VLE, LLE and VLLE in ASPEN PLUS

Mohammad Ali Fanaei, Ferdowsi University of Mashhad
EOS Method
1- Vapor-Liquid Equilibrium

 At Equilibrium:


 Where


 Therefore

l
i
v
i
f f =
t i
l
i
l
i t i
v
i
v
i
P x f P y f o o = = ,
v
i
l
i
i
i
vl
i
x
y
k
o
o
= =
EOS Method
2- Liquid-Liquid Equilibrium

 At Equilibrium:


 Where


 Therefore

2 1
l
i
l
i
f f =
t
l
i
l
i
l
i t
l
i
l
i
l
i
P x f P x f
2 2 2 1 1 1
, o o = =
1
2
2
1
2 1
l
i
l
i
l
i
l
i
l l
i
x
x
k
o
o
= =
EOS Method
3- Vapor-Liquid-Liquid Equilibrium

 At Equilibrium:


 Where


 Therefore

v
i
l
i
l
i
f f f = =
2 1
t i
v
i
v
i
t
l
i
l
i
l
i t
l
i
l
i
l
i
P y f
P x f P x f
o
o o
=
= =
2 2 2 1 1 1
,
v
i
l
i
l
i
i
vl
i
v
i
l
i
l
i
i
vl
i
x
y
k
x
y
k
o
o
o
o
2
2
2
1
1
1
, = = = =
EOS Method
4- Fugacity Coefficient Formula
o o
o
o
m
V
n V T
i
i
Z dV
V
RT
n
P
RT
j
ln
1
ln
, ,
÷

÷
|
|
.
|

\
|
c
c
÷ =
í
·
Cubic Equations of State in the Aspen Physical Property System
Redlich-Kwong(-Soave) based Peng-Robinson based
Redlich-Kwong (RK) Standard Peng-Robinson(PENG-ROB)
Standard Redlich-Kwong-Soave(RK-SOAVE ) Peng-Robinson(PR-BM)
Redlich-Kwong-Soave (RKS-BM) Peng-Robinson-MHV2
Redlich-Kwong-ASPEN(RK-ASPEN) Peng-Robinson-WS
Schwartzentruber-Renon
Redlich-Kwong-Soave-MHV2
Predictive SRK (PSRK)
Redlich-Kwong-Soave-WS
EOS Method
5- Standard RK-SOAVE
) ( b V V
a
b V
RT
P
m m m
+
÷
÷
=
 Where
¯ ¯¯
= ÷ =
i
i i
i j
ij j i j i
b x b k a a x x a , ) 1 ( ) (
5 . 0
ci
ci
i
ci
ci
i i
P
RT
b
P
T R
a 08664 . 0 , 42747 . 0
2 2
= =o
2 2 5 . 0
176 . 0 57 . 1 48 . 0 , )] 1 ( 1 [ ) (
i i i ri i i
m T m T e e o ÷ + = ÷ + =
EOS Method
6- Standard PENG-ROB
) ( ) ( b V b b V V
a
b V
RT
P
m m m m
÷ + +
÷
÷
=
 Where
¯ ¯¯
= ÷ =
i
i i
i j
ij j i j i
b x b k a a x x a , ) 1 ( ) (
5 . 0
ci
ci
i
ci
ci
i i
P
RT
b
P
T R
a 07780 . 0 , 45724 . 0
2 2
= =o
2 2 5 . 0
26992 . 0 54226 . 1 37464 . 0 , )] 1 ( 1 [ ) (
i i i ri i i
m T m T e e o ÷ + = ÷ + =
EOS Method
7- Advantages and Disadvantages
 Equations of state can be used over wide ranges of
temperature and pressure, including subcritical and
supercritical regions.

 Thermodynamic properties for both the vapor and liquid
phases can be computed with a minimum amount of
component data.

 For the best representation of non-ideal systems, you must
obtain binary interaction parameters from regression of
experimental VLE data. Binary parameters for many
component pairs are available in the Aspen databanks.


