In the Name of God

Petroleum University of Technology

Ahwaz Faculty of Petroleum Engineering
Department of Petroleum Engineering

GAS LIQUID EQUILIBRIA

25/9/90
Abbas Helalizadeh

Physical Properties of Petroleum Fluids

Gas Properties
Oil Properties
Properties of Gas and Liquid (Oil) in
Equilibrium Conditions

Questions ?
Gas
ng
yi

1.

SEPARATOR

( FLASH DRUM )

Feed
n
zi

Liquid
nL
xi
3

2.

Feed
n
zi

Is It Single Phase or Two Phases?

T

If Two Phases;
ng = ?
nL = ?
yi = ?
xi = ?

3.
1800.0
1600.0

Pressure (psia)

1400.0

Bubble Points

1200.0
1000.0
800.0

Dew Points

600.0
400.0
200.0
0.0
0.0

100.0

200.0

300.0

400.0

500.0

600.0

700.0

800.0

900.0

Temperature (R)

Temperature

Pressure

Pressure

4.

Temperature

Equilibrium Ratio or KK-Value can answer to these types of questions.

Equilibrium Ratio Definition :

K i = Equilibrium Ratio

SEPARATOR

yi
xi

( FLASH DRUM )

Ki =

Feed
n
zi

Gas
ng
yi

yi = Mole Fraction in Gas Phase

xi = Mole Fraction in Liquid Phase

Ki = K (P, T, Composition)

This process is called

flash vaporization.

Liquid
nL
xi
7

K-Value can be obtained by:

1. Ideal Solution Principle Method

2. Empirical Correlations Method
3. Empirical Figures Method
4. Equations of State Method

1. Ideal Solution Principle:

Vt = Vi = VA + VB

Ideal Solution Q = 0

A A = B B = A B

A
B

Gases behaves as an ideal gas at low

pressures
Liquids behaves as on ideal solution
when they are homologous

Raoult's Law for Ideal Solutions:

Pi = xi PV i

Gas

Pi = Partial pressure of i-component in gas phase

Pi

xi = Mole fraction of i-component in liquid phase

yi

PVi = Vapor pressure of a pure component (icomponent) at the system temperature.

Liquid

It can be obtained from CoxChart or vapor

xi

pressure correlations (i.e. Lee-Kessler or ..).

Lee-Kessler Correlation:

PV = P * = PC EXP ( A + B )
6.09648

1.2886 ln Tr + 0.16934 ( Tr )6
A = 5.92714 T

B = 15.2518 15.6875 13.4721 ln T + 0.4357 ( T )6

r
r

Tr

10

Cox Chart (Vapor-Pressure Curves):

11

Dalton's Low for Ideal Gases:

Pi = Pt yi = P yi

Gas
Pi
yi

Pi = Partial pressure of i-component in gas phase

yi = Mole fraction of i-component in gas phase

Liquid
xi

Pt = P = Total pressure
P

12

Since Gas and Liquid are co-existed (in Equilibrium), then

xi PVi = Pt yi
If ;

Ki =
then

y i Pv i
=
xi
Pt

if

then

Ki

if

then

Ki

then

Ki

if

MW

13

2. Empirical Correlations:
a) Wilson Correlation (for pressures below 500 psia):
K

Pci
T

Exp 5 . 37 ( 1 + i ) ( 1 ci )
P
T

b) Modified Wilson Correlation (for pressures more than 500 psia):

P
K i = ci
Pk
where

A1

Pci
T

Exp 5.37 A (1 + i ) (1 ci )
P
T

P Pa
A = 1

Pk Pa

and Pk is the convergence pressure , as correlated by standing ;

Pk = 60MWC7+ 4200

The exponent n varies between 0.5 and 0.8, depending on the fluid. The default value is
14 0.6.

c) Standing Correlation:
Ki =

1
10
P

a + cF i

a = 1 . 2 + 0 . 00045 P + 15 (10 8 ) P 2
c = 0 . 89 0 . 00017 P 3 . 5 (10 8 ) P 2
1
1
Fi = bi

T
T
bi

bi =

Log ( Pci / 14 . 7 )
1
1

T bi
T ci

Where Tbi is normal boiling point of component i

15

3. Empirical Figures:

K-Values for pure components can

be obtained using these figures (in
a specified convergence pressure).

