TMB 95 HK 0.3 30 1.5 28.5 0.02 0.95
Sum = 1 100 70 30 1.00 1

Benzene: B F= 100
Toluene: T D= 70
1,2,3trimethylbenzene: TMB W= 30

TW , K = 442.3 bubble point calculation using Raoult's law

TD , K = 363.6 bubble point calculation using Raoult's law
TF , K = 424 dew point calculation using Raoult's law

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Multicomponent Distillation

Tbubble,D,W P*, T P*, TMB P*I /P*HK

(T-TMB)W 442.3 3121.02 637.047 4.9
(T-TMB)D 363.6 412.679 48.2536 8.55
(T-TMB)avg 6.47

Tbubble,D,W P*, B P*, TMB P*I /P*HK

(B-TMB)W 442.3 6308.63 637.047 9.9029261
(B-TMB)F 424 4436.16 386.868 11.466851
(B-TMB)D 363.6 1034.26 48.2536 21.433902
(B-TMB)avg 13.45147

̅ 𝐿,𝑎𝑣𝑔 = √∝𝐿𝐷 ∝𝐿𝑊 = √4.899 × 8.552 = 6.47

∝

3
̅ 𝑘𝑗 = 3√∝𝐷𝑘𝑗 ∝𝐹𝑘𝑗 ∝𝑊𝑘𝑗 = √9.903 × 11.467 × 21.434 = 13.45
∝

𝑥𝐷𝑖 ⁄𝑥𝑊𝑖 0.41⁄0.05

𝑙𝑛 ( ) ln ( )
𝑥𝐷𝑗 ⁄𝑥𝑊𝑗 0.02⁄0.95
𝑁𝑚𝑖𝑛 = = = 3.15
̅ 𝐿,𝑎𝑣𝑔
𝑙𝑛 ∝ ln (6.47)

̅𝑁
∝ 𝑚𝑖𝑛
𝑘𝑗 13.453.15
𝐹𝑅𝑘 = = = 0.995
𝐹𝑅𝑗,𝑊 0.95
̅ 𝑁𝑚𝑖𝑛 + 13.453.15
1 − 𝐹𝑅𝑗,𝑊 +∝𝑘𝑗 1 − 0.95

Recalculation of the composition based on the benezene recovery

Component %recovery classifications xF F×xF D×xD W×xW xD xW
B 99.5 LNK 0.4 40 39.80 0.20 0.5686 0.0067
T 95 LK 0.3 30 28.50 1.50 0.4071 0.0500
TMB 95 HK 0.3 30 1.50 28.50 0.0214 0.9500
Sum = 1 100 69.80 30.20 0.9971 1.0067
‫ ر‬، bubble point in distilled and bottom ‫ وإعادة حساب‬، ‫ باستخدام تركيبة نواتج التقطي الجديدة‬، ‫ومن ثم‬
‫بافياض‬ ‫ر‬
ً
‫جدا من ال رت تم الحصول عليها عندما تكون كمية ر‬ ‫ر‬
‫التقطي‬
‫ر‬ ‫افياض نواتج‬ ‫ي‬ ‫تعط قيمة محسوبة قريب‬
‫ي‬ ‫والت سوف‬
‫درجات جديدة ي‬
. Nmin ‫تتغي ويتم اعتماد‬
‫ لن ر‬bubble point in top and bottom. ‫ فإن‬، ‫البيين ومن ثم‬‫ للمركب ز ز‬%100 ‫عىل أنها‬

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Nmin‫ فأن القيم الجديدة يتم أستخدامها ز يف إعادة حساب‬، ‫تغيت‬

‫ ر‬bubble point in top or bottom ‫إذا كان أي من درجات‬

𝑹𝒎𝒊𝒏 – Underwood Equations

∝𝑖 𝐷 𝑥𝑖,𝐷 ∝𝑖 𝑊 𝑥𝑖,𝑊
𝑉𝑚𝑖𝑛 = ∑ 𝑎𝑛𝑑 − 𝑉𝑠𝑡,𝑚𝑖𝑛 = ∑ (3.44)
∝𝑖 − 𝚽 ∝𝑖 − 𝚽𝒔𝒕
𝑖 𝑖

This equation is referred to as the second Underwood equation and it is used to calculate 𝑉𝑚𝑖𝑛 and
once 𝑉𝑚𝑖𝑛 is known, 𝐿𝑚𝑖𝑛 is calculated from the mass balance : 𝐿𝑚𝑖𝑛 = 𝑉𝑚𝑖𝑛 − 𝐷

𝛼𝑖 𝑧𝑖
1 − 𝑞 = ∑[ ] (3.45)
𝛼𝑖 − 𝚽
𝑖

This is known as the first Underwood equation. It can be used to calculate appropriate values for .

