Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Module 1: Polymer Physical Properties

Phase Equilibrium – Polymer
Equations-of-State
Process Simulation with Polymers Plus

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Course Agenda – Day 1

1. Component Characterization
– Polymers Plus Component Types
– Polymer Component Attributes
– Molecular Weight Distributions

2. Polymers Plus Property Option Sets

3. Polymer Thermo / Physical Property Models
– Workshop – Estimating and Regressing Property Data

4. Polymer Phase Equilibrium

– Activity Coefficient Models
– Polymer Equations of State
– Workshop – Fitting VLE Data

5. User Prop-Set Properties

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Course Agenda – Day 2 and 3

6. Polymerization Reaction Kinetics
– Overview of Reaction Types
– Theory of Instantaneous Properties (MWD)
– Free-Radical Kinetics
Day 2
– Ziegler-Natta Kinetics
– Step-Growth Kinetics
– Segment-Based Power-Law kinetics Day 3
– Emulsion Kinetics [optional module]
– Ionic Kinetics [optional module]
7. Reactor Modeling

8. Reactor and Flowsheet Convergence

9. Using Data Fit to Regress Data

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Workflow of a Typical Simulation Project

Properties

Identify and Select Fit / Verify Pure Fit / Verify

Characterize Property Component Phase Equilibrium
Components Option Set Properties Data

Develop User Prop-Set

Property Routine (IV, Etc.)
Kinetics

Determine Customize Verify Model

Define
Rate Rate Expression (Use Batch Data
Reactions Constants if Necessary if it is Available)
Flowsheet

Close Recycle Add Details Test Model

Build “Open”
and Control (Heat Transfer,
Flow Sheet Loops Etc.)
Apply Model
May be necessary to return
to previous step to improve model

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Equation-of-State Models (1)

• Provide a relationship between pressure P,
temperature T , density ρ, and composition
x = { xi }
• Composition dependence through EOS theoretical
formulation/parameter mixing rules

P = f (T , ρ , x )

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Equation-of-State Models (2)

• The same model is used for fugacity coefficients of both
liquid and vapor phases
• The same model is used for thermodynamic properties of
both pure components and mixtures
• Physical properties like density, enthalpy and heat
capacity can be derived from the equation of state
• EOS can be used safely at low as well as high
pressures; they must be preferred at pressures higher
than about 20 bar
• Not necessary to treat light gases as Henry's
components

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Equation-of-State Models (3)

• Phase Equilibrium Calculations (VLE)
ϕ iv y i = ϕ il x i
• Phase Equilibrium Calculations (VLLE)
ϕ iv y i = ϕ il1 x il1 = ϕ il 2 x il2
• Polymer components are non-volatile

1 Vα
  ∂p  RT 
ln ϕ αi = −
RT ∫
∞

  ∂ n i

 T ,V , n j ≠ i
−
V
 d V − ln Z α

α = v, l
 
= Z (T , V α , {x i }or {y i })
PV α
Zα =
nRT

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Equation-of-State Models (4)

• Mixture enthalpy is calculated as the sum of ideal gas and departure
contribution from an EOS
H (T , P, x ) = H IG (T , x) + ∆H EOS (T , P, x)
 
H IG(T, x) = ∑xi HiIG (T) = ∑xi HiIG(Tref ) + ∫ CpiIG (T)dT
T

i i  Tref 

• Mixture entropy and Gibbs free energy are calculated similarly

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Equation-of-State Models: H vs. T for a Pure

Conventional Component
increasing pressure

ideal gas
Enthalpy

sat'd vapor

sat'd liquid

Temperature

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Equation-of-State Models: Ideal Gas Model

Parameters – H iIG (Tref ) and CpiIG (T )
• Conventional components
– Values retrieved from Aspen Plus databanks

• Polymer and oligomer components

– Parameters are not measurable
– Polymers Plus calculates default values based on group
contribution techniques (van Krevelen methods)
– We recommend that the default values for the polymer be
overridden based on measured data:
• Heat of formation can be estimated from heat of reaction information
• Ideal-gas heat capacity can be determined by fitting liquid heat capacity
data for the polymer

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Equation of State Property Methods: Three