References:
NGPSA (GPSA) HANDBOOK
McCain Text Book:
Fig. A-1 to Fig. A-14
Tarek-Ahmed Text Book:
Fig. A-1 to Fig. A-12
Campbell Text Book:
Fig. A-1 to Fig. A-16

K-Values for Ethane. Convergence Pressure =5000 psia.

K-Values
forEngineering
Ethane. Convergence
Pressure
=5000 psia.
(Ref.: NGPSA
Data Book, Tenth
Edition).
(Ref.: NGPSA Engineering Data Book, Tenth Edition).

16

4. Equations of State:
f Li
y
x P

Ki = i = i
= Li
f gi
xi
gi
yi P

or K i =

Li
gi

Li and gi (Fugacity Coefficients) for each component in a

mixture could be obtained by any Equation of State (i.e. PR,
SRK and etc. ).
17

Gas
ng
yi

Flash Calculations:

1. and 2.

Feed

SEPARATOR

n
zi

Material balance must be used to calculate

the above parameters.

Liquid

Basis: n=1 lbmole (for simplicity)

nL
xi

Feed

OMB:

n = ng + nL

1 = ng + nL

n
zi
T

CMB:

nzi = ng yi + nL xi

zi = ng yi + nL xi *

18

*
xi
n
) = yi (n g + L )
yi
Ki

yi =

+ n L ) = xi (n g K i + n L )

xi =

zi = yi (n g + n L

*
z i = xi (n g

=1

=1

*y

xi

zi
n
ng + L
Ki

=1

zi
=1
i + nL

n K
g

zi
n
1 nL + L
Ki

n K
g

=1

zi
=1
+
1 ng
i

zi
ng +

zi
n g K i + nL

zi
1 + nL (

1+ n

nL
Ki

1
1)
Ki

=1

zi
=1
(
g K i 1)

19

1800.0
1600.0

zi
1 + nL (

Pressure (psia)

3.
=1

1
1)
Ki

z
1 + n (Ki 1) = 1
g
i

1400.0

Bubble Points

1200.0
1000.0
800.0

Dew Points

600.0
400.0
200.0

At Bubble Points: n g 0 , nL 1
zi
=1
1
1 + ( 1)
Ki
zi

=1
1 + 0 ( K i1)

1 + 0(

zi
=1
1
1)
Ki

zi
=1
1 + ( K i 1)

0.0

100.0

200.0

300.0

400.0

500.0

600.0

700.0

800.0

900.0

Temperature (R)

Ki = 1

=1

nL 0 , n g 1

At Dew Points:

0.0

At Bubble Points:

=1

zi
=1
Ki

At Dew Points:

Ki = 1

zi
=1
Ki
20

10

If Ki is obtained by method 1 (Ideal solution principle method), therefore;

therefore;

Pv i

Pt

At Bubble Points:

Pb = Pt = z i Pvi

Pv i
=1
pt

At Dew Points:

zi
=1
p vi
pt

1
1
=
=
Pt
pd

zi
Pvi

Pdd == P
P tt =

zi
P
p vivi
21

If Ki is obtained by methods 2, 3 and 4, then an iteration method should

should be sued.

Bubble Points Calculations:

T is fixed, P is calculated.

P ressure

P is fixed, T is calculated or

For Example:
1. Fix a valve for Pb
2. Assume a T

Temperature

3. Obtain K-values
4. Calculate (ziKi)
5. If (ziKi)=1, then T = Tb
6. If (ziKi) #1, Go To Step 2
22

11

Dew Points Calculations:

P is fixed, T is calculated or

Pressure

T is fixed, P is calculated.

For Example:
1. Fix a valve for Pd
2. Assume a T
3. Obtain K-values
4. Calculate (zi / Ki)

Temperature

5. If (zi / Ki)=1, then T = Td

6. If (zi / Ki )#1, Go To Step 2
23

4.