Solution of the first Underwood equation

𝛼𝑖 𝑧𝑖
1 − 𝑞 = ∑[ ]
𝛼𝑖 − 𝚽
𝑖

Case I Case II Case III

Distributions of all Distributions of Nonkey Distributions of Nonkey
components are known components can be predicted components are not known

Note:  in the first Underwood equation has more than one solution (number of solutions equals the
number of components in the system).

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Multicomponent Distillation

How to determine 𝑽𝒎𝒊𝒏

∝𝑖 𝐷 𝑥𝑖,𝐷 ∝𝑖 𝑊 𝑥𝑖,𝑊 𝛼𝑖 𝑧𝑖
𝑉𝑚𝑖𝑛 = ∑ 𝑎𝑛𝑑 − 𝑉𝑠𝑡,𝑚𝑖𝑛 = ∑ 1 − 𝑞 = ∑[ ]
∝𝑖 − Φ ∝𝑖 − Φ𝑠𝑡 𝛼𝑖 − Φ
𝑖 𝑖 𝑖

Case I Case II
Distributions of all Distributions of Nonkey
components are known components can be predicted

αHK < Φ < αLK

Number of unknowns are one (only 𝑉𝑚𝑖𝑛 ) and number of equations is one (using one solution of Φ)

∝𝑖 𝐷 𝑥𝑖,𝐷 ∝𝑖 𝑊 𝑥𝑖,𝑊 𝛼𝑖 𝑧𝑖
𝑽𝒎𝒊𝒏 = ∑ 𝑎𝑛𝑑 − 𝑉𝑠𝑡,𝑚𝑖𝑛 = ∑ 1−𝑞 = ∑[ ]
∝𝑖 − Φ ∝𝑖 − Φ𝑠𝑡 𝛼𝑖 − 𝚽
𝑖 𝑖 𝑖

Case III
Distributions of Nonkey
components are not known

In this case we have to use a number of solutions of Φ that is required to set up a number of equations
that equals to the number of unknowns.
For example, there is one nonkey component for which we don’t know its distribution (i.e. we don’t
know its amount in the distillate 𝑥𝑁𝐾,𝐷 × 𝐷 =?). Thus we have two unknowns(𝑉𝑚𝑖𝑛 , 𝑎𝑛𝑑 𝑥𝑁𝐾,𝐷 × 𝐷),
and therefore we need to use two solutions of (Φ1 𝑎𝑛𝑑 Φ2 ), in the second Underwood equation.

Where 1 < Φ1 < 𝛼𝑁𝐾−𝐻𝐾

𝛼𝑁𝐾−𝐻𝐾 < Φ2 < 𝛼𝐿𝐾−𝐻𝐾

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Shiras et al. (1950)

Developed the following equation to determine whether or not a component is distributed at
minimum reflux. This equation is very useful in cases where there is nonkey between light and heavy
keys.
𝛼𝑖 − 1 𝛼𝐿𝐾 − 𝛼𝑖
𝐷𝑖,𝑅 = 𝐹𝑅𝐿𝐾,𝐷 + 𝐹𝑅𝐻𝐾,𝐷 (3.45)
𝛼𝐿𝐾 − 1 𝛼𝐿𝐾 − 1

Shiras et al. criterion applies at minimum reflux as follows:

𝐷𝑖,𝑅 > 1 Component is not distributed; contained entirely in distillate.
0 < 𝐷𝑖,𝑅 < 1 Component is distributed; component appears in both distillate and bottoms.
𝐷𝑖,𝑅 < 0 Component in not distributed; contained entirely in the bottoms.

Solution procedure: For example if there is C (number of components) whose their distributions are
unknown then an exact solution without further assumptions is needed. Solving the first Underwood
equation and find the roots of Φ′𝑠 (equals C+1). Then solving the second Underwood equation
simultaneously for all values of Φ to obtain 𝑉𝑚𝑖𝑛 and the amount of each unknown nonkeys in the
distillate.