Sphere-Chain Based Polymer EOS, POLYSL,
POLYSAFT and POLYPCSF and a Polymer
Cubic EOS, POLYSRK
Property Method Liquids + Solids Vapor Phase
Thermophysical Transport Properties Equilibrium

Cp, H, S, G, ρ η, k
POLYSL Sanchez- van Sanchez-Lacombe EOS
Lacombe EOS Krevelen
POLYSRK Polymer SRK van Polymer SRK EOS
ρ from VK model Krevelen

POLYSAFT SAFT EOS van Polymer SAFT EOS

Krevelen
POLYPCSF PC-SAFT EOS van PC-SAFT EOS
(PC-SAFT) Krevelen

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Equation-of-State Models: Sphere-Chain Based

Polymer EOS – Three Pure Parameters (1)
• Share similar theoretical basis and physical meanings on
parameters
• A molecule modeled by a series of m freely-jointed tangent spheres
(segment). m Is often called the number of segments per molecule
• Each sphere (segment) has two parameters: diameter σ and energy
parameter ε

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Equation-of-State Models: Sphere-Chain Based

Polymer EOS – Three Pure Parameters (2)
• For a conventional component, molecular chain length m
is fixed
• For a polymer component, m is not fixed and calculated
from r (fixed for polymer component) and the molecular
weight M n

m = rMn

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Equation-of-State Models: Sphere-Chain Based

Polymer EOS – One or Two Binary Parameters
• k ij accounts for the difference between energy parameters

ε ij = (1 − kij ) ε ii ε jj
• η ij accounts for the difference between size (diameter)
parameters

σ ij = (1 − ηij )(σ ii + σ jj ) / 2

• Most cases, only k ij is needed

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Equation-of-State Models: Sphere-Chain Based

Polymer EOS – Pure Component Parameters
• For conventional components, pure parameters are fit against
component vapor pressure and saturated liquid density data

• For light gas components (i.e. ethylene, etc.), additional density data
in supercritical region may be used

• For polymer components, pure parameters are fit against

component liquid density data

• For trace components (i.e. catalyst, initiator, etc.), the molecular

chain length parameter m is set equal to a relatively high value ( m >
20) so that they remain in the liquid phase, and the segment size
and energy parameters, σ and ε , are set equal to the values of the
key component so that they are miscible with the key component in
the streams where no polymer exists

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Equation-of-State Models: Sphere-Chain Based

Polymer EOS – Pure Component Data Sources
• For conventional components, DIPPR database (2003).
DIPPR correlation models are implemented in Aspen
Plus and can be used to generate component vapor
pressure and liquid density data
• For polymer components, Handbook of Polymer Solution
Thermodynamics (1992). When no data available, van
Krevelen Group Contribution Method implemented in
Polymers Plus can be used to generate polymer liquid
density data
• Use Aspen Plus “Property Analysis Tool” to generate
property data tables and charts for components

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Equation-of-State Models: Sphere-Chain Based

Polymer EOS – Binary Parameters
• Binary parameters are fit against VLE and LLE data

• VLE and LLE data sources:

– Handbook of Polymer Solution Thermodynamics (1992)
– DECHEMA polymer solution data collection (1992)
– DETHERM Online database (2004)

• For non-polymer mixtures, VLE data can be generated

by cubic EOS such as SRK and Peng-Robinson using
Aspen Plus “Property Analysis Tool”

©2004 AspenTech. All Rights Reserved.

Design Philosophy for Polymer EOS:

Copolymers
• To date, all of available polymer EOS models are based
on homopolymers
• We have extended these models to account for
copolymer composition using mixing rules to convert
segment-based parameters into polymer parameters
– See Online Polymers Plus Help->Polymers Plus Reference
->Equation-of-State Models

• Parameters may be specified for the polymer component

or the segments in the polymer component
– Polymer parameters are used directly if they are specified,
otherwise they are calculated from segment parameters

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Sanchez-Lacombe EOS
• Applicable for polymers and conventional components
– Not very good for conventional components near critical point

• Pure component parameters: T*, P* and ρ. They are related to the

*

molecular chain length m , the segment diameter σ , and the

segment energy parameter ε
ε ε Mn π
T* = P* = ρ* = v = σ3
k v mv 6
• Symmetric binary parameters: k ij and η ij
• Pure component parameters for some polymers and conventional
components available
– See Online Polymers Plus Help->Polymers Plus Reference
->Equation-of-State Models->Sanchez -Lacombe EOS Model