EOS Method
7- Advantages and Disadvantages…

 Equations of state are suitable for modeling
hydrocarbon systems with light gases such as CO
2
, N
2

and H
2
S .

 The assumptions in the simpler equations of state
(SRK, PR, Lee-Kesler , … ) are not capable of
representing highly non-ideal chemical systems, such
as alcohol-water systems. Use the activity-coefficient
options sets for these systems at low pressures. At high
pressures, use the predictive equations of state.

Activity Coefficient Method
1- Vapor-Liquid Equilibrium
 At Equilibrium:

 Where

 Therefore

 F0r ideal gas and liquid

l
i
v
i
f f =
l
i i i
l
i t i
v
i
v
i
f x f P y f
*,
, ¸ o = =
t
v
i
l
i i
i
i
vl
i
P
f
x
y
k
o
¸
*,
= =
Law s Raoult
P
P
x
y
k
t
i
i
i
vl
i
v
i i
' 1 , 1
*
= = ¬ = = o ¸
Activity Coefficient Method
2- Liquid-Liquid Equilibrium

 At Equilibrium:


 Where


 Therefore

2 1
l
i
l
i
f f =
l
i
l
i
l
i
l
i
l
i
l
i
l
i
l
i
f x f f x f
*, *,
2 2 2 1 1 1
, ¸ ¸ = =
1
2
2
1
2 1
l
i
l
i
l
i
l
i
l l
i
x
x
k
¸
¸
= =
Activity Coefficient Method
3- Vapor-Liquid-Liquid Equilibrium

 At Equilibrium:


 Where


 Therefore

v
i
l
i
l
i
f f f = =
2 1
t i
v
i
v
i
l
i
l
i
l
i
l
i
l
i
l
i
l
i
l
i
P y f
f x f f x f
o
¸ ¸
=
= =
*, *,
2 2 2 1 1 1
,
t
v
i
l
i
l
i
l
i
i
vl
i
t
v
i
l
i
l
i
l
i
i
vl
i
P
f
x
y
k
P
f
x
y
k
o
¸
o
¸
*, *,
2
2
2
1
1
1
, = = = =
Activity Coefficient Method
4- Liquid Phase Reference Fugacity
 For solvents: The reference state for a solvent is defined as
pure component in the liquid state, at the temperature and
pressure of the system.


 o
i
*,v
= Fugacity coefficient of pure component i at the system
temperature and vapor pressures, as calculated from the vapor phase
equation of state

 u
i
*,l
= Poynting factor
) 1 1 ( , ) , (
*, *, *, *, *,
÷ ÷ =
i i
l
i
l
i
l
i
v
i
l
i
x as P P T f ¸ u o
|
.
|

\
|
=
í
P
P
l
i
l
i l
i
dP V
RT
*,
*, *,
1
exp u
Activity Coefficient Method
4- Liquid Phase Reference Fugacity

 For dissolved gases: Light gases (such as O
2
and N
2
) are
usually supercritical at the temperature and pressure of the
solution. In that case pure component vapor pressure is
meaningless and therefore it cannot serve as the reference
fugacity.


0 1
* *,
*, *
÷ ÷ =
=
i i i
l
i
l
i i i
l
i
x as and H f where
f x f
¸
¸
Activity Coefficient Method
5- NRTL (Non-Random Two-Liquid)

 The NRTL model calculates liquid activity coefficients for the
following property methods: NRTL, NRTL-2, NRTL-HOC,
NRTL-NTH, and NRTL-RK. It is recommended for highly
nonideal chemical systems, and can be used for VLE, LLE and
VLLE applications.