Gilliland correlation for actual reflux ratio

- The Gilliland correlation provides an approximate relationship between number of stages and
reflux ratio so that an optimal reflux ratio can be determined with a minimum of calculations.
- Gilliland did a series of accurate stage-by-stage calculations and found that he could correlate
the variable
𝑁 − 𝑁𝑚𝑖𝑛
𝑌= (3.46)
𝑁+1
With the variable
𝑅 − 𝑅𝑚𝑖𝑛
𝑋= (3.47)
𝑅+1

The original Gilliland correlation was graphical. Molkanov et al (1972) fit the Gilliland correlation to
the equation
1 + 54.4𝑋 𝑋 − 1
𝑌 = 1 − 𝑒𝑥𝑝 [ ( )] (3.48)
11 + 117.2𝑋 𝑋 0.5

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

𝑅 − 𝑅𝑚𝑖𝑛
𝑋= (3.49)
𝑅+1

𝑁 − 𝑁𝑚𝑖𝑛 1 + 54.4𝑋 𝑋−1

𝑌= = 1 − 𝑒𝑥𝑝 [( ) ( 0.5 )] (3.50)
𝑁+1 11 + 117.2𝑋 𝑋

Optimum feed stage location

A reasonably good approximation of optimum feed stage location can be made by employing the
empirical equation of Kirkbride (1944)

2 0.206
𝑁𝑅 𝑧𝐻𝐾,𝐹 𝑥𝐿𝐾,𝑊 𝑊
=[ ( ) ] (3.51)
𝑁𝑆 𝑧𝐿𝐾,𝐹 𝑥𝐻𝐾,𝐷 𝐷

𝑁𝑅 = The number of theoretical stages above the feed plate

𝑁𝑆 = The number of theoretical stages below the feed plate

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Example 3.4

For the distillation problem described in Example (3.3), find the minimum reflux ratio. Use a basis of
100 kmol/h of feed.
𝛼𝑖 𝑧𝑖
1−𝑞 = ∑[ ]
𝛼𝑖 − Φ
𝑖

Component %recovery classifications xF F×xF D×xD W×xW xD xW

B 99.5 LNK 0.4 40 39.80 0.20 0.5686 0.0067
T 95 LK 0.3 30 28.50 1.50 0.4071 0.0500
TMB 95 HK 0.3 30 1.50 28.50 0.0214 0.9500
Sum = 1 100 69.80 30.20 0.9971 1.0067

 i Dx i ,D
V min = 
i i − 

By trial and error the value of Φ should be determined ∝𝐻𝐾 < Φ < 𝛼𝐿𝐾 or using solver software in
Excel.

Calculation of Φ
q= 0 Feed is saturated vapor Φ = 3.2613
component classifications xF αi-TMB xF × αi-TMB [xF ×αi-TMB]/[αi-TMB-Φ]
B LNK 0.4 13.4515 5.38 0.528
T LK 0.3 6.47 1.94 0.605
TMB HK 0.3 1 0.30 -0.133
0.999999822
1.77693E-07

Calculation of Vmin
component classifications xF αi-TMB xD × D [xDD×αi-TMB]/[αi-TMB-Φ]
B LNK 0.4 13.4515 39.80 52.538
T LK 0.3 6.47 28.50 57.441
TMB HK 0.3 1 1.50 -0.663
Vmin = 109.32
Lmin = 39.52
Rmin = 0.566

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Example 3.5

The feed to a depropanizer is 66% vaporized at the column inlet. The feed composition and average
relative volatilities are given in the table below. It is required that 98% of the propane in the feed is
recovered in the distillate, and 99% of the pentane is to be recovered in the bottoms product.
Calculate the minimum reflux ratio for this case using Underwood’s method.

Component Mole fraction in feed Relative volatility ()

Methane (LNK) 0.26 39.47
Ethane (LNK) 0.09 10
Propane (LK) 0.25 4.08
Butane (unknown) 0.17 2.11
Pentane (HK) 0.11 1
Hexane (HNK) 0.12 0.5

Check on 𝐂𝟒 using Shiras et al Equation

𝛼𝑖 − 1 𝛼𝐿𝐾 − 𝛼𝑖 (2.11 − 1) (4.08 − 2.11)

𝐷𝑖,𝑅 = 𝐹𝑅𝐿𝐾,𝐷 + 𝐹𝑅𝐻𝐾,𝐷 = 0.98 + 0.01 =
𝛼𝐿𝐾 − 1 𝛼𝐿𝐾 − 1 (4.08 − 1) (4.08 − 1)

𝐷𝐶4,𝑅 = 0.36

Component Butane will undoubtedly distribute because 0 < 𝐷𝑖,𝑅 < 1 , then component is
distributed; component appears in both distillate and bottoms.

