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

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

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

or Bubble point P , T is known

2. Dew point calculations

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

∑

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

or Dew point P , T is known

Flash calculations at constant P

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

OR at constant T

Material balance

Component balance

But ,

For 1.0 lbmole or kgmole of feed

[ ]

∑ ∑
[ ] [ ]

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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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

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

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

Total material balance

Component material balance

On the basis of 1 mole of feed .

Let be the molal fraction of the feed that is vaporized molal fraction of the liquid
left.
, , and

(straight line equation)

Vapor
f

Feed
F = 1 mole

Liquid
(1-f)

Slope is
Intercept of equation is
The equation a straight line with a slope of and can be plotted on the equilibrium
diagram, the coordinates the inter section of the line and the equilibrium curve are at
and .

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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 can be used as a point on
the line.

ii) For Multicomponent systems

Equation (3.9) can be written for each component as

For 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)

2) If the system is vapor ideal & liquid non ideal (modified Roualt’s law)

3) If the system is vapor non ideal & liquid non ideal (Real system)

Distribution coefficient

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

1) ideal system (Roualt’s law)

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

3) Non ideal liquid and vapor (Real system)

The use of relative volatility

⁄
⁄

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

Equation (3.9) can be written as

[ ]

Divide Equation (3.19) by gives

[ ]

[ ]

[ ]
Equation (3.22) can be solved for

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

[ ]

Summering overall components gives

∑{ }
[ ]

∑{ }
[ ]
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:
moles of the material in the still.
mole fraction of the component (mole volatile component) m.v.c.
Suppose an amount containing a mole fraction y of be vaporized.
Amount left in the liquid .

Still Q (heat)

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

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

Neglect

i) For Binary systems

Integrate:

∫ ∫

1/(y-x)
1/(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.

( ) [ ]

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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

( ) [ ]

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

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)

∑ ∑

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

∑ ∑

}
Using the flash Equation

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

Assume

, ,

∑
[ ] [ ]

[ ]
This trial is not correct

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

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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

( ) [ ]

‫ لمعرفة ماذا نفرض من درجة الحرارة‬Bubble point Temperature ‫الغرض من معرفة‬

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

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

∑ ∑

Assume the temperature 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

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

198.5411 0.3568896 0.336014 0.07135

1 1

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

( ) [ ]

( ) [ ]

Solving simultaneously the Equations (3.30), (3.31), and (3.32) by assuming values if computing
and checking the sum until it equals unity by using solver software in Excel.
From component balance you can get

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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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

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

 Non-key components
 Splits – distributing and non-distributing systems
Note that binary systems can be handled in the same terms.

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:

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:

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

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.

Relative volatility:
It is always computed with expect to the heavy key

If the system is ideal

, for components lighter than the heavy key and for heavier than the heavy
key .

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

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

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

Estimating the
composition and product
flow rates

𝑵 – Fenske Equations
⁄
( )
⁄
̅

̅ √

relative volatility of light key at distillate temperature =

relative volatility of light key at bottom temperature

equilibrium constant (K-value) for light key component at distillate temperature.

equilibrium constant (K-value) for heavy key component at distillate temperature.
equilibrium constant (K-value) for light key component at bottom temperature.
equilibrium constant (K-value) for heavy key component at bottom temperature.
vapor pressure for light key component at distillate temperature.
vapor pressure for heavy key component at distillate temperature.

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

fraction recovery of component k.

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

̅ √

relative volatility component k to heavy key at distillate temperature

relative volatility component k to heavy key at feed temperature

relative volatility component k to heavy key at bottom temperature

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

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

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

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

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

B-TMB)D 363.6 1034.26 48.2536 21.433902

B-TMB)avg 13.45147

̅ √ √

̅ √ √

⁄ ⁄
( ) ( )
⁄ ⁄
̅

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%011 ‫عىل أنها‬

‫ز‬
Nmin‫ فأن القيم الجديدة يتم أستخدامها يف إعادة حساب‬، ‫تغيت‬
‫ ر‬bubble point in top or bottom ‫إذا كان أي من درجات‬

𝑹 – Underwood Equations

∑ ∑
𝚽 𝚽

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

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

∑[ ]
𝚽

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

Solution of the first Underwood equation

∑[ ]
𝚽

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).

How to determine 𝑽

∑ ∑ ∑[ ]

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

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 ) and number of equations is one (using one solution of )

𝑽 ∑ ∑ ∑[ ]
𝚽

Case III
Distributions of Nonkey
components are not known

In this case we have to use a number of solutions of 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 ?). Thus we have two unknowns( ),
and therefore we need to use two solutions of , in the second Underwood equation.

Where

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.
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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

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

Component is not distributed; contained entirely in distillate.
Component is distributed; component appears in both distillate and bottoms.
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 (equals C+1). Then solving the second Underwood equation
simultaneously for all values of to obtain 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

With the variable

𝑋

The original Gilliland correlation was graphical. Molkanov et al (1972) fit the Gilliland correlation to
the equation
𝑋 𝑋
[ ( )]
𝑋 𝑋

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

𝑋 𝑋
[( )( )]
𝑋 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)

[ ( ) ]

The number of theoretical stages above the feed plate

The number of theoretical stages below the feed plate

Example 3.4

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

For the distillation problem described in Example (3.3), find the minimum reflux ratio. Use a basis of
100 kmol/h of feed.

∑[ ]

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 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
Example 3.5

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

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 𝐂 using Shiras et al Equation

Component Butane will undoubtedly distribute because , 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

Solving the first Underwood equation

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Mass Transfer II (ChE422) Chapter Three
Multicomponent Distillation

By trial and error the value of Φ1 should be determined and the value Φ2 should be
determined 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

𝑽 ∑ 𝑫𝒙 𝑫

𝑽 ∑ 𝑫𝒙 𝑫

‫نحصل على معادلتين في مجهولين وبتالي تستطيع‬ ‫و‬ ‫وبالتعويض في معادلة اندروود باستخدام الجذور االثنين‬
‫وأصغر التدفق‬ ‫حلهما والحصول على كمية هذه المادة في أعلى البرج‬

Dr Mawaheb Mohamed Derdar Spring 2023

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

Dr Mawaheb Mohamed Derdar Spring 2023

88