Vapor-Liquid Equilibrium and Flash Distillation of

Multiple Components
Mohammad Mohammadi1
1 Office: QNC-5321
Office Hours: Mondays, 5 - 6:30 PM

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CHE291: Lab6

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Process Description

Mass Conversation:
F =V +L
Fzi = Vyi + Lxi
In Equilibrium:
fi V = fi L

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Process Calculations
Known variables
F , Zi , T , and P
We can define = V /F , and if n =number of components:

Unknown variables
, xi , and yi
Number of unknown variables= 2n+1
If we know ki s, we can find unknown variables by solving following
equations:

Governing equations in Equilibrium

yi = ki xi
for i = 1, . . . , n
zi
for i = 1, . . . , n
xi =
1 + (ki 1)
n
X
zi (1 ki )
=0
1 + (ki 1)
i=1

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Do we know ki s ?

In a general form, ki = f (xi , yi , T , P).

Pi
P
For non-ideal gas phase and liquid phase, ki can be obtained from
fugacity coefficient of individual component in each phase:
For ideal gas phase and liquid phase: ki =

ki =

M.Mohammadi

Li
V
i

i = 1, . . . , n

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How to calculate Li , Vi ?

Using Peng-Robinson (PR) Equation:

Suitable for non polar compounds such as hydrocarbons
RT
a(T )
General form: P =

V b V (V + b) + b(V b)
An alternative form, written in terms of compressibility factor, Z :

PR EOS
2
3
2
Z 3 + (Bm 1)Z 2 + (Am 2Bm 3Bm
)Z + (Bm
+ Bm
Am Bm ) = 0

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Parameters of PR EOS

Parameters in PR EOS are Am and Bm :

Bm =
Am =

n
X

i Bi
i=1
n X
n
X

i j Aij

i=1 j=1

p
Aij = Aji = (1 kij ) Ai Aj
where
i = xi for Liquid phase
i = yi for Vapor phase

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where Ai and Bi can be calculated from:

ai P
R 2T 2
bi P
Bi =
RT

Ai =

where
q
R 2 Tc2i
[1 + (0.37464 + 1.54226i 0.26992i2 )(1 T /Tci )]2
Pc i
RTci
bi = 0.07780
Pci
ai = 0.45724

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CHE291: Lab6

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Li , Vi
PR EOS
2
3
2
Z 3 + (Bm 1)Z 2 + (Am 2Bm 3Bm
)Z + (Bm
+ Bm
Am Bm ) = 0

From PR EOS we get 3 roots for Liquid phase parameters and 3 roots for
Vapor phase parameters:
Z L = The smallest root of PR equation from the liquid phase parameters
Z V = The largest root of PR equation from the vapour phase parameter

n
X
i Aij
2


Bi
Am
Bi
Bm
j=1

lni =
(Z 1) ln(Z Bm )

ln 1 +
Bm
Bm
Am
Bm
Z

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Li , Vi . . .

Using Z L and liquid phase parameters = Li

Using Z V and gas phase parameters = V
i
ki =

Li
V
i

i = 1, . . . , n

- Needs an iterative method to find the xi , yi , and

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Soave-Redlich- Kwong (SRK) equation of state

Suitable for polar compounds such as hydrocarbons
RT
a(T )
General form: P =

V b V (V + b)
An alternative form, written in terms of compressibility factor, Z :

SRK EOS
2
)Z Am Bm ) = 0
Z 3 Z 2 + (Am Bm Bm

q
R 2 Tc2i
[1 + (0.48508 + 1.55171i 0.15613i2 )(1 T /Tci )]2
Pc i
RTci
bi = 0.08664
Pci
ai = 0.42747

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CHE291: Lab6

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Algorithm for Flash calculations

Process model function

m=fsolve(@ProcessEqua2ons,m0);

Using

xi , yi, T, P, Tc,Pc,

Initial Guess
for xi , yi,

Am and Bm calculation for

gas and liquid phases

Process equations in
equilibrium

(using fsolve)

Calculation of ZL and ZV
from PR or SRK equation
(using roots)

New

xi , yi,

iL and iV calculation

ki =iL /iV

Governing equations in
equilibrium

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fsolve and roots function

fsolve
Solves a problem specified by F (x) = 0
for x, where F (x) is a function that returns a vector value.
Syntax: x = fsolve(fun,x0)

roots
To find the roots of a polynomial c1 s n + + cn s + cn+1=0
c = [c1 . . . cn cn+1 ]
r = roots(c)

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Bubble point and Dew point calculations

Bubble point
In bubble point, when the fist molecule is evaporating, the only phase
of the feed is liquid phase = = V /F = 0
n
X
i=1

zi (1 ki )
=0
1 + (ki 1)

n
X

zi ki = 1

i=1

Dew point
In Dew point, when the fist molecule is condensing, the only phase of
the feed is vapour phase = = V /F = 1
n
X
i=1

zi (1 ki )
=0
1 + (ki 1)

n
X
zi
=1
ki
i=1

Instead of initial guess for , They need an initial guess for T

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