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Parameters for Sanchez-Lacombe EOS

Parameter Name / Symbol Default Lower Upper MDS Units Comments
Element Limit Limit Keyword

SLTSTR T* --- --- --- X TEMP Unary

SLPSTR P* --- --- --- X PRESSURE Unary
SLRSTR ρ* --- --- --- X DENSITY Unary
SLKIJ kij 0.0 --- --- X --- Binary,
Symmetric
SLETIJ ηij 0.0 --- --- X --- Binary,
Symmetric

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Sanchez Lacombe EOS

• Key references:
– Sanchez, I. C. and R. H. Lacombe, "An Elementary Molecular
Theory of Classical Fluids. Pure Fluids," J. Phys. Chem.,
80(21), 2352-2362 (1976)
– Sanchez, I. C. and R. H. Lacombe, "Statistical
Thermodynamics of Polymer Solutions,” Macromolecules,
11(6), 1145-1156 (1978)

• Additional background:
– See Online Polymers Plus Help->Polymers Plus Reference
->Equation-of-State Models->Sanchez-Lacombe EOS Model

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Statistical Associating Fluid Theory (SAFT)

EOS
• State of art EOS
• Rigorous thermodynamic model based on perturbation
theory
• Better than Sanchez-Lacombe for monomers and
solvents, especially around critical point

• Incorporates effects of
– Molecular size
– Chain connectivity
– Attractive interactions

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

SAFT EOS
• Pure component parameters: m , v 00 , and u 0 . v 00 and u 0
are related to the segment diameterσ and energy
parameter ε :
π
v 00 = σ 3 u0 = ε
6
• For a polymer component,m is calculated from:
m = rM n
• Symmetric binary parameter: k ij

• Pure component parameters for some polymers and

conventional components available
– See Online Polymers Plus Help->Polymers Plus Reference
->Equation-of-State Models->SAFT EOS Model
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Parameters for SAFT EOS

Parameter Name / Symbol Default Lower Upper MDS Units Comments
Element Limit Limit Keyword

SAFTM m --- --- --- X --- Unary

SAFTV voo --- --- --- X MOLE- Unary
VOLUME
SAFTU uo / k --- --- --- X TEMP Unary
SAFTR r --- --- --- X --- Unary
SFTEPS e/k 10 --- --- --- --- Unary
SFTKIJ kij 0.0 --- --- X --- Binary,
Symmetric

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

SAFT EOS
• Key references:
– Chapman, W.G., K.E. Gubbins, D. Jackson, and M. Radosz. “A
New Reference Equation of State for Associating Liquids,” Ind.
Eng. Chem. Res., 29, 1709 (1990)
– Huang S. H. and M. Radosz, “Equation of State for Small,
Large, Polydisperse, and Associating Molecules,” Ind. Eng.
Chem. Res., 29, 2284 (1990)
– Huang S. H. and M. Radosz, “Equation of State for Small,
Large, Polydisperse, and Associating Molecules: Extension to
Fluid Mixtures,” Ind. Eng. Chem. Res., 30, 1994 (1991)

• Additional background:
– See Online Polymers Plus Help->Polymers Plus Reference
->Equation-of-State Models->SAFT EOS Model

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Perturbed-chain SAFT (PC-SAFT) EOS

• Based on SAFT EOS

• Incorporates effects of:

– Molecular size: identical to SAFT
– Chain connectivity: identical to SAFT
– Molecular interactions: improvement over SAFT
• Accounts for attractive interactions between connected chains more
realistically

SAFT
PC-SAFT

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

PC-SAFT EOS Advantages

Decane - Ethane at 238°C

120 PC-SAFT, kij=0

100
SAFT, kij=0 • Better than SAFT for
Raemer ,Sage,1962 monomer components
80 near the critical point
P (bar)
60
• Better predictive
40 capability than SAFT
20

0
0.0 0.2 0.4 0.6 0.8 1.0
xEthane

• PC-SAFT is focus of considerable research attention, so

improvement opportunities will be easily identified, e.g.,
random and block co-polymers
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PC-SAFT EOS
• Pure component parameters: number of segments per
molecule m, segment diameter σ , and segment energy
parameter ε
• For a polymer component, m is calculated from the
number average molecular weight M n :
m = rM n
• Symmetric binary parameter: k ij

