VLE, LLE and VLLE in ASPEN PLUS

Mohammad Ali Fanaei, Ferdowsi University of

Mashhad

EOS Method
1- Vapor-Liquid Equilibrium
fi fi
v

At Equilibrium:

Where

Therefore

f i yi Pt
v

v
i

fi x P
l

yi
k
xi
vl
i

l
i
v
i

l
i i t

EOS Method
2- Liquid-Liquid Equilibrium
fi fi
l1

At Equilibrium:

Where

Therefore

fi x P
l1

l1 l1
i i t

l1l 2
i

l2

f i x Pt
l2

l1
i
l2
i

l2
i
l1
i

l2
i

l2
i

EOS Method
3- Vapor-Liquid-Liquid Equilibrium
At Equilibrium:

fi fi fi
l1

l2

f i x P , f i x Pt
v
f i yi Pt
l1

Where

Therefore

vl1
i

l1 l1
i i t
v
i

yi
l1
xi

l1
i
v
i

l2

, k

l2
i

vl 2
i

l2
i

yi
l2
xi

l2
i
v
i

EOS Method
4- Fugacity Coefficient Formula
1

ln i
RT

n
i

T ,V , n j

RT
dV ln Z m

Cubic Equations of State in the Aspen Physical Property System

Redlich-Kwong(-Soave) based
Peng-Robinson based
Redlich-Kwong (RK)
Standard Peng-Robinson(PENGROB)
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
RT
a
P

Vm b Vm (Vm b)
Where

a xi x j (ai a j ) 0.5 (1 kij ), b xi bi

i

R 2Tci2
RTci
ai i 0.42747
, bi 0.08664
Pci
Pci

i (T ) [1 mi (1 Tri0.5 )]2 , mi 0.48 1.57i 0.176i2

EOS Method
6- Standard PENG-ROB
RT
a
P

Vm b Vm (Vm b) b(Vm b)
Where

a xi x j (ai a j ) 0.5 (1 kij ), b xi bi

i

R 2Tci2
RTci
ai i 0.45724
, bi 0.07780
Pci
Pci
i (T ) [1 mi (1 Tri0.5 )]2 , mi 0.37464 1.54226i 0.26992i2

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 CO2

, N2 and H2 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 activitycoefficient options sets for these systems at low
pressures. At high pressures, use the predictive
equations of state.

Activity Coefficient Method

1- Vapor-Liquid Equilibrium
fi fi
v

At Equilibrium:
Where
Therefore

f i v iv yi Pt

f i l i xi f i *,l

yi i f i
k v
xi
i Pt
vl
i

*,l

F0r ideal gas and liquid

*
y
P
v
vl
i 1, i 1 ki i i Raoult ' s Law
xi Pt

Activity Coefficient Method

2- Liquid-Liquid Equilibrium
fi fi
l1

At Equilibrium:

Where

Therefore

fi x fi
l1

l1 l1
i i

l1l 2
i

*,l

l2

fi x fi

l1
i
l2
i

l2

l2
i
l1
i

l2
i

l2
i

*,l

Activity Coefficient Method

3- Vapor-Liquid-Liquid Equilibrium
At Equilibrium:

Where

fi fi fi
l1

l2

fi x fi
, fi x fi
v
v
f i i yi Pt
l1

Therefore

vl1
i

l1 l1
i i

l2

*,l

yi f i
l1 v
xi
i Pt
l1
i

*,l

, k

l2
i

vl2
i

l2
i

*,l

yi f i
l2 v
xi
i Pt
l2
i

*,l

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.

fi

*,l

(T , Pi ) Pi , ( i 1 as xi 1)
*,v
i

*,l

*,l

*,l
i

i*,v = Fugacity coefficient of pure component i at the system

temperature and vapor pressures, as calculated from the vapor phase
equation of state
i*,l = Poynting factor

*,l
i

1
exp
RT

Pi

*,l
V
*,l i dP

Activity Coefficient Method

4- Liquid Phase Reference Fugacity
For dissolved gases: Light gases (such as O2 and N2 ) 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.

f i xi f
l

where

f i *,l H i

* *,l
i i

and

i* 1 as xi 0

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.

x G

x G
j

ln i

ji

ki

ji

x j Gij

x G
k

kj

ij

x G

x G
m mj

mj

kj

Activity Coefficient Method

5- NRTL (Non-Random Two-Liquid)
x G

x G
j

ln i

ji

Where

ki

ji

x j Gij

x G
k

kj

ij

x G

x G
m mj

mj

kj

Gij exp( ij ij ) , Gii 1

ij aij bij T eij ln T f ijT

, ii 0

ij cij d ij (T 273.15)
The binary parameters aij, bij, cij, dij, eij and fij 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.

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).

Principle Steps in Selecting the Appropriate

Thermodynamics Package
1. Choosing the most suitable model/thermo method.
2. Comparing the obtained predictions with data from

the literature.

3. Estimate

or obtain binary
experimental data if necessary.

parameters

from

4. Generation of lab data if necessary to check the

thermo model.

Eric Carlsons Recommendations

Non-electrolyte

Figure 1
Polar

See Figure 2

E?
Electrolyte NRTL
Or Pizer

Electrolyte
Real
All
Non-polar

Peng-Robinson,
Redlich-Kwong-Soav
Lee-Kesler-Plocker

R?

Polarity
R?

Real or
Pseudo &
pseudocomponents

P?

Pressure

E?

Electrolytes

Real

P?
Vacuum

Chao-Seader,
Grayson-Streed or
Braun K-10

Braun K-10 or ideal

Yes
Yes

Figure 2

LL?

P < 10 bar
ij?
(See also
Figure 3)

P?

NRTL, UNIQUAC
and their variances
WILSON, NRTL,
UNIQUAC and
their variances

No
Yes
No

LL?

Polar
Non-electrolytes

No
Yes

LL? Liquid/Liquid
P?

Pressure

ij?

Interaction Parameters
Available

P > 10 bar

UNIFAC LLE

ij?
No

UNIFAC and its

extensions

Schwartentruber-Renon
PR or SRK with WS
PR or SRK with MHV2

PSRK
PR or SRK with MHV2

Hexamers

Figure 3
Yes

DP?
Dimers

VAP?
Wilson
NRTL
UNIQUAC
UNIFAC
VAP?
DP?

Wilson, NRTL, UNIQUAC,

or UNIFAC with special EOS
for Hexamers

No

Wilson, NRTL, UNIQUAC,

UNIFAC with Hayden OConnel
or Northnagel EOS
Wilson, NRTL,
UNIQUAC, or UNIFAC*
with ideal Gas or RK EOS

Vapor Phase Association

Degrees of Polymerizatiom

UNIFAC* and its Extensions

Eric Carlsons Recommendations

Figure 1
Polar

for 1-Propanol ,H2O mixture

Non-electrolyte

E?

Polarity
R?

Real or
pseudocomponents

P?

Pressure

E?

Electrolytes

See Figure 2

Figure 2

Yes

P < 10 bar
ij?
(See also
Figure 3)

P?

Polar
Non-electrolytes

LL? Liquid/Liquid
P?

Pressure

ij?

Interaction Parameters
Available

LL?

WILSON, NRTL,
UNIQUAC and
their variances

No

No

LL?
No

UNIFAC and its

extensions