¯
¯
¯
¯ ¯
¯
|
|
|
.
|

\
|
|
|
|
.
|

\
|
÷ + =
j
k
kj k
m
mj mj m
ij
k
kj k
ij j
k
ki k
j
ji ji j
i
G x
G x
G x
G x
G x
G x
t
t
t
¸ ln
Activity Coefficient Method
5- NRTL (Non-Random Two-Liquid)



 Where





 The binary parameters a
ij
, b
ij
, c
ij
, d
ij
, e
ij
and f
ij
can be determined
from VLE and/or LLE data regression. The Aspen Physical Property
System has a large number of built-in binary parameters for the
NRTL model.





¯
¯
¯
¯ ¯
¯
|
|
|
.
|

\
|
|
|
|
.
|

\
|
÷ + =
j
k
kj k
m
mj mj m
ij
k
kj k
ij j
k
ki k
j
ji ji j
i
G x
G x
G x
G x
G x
G x
t
t
t
¸ ln
) 15 . 273 (
0 , ln
1 , ) exp(
÷ + =
= + + + =
= ÷ =
T d c
T f T e T b a
G G
ij ij ij
ii ij ij ij ij ij
ii ij ij ij
o
t t
t o
Activity Coefficient Method
6- Advantages and Disadvantages

 The activity coefficient method is the best way to represent
highly non-ideal liquid mixtures at low pressures.

 You must estimate or obtain binary parameters from
experimental data, such as phase equilibrium data.

 Binary parameters are valid only over the temperature and
pressure ranges of the data.

 The activity coefficient approach should be used only at low
pressures (below 10 atm).
1. Choosing the most suitable model/thermo method.

2. Comparing the obtained predictions with data from
the literature.

3. Estimate or obtain binary parameters from
experimental data if necessary.

4. Generation of lab data if necessary to check the
thermo model.
Principle Steps in Selecting the Appropriate
Thermodynamics Package
Eric Carlson’s Recommendations
E?
R?
P?
Polar
Real
Electrolyte
Pseudo & Real
Vacuum
Non-electrolyte
Braun K-10 or ideal
Chao-Seader,
Grayson-Streed or
Braun K-10
Peng-Robinson,
Redlich-Kwong-Soave,
Lee-Kesler-Plocker
Electrolyte NRTL
Or Pizer
See Figure 2
Figure 1
Polarity
R?
Real or
pseudocomponents
P?
Pressure
E?
Electrolytes
All
Non-polar
P?
ij?
ij?
LL?
(See also
Figure 3)
P < 10 bar
P > 10 bar
PSRK
PR or SRK with MHV2
Schwartentruber-Renon
PR or SRK with WS
PR or SRK with MHV2
UNIFAC and its
extensions
UNIFAC LLE
Polar
Non-electrolytes
No
Yes
Yes
LL?
No
No
Yes
Yes
No
WILSON, NRTL,
UNIQUAC and
their variances
NRTL, UNIQUAC
and their variances
LL?
Liquid/Liquid
P?
Pressure
ij?
Interaction Parameters
Available
Figure 2
VAP?
DP?
Yes
No
Wilson, NRTL,
UNIQUAC, or UNIFAC*
with ideal Gas or RK EOS
Wilson
NRTL
UNIQUAC
UNIFAC
Hexamers
Dimers
Wilson, NRTL, UNIQUAC,
UNIFAC with Hayden O’Connell
or Northnagel EOS
Wilson, NRTL, UNIQUAC,
or UNIFAC with special EOS
for Hexamers
VAP? Vapor Phase Association
Degrees of Polymerizatiom DP?
UNIFAC* and its Extensions
Figure 3
Eric Carlson’s Recommendations
for 1-Propanol ,H
2
O mixture
E?
Polar
Non-electrolyte
See Figure 2
Figure 1
Polarity
R?
Real or
pseudocomponents
P?
Pressure
E?
Electrolytes
P?
ij?
LL?
(See also
Figure 3)
P < 10 bar
UNIFAC and its
extensions
Polar
Non-electrolytes
Yes
LL?
No
No
No
WILSON, NRTL,
UNIQUAC and
their variances
LL?
Liquid/Liquid
P?
Pressure
ij?
Interaction Parameters
Available
Figure 2

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