• Pure component parameters for some polymers and

conventional components available in built-in library
– See Online Polymers Plus Help->Polymers Plus Reference
->Equation-of-State Models->PC-SAFT EOS Model
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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

PC-SAFT Parameters
Parameter Name / Symbol Default Lower Upper MDS Units Comments
Element Limit Limit Keyword
PCSFTM m --- --- --- X --- Unary
PCSFTV σ --- --- --- X --- Unary
PCSFTU ε/k --- --- --- X TEMP Unary
PCSFTR r --- --- --- X --- Unary
PCSKIJ kij 0.0 --- --- X --- Binary,
Symmetric

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PC-SAFT EOS
• Key references:
– Gross, J. and G. Sadowski, “Application of perturbation theory
to a hard-chain reference fluid: An equation of state for square-
well chains”, Fluid Phase Equilib.,168, 183 (2000)
– Gross, J. and G. Sadowski, “Perturbed-Chain SAFT: An
equation of state based on a perturbation theory for chain
molecules”, Ind. Eng. Chem. Res., 40, 1244 (2001)
– Gross, J., and G. Sadowski, “Modeling polymer systems using
the perturbed-chain statistical associating fluid theory equation
of state”, Ind. Eng. Chem. Res., 41, 1084-1093 (2002) [has
some pure polymer parameters, and polymer-monomer binary
parameters]

• Additional background:
– See Online Polymers Plus Help->Polymers Plus Reference
->Equation-of-State Models->PC-SAFT EOS Model
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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Polymer SRK EOS

• Activity coefficient models and EOS models have
complementary strengths and weaknesses
– Activity coefficient models: flexible approach for representing
composition dependence of phase equilibrium, but ignores
effect of pressure
– EOS models: pressure dependence is directly included, but not
as much flexibility with composition dependence

• Polymer SRK EOS overcomes these deficiencies by

combining the two approaches through application of
Huron-Vidal mixing rules

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Polymer SRK: Huron-Vidal Mixing Rules

• Equation of state: P = f [T , V , a( x), b( x)]
– Helmholtz free energy can be calculated from pressure because of
fundamental relationships between thermodynamic variables:
AEOS = g [T , V , a ( x ), b ( x )]
• Activity coefficient model: γ = f (T , x , τ ij )
– Helmholtz free energy: A = g ( T , x , τ )
γ ij
• Huron-Vidal mixing rules:
– Find a(x) from:

A γ = A EOS
– Find b(x) from

b( x) = ∑
i
xi bi

•
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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Polymer SRK
• Pure component parameters: T c , Pc , c1 , c 2 , c 3
– Critical parameters and Mathias -Copeman constants are available in
databanks for conventional components

α = [1 + c1(1 − Tr0. 5 ) + c2 (1 − Tr0.5 ) 2 + c3 (1 − Tr0.5 )3 ]2 Tr = T / Tc

– User must supply values for polymer/oligomers

• Binary parameters:
– NRTL parameters for conventional-conventional and conventional-
segment pairs
• Details and key references:
– See Online Polymers Plus Help->Polymers Plus Reference
->Equation-of-State Models->Polymer SRK EOS Model
Critical constants for polymers will significantly affect phase equilibrium
calculations. Unfortunately, there is no systematic way to predict
appropriate values. Therefore, we no longer recommend using this model
for polymer systems
©2004 AspenTech. All Rights Reserved.

Equation-of-State Models-Recommendation

• POLYPCSF (PC-SAFT) is more accurate for

conventional components near critical point
• POLYPCSF provides a more realistic description for
connectivity of segments when considering attractive
interactions

• POLYPCSF provides a better predictive capability

• POLYPCSF has a built-in parameter databank for over
70 components in Polymers Plus 12.1

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

PC-SAFT for Ethylene (1)

Ethylene Vapor Pressure

55

45 Experimental data

PC-SAFT

35
Pressure (bar)

25

15

-5
100 150 200 250 300
Temperature (K)

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PC-SAFT for Ethylene (2)