FR (LK),D 0.98
FR (HK),D 0.01

Component Class. zF αi-HK Shiras et al value D×xD W×xW

Methane LNK 0.26 39.47 12.13 26 0
Ethane LNK 0.09 10 2.84 9 0
Propane LK 0.25 4.08 0.98 24.5 0.5
Butane Unknown 0.17 2.11 0.36 ? ?
Pentane HK 0.11 1 0.01 0.11 10.89
Hexane HNK 0.12 0.5 -0.15 0 12

Dr Mawaheb Mohamed Derdar Spring 2024

86
 University of Tripoli
Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

Solving the first Underwood equation

By trial and error the value of Φ1 should be determined 1 < Φ1 < 𝛼𝑁𝐾 and the value Φ2 should be
determined ∝𝐻𝐾 < Φ2 < 𝛼𝐿𝐾 or using solver software in Excel.

q = 0.34 Φ1 = 1.2629 1 < Φ1 < αi-HK

Solving the equation to obtain two
Φ2 = 2.8460 αi-HK < Φ2 < αi-LK
roots (C+1)

Component Class. zF αi-HK xF × αi-HK [xF × αi-HK]/[ αi-HK - Φ1 ] [xF × αi-HK]/[ αi-HK - Φ2 ]

Methane LNK 0.26 39.47 10.26 0.269 0.280

Ethane LNK 0.09 10 0.90 0.103 0.126
Propane LK 0.25 4.08 1.02 0.362 0.827
Butane Unknown 0.17 2.11 0.36 0.423 -0.487
Pentane HK 0.11 1 0.11 -0.418 -0.060
Hexane HNK 0.12 0.5 0.06 -0.079 -0.026
0.660 0.660
0.000 0.000

Solving the second Underwood equation

∝𝑖 𝐷 𝑥𝑖,𝐷
𝑽𝒎𝒊𝒏 = ∑ = 72.2 + 2.4908𝑫𝒙𝑪𝟒,𝑫 (1)
∝𝑖 − Φ1
𝑖

∝𝑖 𝐷 𝑥𝑖,𝐷
𝑽𝒎𝒊𝒏 = ∑ = 121.5 − 2.8670𝑫𝒙𝑪𝟒,𝑫 (2)
∝𝑖 − Φ 2
𝑖

‫ نحصل على معادلتين في مجهولين وبتالي تستطيع‬Φ2 ‫ و‬Φ1 ‫وبالتعويض في معادلة اندروود باستخدام الجذور االثنين‬
𝑉𝑚𝑖𝑛 ‫𝐶𝑥𝐷 وأصغر التدفق‬4,𝐷 ‫حلهما والحصول على كمية هذه المادة في أعلى البرج‬

Dr Mawaheb Mohamed Derdar Spring 2024

87
 University of Tripoli
Chemical Engineering Department
Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

solving the second Underwood equation to find Vmin and D*xButane,D

Vmin = 95.1523
Lmin = 26.337
Rmin = 0.383

Component Class. ai-HK D×xD [ αi-HK×D×xi,D ]/[αi - Φ1] [ αi-HK×D×xi,D ]/[αi - Φ2]

Methane LNK 39.47 26 26.9 28.0

Ethane LNK 10 9 10.3 12.6
Propane LK 4.08 24.5 35.5 81.0
Butane Unknown 2.11 9.20
Pentane HK 1 0.11 -0.4 -0.1
Hexane HNK 0.5 0 0.0 0.0
68.815 72.2 121.5
2.4908 -2.8670

Shiras et al
Component Class. zF αi-HK D×xD W×xW xD xW
value
Methane LNK 0.26 39.47 12.1256 26 0 0.3778 0.0000
Ethane LNK 0.09 10 2.8444 9 0 0.1308 0.0000
Propane LK 0.25 4.08 0.9800 24.5 0.5 0.3560 0.0160
Butane Unknown 0.17 2.11 0.3596 9.205 7.795 0.1338 0.2500
Pentane HK 0.11 1 0.0100 0.11 10.89 0.0016 0.3492
Hexane HNK 0.12 0.5 -0.1475 0 12 0.0000 0.3848
68.81 31.19 1 1
X Y Nmin = 6.036
0.12157 0.5322 From Equation Gilliland correlationn
N= 14.0402 0.5322 solver Vmin = 95.152
N= 14.0401 Equation Lmin = 26.337
Rmin = 0.383
NR/NS = 0.19999 R= 0.574
N= NR+NS
N= 0.19999NS+NS
NS = 11.7003
NR = 2.3399

Dr Mawaheb Mohamed Derdar Spring 2024

88