In this case, the flash calculations procedure could be used. Hence:

zi
=1
g ( K i 1)

zi
1 + nL (

yi =

1
1)
Ki

zi
ng +

xi =

nL
Ki

=1

or

nL = 1 ng
Pressure

1+ n

zi
n g K i + nL
Temperature

24

12

Quick Phase Determination:

Feed

n
zi
T

zi K i

z
K

i
i

Sub-cool

Bubble Point

Two Phases

Dew Point

Superheat

<1

>1

>1

>1

>1

>1

>1

<1

25

Heptanes Plus and CO2 K-Valves:

1. Log K vs. Tc2

2. Volatility Exponent
3. Log K vs. 1/Tb
1 1
4. KP vs. b
Tb T

5. K C 7 + = 0.15 K C 7
6. K C 7 + = K C10
7. K-Value of the Closest n-Alkane

K CO 2 = K C1 .26
KC 2

13

K-Value can be obtained by:

1. Ideal Solution Principle

2. Empirical Correlations
3. Empirical Figures
4. Equations of State

27

GasGas-Liquid Equilibria Calculations Using Equations of State:

Equilibrium Criteria
1

T1
P1
C1

T2
P2
C2

T Causes Heat Transfer

P Causes Momentum Transfer

Transport Phenomena

C Causes Mass Transfer

In Equilibrium:
Chemical Potential of the Gas = Chemical Potential of the Liquid
28

14

Chemical potential of the gas and the liquid must be

Gas

equal at the equilibrium conditions.

Liquid

Chemical Potential: dG = VM dP
Chemical potential is also called Gibbs Molar Free Energy.

29

For Ideal Gases:

PV = nRT

or PVM = RT

Thus dG =

RT
dP = RT d (ln P )
P

(n=1 1bmole)

For Real Fluids:

dG = ZRT d (ln P )

or

dG = RT d (ln f )

(1)

(2)

where lim f = P if P 0
30

15

Calculation of Fugacity Coefficient for Pure Components:

For pure components, when the equilibrium is existed between

gas and liquid;
GL = Gg

f
P

or

dGL = dGg

thus

f L = fg

f = P

31

dP
P

(1)

dG = ZRT d (ln P ) = ZRT

( 2)

dG = RT d (ln f ) = RT d ln( P )

dG = RT d (ln P ) + RT d ln( )
dG = RT

dP
+ RT d ln( )
P

dp
dp
= R/ T/
+ R/ T/ d ln
P
P

Z R/ T/

d ln = ( Z 1)

ln =

dp

( Z 1)

d ln =

dp

( Z 1)

dp
P

(3)

32

16

PV = ZnRT

P
ZRT

lbmole
ft 3

PMW
ZRT

lbm
ft 3

(molar density)

( mass density )

P = ZRT

dP = RT ( Z d + dZ )

R/ T/
dp
RT
=
( Z d + dZ ) =
( Z d + dZ )
P
P
Z R/ T/
dp
d
dZ
=
+
P

(4)
33

Substituting Equation (4) in Equation (3)

ln = ( Z 1) (
0

Z
dZ
d
dZ
) = ( Z 1)
+ ( Z 1)
0
1
Z

0 p

1 Z

P :

Z :

ln = Z 1 ln Z +

PV M
d
1)

RT

1
P
) d( )
dVM
V
M
ZRT =
=
P
1
VM
ZRT
VM

d(

34

17

 : o
VM : VM

PV M
d
1
1)
=
RT

RT

VM

( PV M RT )

ln = ( Z 1) ln Z +

1
RT

VM

dV M
VM

RT
P ) dV M
VM

(5)

It is clear that ZL and Zg can be calculated from an EOS (i.e. PR, SRK or etc.).
Therefore, it is possible to calculate the fugacity coefficient for any component
(icomponent), in any phase (i.e. Liquid or Gas).