Ethylene Saturated Liquid Density

700

650

600

550
Density (kg/m3)

500

450
Experimental data
400 PC-SAFT

350

300

250

200
100 150 200 250 300
Temperature (K)

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

PC-SAFT for Ethylene (3)

Ethylene Supercritical Density

120

100
Experimental data

PC-SAFT
80
Density (kg/m3)

60

40
P = 50 bar

20

0
200 300 400 500 600
Temperature (K)

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PC-SAFT for LDPE (1)

Density of LDPE

0.80

0.80

0.79 Data

PC-SAFT
0.79
Density (gm/cc)

0.78

0.78

0.77

0.77
P=1bar
0.76

0.76

0.75
400 410 420 430 440 450 460 470 480
Temperature (K)

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

PC-SAFT for LDPE (2)

Density of LDPE

0.80

0.80
Data
0.79
PC-SAFT
Density (gm/cc)

0.79

0.78

0.78

P=100bar
0.77

0.77

0.76
400 410 420 430 440 450 460 470 480
Temperature (K)

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PC-SAFT for LDPE (3)

Density of LDPE

0.85

0.84 Data

PC-SAFT
Density (gm/cc)

0.83

0.82

P=1000bar
0.81

0.80
420 430 440 450 460 470 480
Temperature (K)

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

PC-SAFT for LDPE (4)

Heat capacity of amorphous LDPE

25
Heat capacity (cal/mol-K)

22
P=1atm

19

16 Data

13
PC-SAFT

10
0 50 100 150 200 250 300 350
Temperature (C)

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PC-SAFT for LDPE-Ethylene Mixtures (1)

VLE of LDPE-Ethylene

0.16

0.14 T=403K

0.12 kij=-0.0464992
Mass fraction of ethylene

0.1

0.08

0.06 Data

0.04 PC-SAFT

0.02

0
0 50 100 150 200 250
Pressure (bar)

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

PC-SAFT for LDPE-Ethylene Mixtures (2)

VLE of LDPE-Ethylene

0.14

0.12 T=493K

0.1 kij=-0.0464992
Mass fraction of ethylene

0.08

0.06
Data
0.04 PC-SAFT

0.02

0
0 50 100 150 200 250
Pressure (bar)

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Workshop 1 (1)
• Objective: To properly model the heat of polymerization and the
heat capacity of polyethylene using the PC-SAFT (POLYPCSF)
EOS method
• Background: The heat of polymerization is defined as the energy
required to convert a mole of monomers to a mole of segments on
the polymer chain. In Polymers Plus, the reference molecular
weight of the polymer is that of the segment (for homopolymers).
Thus, the heat of polymerization is the difference in enthalpy
between polymer and monomer. The experimental value from gas
ethylene to amorphous, liquid polyethylene is –1.105E8 J/Kmol
(Polymer Handbook)

A. We are going to use a sensitivity analysis to vary the heat of formation of

polyethylene so that we match the reported heat of polymerization

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Workshop 1 (2)
1. Create a new simulation “Polymers with Metric Units”,
type: Flowsheet
2. Select the components: Polyethylene, ethylene, and
ethylene segment. Use oligomer type for polyethylene
and assign 1000 ethylene segments to it

3. Choose POLYPCSF as the base property method

4. Create a pure component parameter form to enter the
necessary PC-SAFT parameters: Segment (PCSFTR =
0.0263, PCSFTV = 4.0217, PCSFTU = 252.0) and
Ethylene (obtain from User Guide Appendix)

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Workshop 1 (3)
5. Create a simple flowsheet that consists of a heater
block that operates at 25 degrees C and 1 bar, and has
one inlet (at same conditions) and one outlet stream
6. Create two PROP-SETs: one to pick up the liquid
enthalpy of polymer and the other for the vapor
enthalpy of ethylene
7. Create a sensitivity analysis case. Define the polymer
enthalpy and the monomer enthalpy for the outlet
stream using the two PROP-SETs. Vary the DHFVK
unary parameter for the polymer between –1E7 and –
1E8 to minimize the difference between reported and
calculated heat of polymerization. [Hint: Use Fortran to
compute the heat of polymerization and the percent
difference from the reported value]
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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Workshop 1 (4)
B. The second task is to regress the appropriate
parameters in order to match reported heat capacities
for polyethylene
– From the Setup section change the Run Type to Data
Regression
– From the Properties menu, create a new Data Set (Type:
PURE-COMP); select CPL (liquid heat capacity) as the
property, polyethylene as the component, and pressure 1 atm
– Enter the following experimental data:

