VLE, LLE and VLLE in ASPEN PLUS

Mohammad Ali Fanaei, Ferdowsi University of Mashhad

 EOS Method
1- Vapor-Liquid Equilibrium
At Equilibrium: fi  fi
v l

Where f i   yi Pt
v
i
v
, fi   x P
l l
i i t

yi  l
Therefore k  
vl i
xi 
i v
i
 EOS Method
2- Liquid-Liquid Equilibrium
At Equilibrium: fi  fi
l1 l2

Where fi   x P
l1 l1 l1
i i t , f i   x Pt
l2
i
l2 l2
i

x l1 l2
Therefore k l1l 2
  i i

i l2 l1
x i i
 EOS Method
3- Vapor-Liquid-Liquid Equilibrium
At Equilibrium: fi  fi  fi
l1 l2 v

Where f i   x P , f i   x Pt
l1 l1 l1
i i t
l2
i
l2 l2
i
f  i yi Pt
v
i
v

Therefore yi  l1
yi  l2
k vl1
 l1  i
, k vl2
 l2  i
 
i v i v
xi i xi i
 EOS Method
4- Fugacity Coefficient Formula
1 V
 P  RT 
   dV  ln Z m

ln i    
RT 
 ni T ,V ,n j V 
 
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
RT a
P 
Vm  b Vm (Vm  b)
Where

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

i j i

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

 i (T )  [1  mi (1  Tri0.5 )]2 , mi  0.48  1.57i  0.176i2

 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 j i

R 2Tci2 RTci
ai   i 0.45724 , bi  0.07780
Pci Pci

 i (T )  [1  mi (1  Tri0.5 )]2 , mi  0.37464  1.54226i  0.26992i2

 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 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: fi  fi
v l

Where f i v  iv yi Pt , f i l   i xi f i *,l

yi  i f i *,l
Therefore k   v
vl

i Pt
i
xi
F0r ideal gas and liquid
*
y P
 i  1, i  1  ki  i  i Raoult' s Law
v vl

xi Pt
 Activity Coefficient Method
2- Liquid-Liquid Equilibrium
At Equilibrium: fi  fi
l1 l2

Where fi   x fi
l1 l1 l1
i i
*,l
, fi   x fi
l2 l2
i
l2
i
*,l

x  l1 l2
Therefore k l1l 2
  i i

i l2 l1
x i i
 Activity Coefficient Method
3- Vapor-Liquid-Liquid Equilibrium
At Equilibrium: fi  fi  fi
l1 l2 v

Where fi   x fi
l1
, fi   x fi
l1 l1
i i
*,l l2 l2
i
l2
i
*,l

f i  i yi Pt
v v

Therefore
yi  f i l1 *,l
yi  f i l2 *,l
k vl1
 l1  v i
, k vl2
 l2  v i
i Pt i Pt
i i
xi xi
 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)
i
*,v *,l *,l
i
*,l

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

temperature and vapor pressures, as calculated from the vapor phase
equation of state

 1 P 
   exp Pi*,l i 
*,l *,l
i
*,l
= Poynting factor i V dP
 RT
 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 * *,l
i i

where f i *,l  H 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 j ji ji 
 x j Gij

  xm mj Gmj 

ln  i   
j
  ij  m

x G k ki j   xk Gkj 

 xk Gkj 

k  k k
 Activity Coefficient Method
5- NRTL (Non-Random Two-Liquid)
x  G j ji ji 
 x j Gij

 m xm mj Gmj 

ln  i    ij 
j
 
x G k ki j   xk Gkj 

 xk Gkj 

k  k k

Where
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 parameters from

experimental data if necessary.

4. Generation of lab data if necessary to check the

thermo model.
 Eric Carlson’s Recommendations
Figure 1 Non-electrolyte
See Figure 2

Polar
E?

Electrolyte Electrolyte NRTL

Or Pizer

Real Peng-Robinson,
All Redlich-Kwong-Soave,
Non-polar Lee-Kesler-Plocker
R?
Chao-Seader,
Polarity Grayson-Streed or
Real or Pseudo & Real Braun K-10
R?
pseudocomponents P?
P? Pressure
Vacuum
E? Braun K-10 or ideal
Electrolytes
 Yes NRTL, UNIQUAC
and their variances
Figure 2 Yes
LL?
WILSON, NRTL,
P < 10 bar No UNIQUAC and
ij? their variances
(See also
Figure 3) Yes
UNIFAC LLE

P? No
LL?
Polar
Non-electrolytes
No UNIFAC and its
extensions
Schwartentruber-Renon
LL? Liquid/Liquid Yes
PR or SRK with WS
Pressure
PR or SRK with MHV2
P? P > 10 bar
ij?
ij? No PSRK
Interaction Parameters
Available PR or SRK with MHV2
 Wilson, NRTL, UNIQUAC,
Hexamers
Figure 3 or UNIFAC with special EOS
for Hexamers
Yes
DP?
Wilson, NRTL, UNIQUAC,
Dimers
UNIFAC with Hayden O’Connell
or Northnagel EOS
VAP?
Wilson
NRTL Wilson, NRTL,
No
UNIQUAC UNIQUAC, or UNIFAC*
UNIFAC with ideal Gas or RK EOS

VAP? Vapor Phase Association

UNIFAC* and its Extensions
DP? Degrees of Polymerizatiom
 Eric Carlson’s Recommendations
for 1-Propanol ,H2O mixture
Figure 1
Non-electrolyte
See Figure 2

Polar
E?

Polarity
Real or
R?
pseudocomponents
P? Pressure

E? Electrolytes
 Figure 2 Yes
LL?
WILSON, NRTL,
P < 10 bar No UNIQUAC and
ij? their variances
(See also
Figure 3)

P? No
LL?
Polar
Non-electrolytes
No UNIFAC and its
extensions

LL? Liquid/Liquid

P? Pressure

ij? Interaction Parameters

Available