Z =?
I =

1
RT

VM

RT
P ) dV M = ?
VM
35

Z =?
PengPeng-Robinson EOS:

aT
(VM b ) = RT
P+
VM ( VM + b ) + b( VM b )

[PV M (VM

+ b ) + Pb (V M b ) + aT ] (V M b ) = RT [V M (V M + b ) + b (V M b ) ]

VM3 + (b

2R T b
a b R T b2
a
RT
) VM2 + ( T
3b 2 )VM + (b 3 T +
)=0
P
P
P
P
P

Substituting

VM =

ZRT
P

A=

aT P
R2 T 2

B=

bP
RT
36

18

The PR EOS is reduced to:

Z 3 + (B 1) Z 2 + A 3B 2 2 B Z AB B 2 B 3 = 0

(6)

This equation will have 3 real roots, when two phases are co-existed.

Zg = ZMax
ZL = ZMim

37

I =

1
RT

VM

RT
P ) dV M = ?
VM

PengPeng-Robinson EOS:

aT
(VM b ) = RT
P+
VM ( VM + b ) + b( VM b )

P =

aT
RT

V M b V M (V M + b ) + b (V M b )

I =

I = ln

VM

a
1
1
1

+ T
) dV M
2
VM
V M b RT V M + 2 bV M b 2

VM
a
+ T
VM b
RT

VM

(V M

1
) dV M
+ b ) 2 2b 2

(7)

38

19

VM

1
) dV
(V M + b ) 2 2 b 2
1
2 b

VM

1
VM + b +

V + b +
1
ln M
2 2 b
VM + b

2 b

1
VM + b

2 b

) dV

(8)

2 b
2 b

Substituting Equation (8) in Equation (7) gives

I = ln

V +b+
VM
a
+ 1 .5 T
ln M
VM b
2 RT b
VM + b

2 b
2 b

39

VM =

Since

Z R T
P

ZRT
ZRT
+b+
aT
P
+ 1 .5
ln P
I = ln
ZRT
ZRT
2 RTb
b
+b
P
P

2 b
2 b

bP
Z + ( 2 + 1)
aT
RT
I = ln
+ 1 .5
ln
bP
bP
RTb
2
Z
Z ( 2 1)
RT
RT
Z

Substituting I into Equation (5);

bP
Z + ( 2 + 1)
aT
Z
RT
ln = Z 1 ln Z + ln
+
ln
bP
bP 21.5 RTb
Z ( 2 1)
Z
RT
RT
40

20

A =

Since

aT P
R 2T 2

ln = Z 1 ln ( Z B) +

and

B =

bP
RT

A
Z + (20.5 + 1) B
ln
21.5 B
Z (20.5 1) B

(9)

Hence
ln g = Z g 1 ln ( Z g B) +

Z g + (20.5 + 1) B
A
ln
21.5 B
Z g (20.5 1) B

ln L = Z L 1 ln ( Z L B ) +

A
Z L + (20.5 + 1) B
ln
Z L (20.5 1) B
21.5 B
41

Calculation of Fugacity Coefficient for Mixtures:

For mixtures, the chemical potential for each components in gas and liquid
phases must be equal.

in equilibrium fLi = fgi

dG i = RT d ln f i

gi

L i

f
P
=
=

gi

P gi

gi

P yi

f Li
f Li
=
P Li
P xi

f g/ i

Ki =

yi P gi

=
= Li
f Li/
xi
gi
P Li

Ki =

Li
gi
42

21

For mixtures, the fugacity coefficient is defined as;

ln i =

1
RT

VM

RT

P
(
) T ,V , n j i dV M ln Z

ni
VM

With the same procedure, we can calculate this integral using PR EOS.

Finally;
ln i = ln ( Z B ) + ( Z 1) B i

where Bi =

bi
b

and

A
2 1 .5 B

Ai =

( Ai B i ) ln

1
0.5
2 aTi
aT

ya
j

Z + ( 2 0 .5 + 1) B
Z ( 2 0 .5 1) B

0.5

Tj

(1 ij )

43

Application of K-Values:
Flash Calculations
Phase Determination
Plotting of the Phase Diagram
Simulation of Flash Vaporization, Differential Vaporization
and Separator Tests
Gas and Liquid Transmission
Optimization of Production Units (Surface Separation)
NGL Plants Design
..
..

44

22

Any Questions?

45

23