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Workshop 1 (5)
T (K) Cp (KJ/kg-K)
280 2.141
290 2.172
300 2.202
350 2.357
400 2.511
450 2.634
500 2.788
550 2.942
600 3.097
650 3.251

• Create a Regression case. Regress the first 3 elements

of the CPIG (ideal-gas heat capacity) parameter
correlation for ETHYLENE SEGMENT
• Plot the results
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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Workshop 2 (1)

• Objective: To regress PC-SAFT pure-component and

binary interaction parameters using literature
experimental data
• Background: In this workshop, you will use liquid density
data for PE to regress the pure-component PC-SAFT
parameters, and VLE binary data for PE-ethylene to
regress the PC-SAFT k ij binary interaction parameter

©2004 AspenTech. All Rights Reserved.

Workshop 2 (2)
• Tasks:
1. Create a new simulation run. Select Template: Polymers with
Metric Units; Run Type: Data Regression
2. Add the components: Polyethylene, ethylene monomer, and
ethylene segment; choose type = OLIGOMER for
polyethylene
3. Under Polymers, Oligomers, assign 1130 ethylene segments
to the PE oligomer
4. Under Properties, Specifications, choose POLYPCSF for
property method
5. Under Properties, Parameters, Pure-Component, create a
scalar parameter set. Assign PCSFTM, PCSFTU, and
PCSFTV values for ethylene (values from User Guide
Appendix)

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Workshop 2 (3)
6. Under Properties, Data, create a Data set for enter liquid
density experimental data for PE (data type: Pure-
component). Select Property=RHOL, Pressure=1 atm. Enter
the following data points:
TEMP (C) Density (gm/cc)
135.1 0.78790
142.7 0.78358
149.5 0.77961
160.5 0.77340
172 0.76705
184.8 0.76005
198 0.75358
7. Create a Regression case that uses the above data set and
regress the PC-SAFT parameters for ethylene segment:
PCSFTR, PCSFTU, PCSFTV (Hint: provide reasonable initial
guesses)
©2004 AspenTech. All Rights Reserved.

Workshop 2 (4)
8. Run the regression. Observe the resulted parameters for PE
and plot the experimental and calculated PE densities

PE Density
0.79
Density (gm/cc)

0.78

0.77

Experimental
0.76 Regressed

0.75
100 120 140 160 180 200
Temperature (C)

©2004 AspenTech. All Rights Reserved.

©2004 AspenTech. All Rights Reserved. 4b – 26 Aspen Technology, Inc.

Process Simulation with Polymers Plus Phase Equilibrium - Polymer Equations-of-State

Workshop 2 (5)
9. The next task is to use VLE data for PE-ethylene binary
mixture and estimate the PC-SAFT k ij binary parameter.
Create a new data set (type=mixture). Select Property=TPXY,
and components: ethylene and PE. Composition basis: Mass
fraction
10. From the Data, Constraints form, remove PE
11. Specify standard deviation for the data: Temp: 0; Pres: 1%;
w.f.: 2%
12. Enter the following VLE data (all at 399.15 K temperature):
Wt. Fraction of Ethylene Pressure ( Kpa) Wt. Fraction of Ethylene Pressure ( Kpa)
0.0018 445.8 0.0285 4580
0.0055 1135 0.0330 5269
0.0107 1824 0.0381 5958
0.0158 2513
0.0198 3202
0.0242 3891
©2004 AspenTech. All Rights Reserved.

Workshop 2 (6)
13. Create a new regression case that uses the VLE data created
above, and regress the binary parameter PCSKIJ between
PE and ethylene. Plot the results in a P-x plot
VLE of PE-Ethylene Mixture

70

60
Pressure (KPa)

50
40

30

20 Experimental
10
Regressed
0
0 0.01 0.02 0.03 0.04 0.05 0.06
ethylene mass fraction

14. How do the results change if you regress the pure component
and binary parameters simultaneously using both the pure
and binary data?
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©2004 AspenTech. All Rights Reserved. 4b – 27 Aspen Technology, Inc.