Process Simulation with Polymers Plus Phase Equilibrium - Polymer Activity Coefficient Models

Module 1: Polymer Physical Properties

Phase Equilibrium – Polymer Activity
Coefficient Models
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 Activity Coefficient Models

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 Activity Coefficient Models

Activity Coefficient Based Option Sets

Activity Coefficient
Property Method Liquids + Solids Vapor Phase
Thermophysical Transport Properties Equilibrium

Cp, H, S, G, ρ η, k
POLYFH van Krevelen RKS EOS / Flory-Huggins
DIPPR
POLYNRTL van Krevelen RKS EOS / Polymer NRTL Recommended
DIPPR models
PNRTL -IG van Krevelen Ideal gas EOS Polymer NRTL
/ DIPPR
POLYUF van Krevelen RKS EOS / Polymer
DIPPR UNIFAC
POLYUFV van Krevelen RKS EOS / UNIFAC-Free-
Tait (density) DIPPR Volume

• An electrolyte-polymer NRTL model is also available as an option;

however no option set uses this model by default

• See the User Guide for details for electrolyte-polymer-NRTL

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Phase Equilibrium Calculations (VLE): Activity

Coefficient Approach – Normal Components
ϕ iv y i p = xi γ i f i *,l f i*,l = ϕ i*,v pi*,lθ i*,l
ϕ iv = Vapor fugacity coefficien t at system pressure (from EOS)
ϕ *,i v = Vapor fugacity coefficien t at pi*,l (from EOS)
pi*,l = Vapor pressure, a function of temperatur e
θ i*,l = Poynting pressure correction
 1 
∫
p
θ i*,l = exp  V i*,l dp 
 RT pi*,l

Vi*,l = Liquid molar volume
• Vapor pressure and activity coefficient are the dominant factors
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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Activity Coefficient Models

Phase Equilibrium Calculations (VLE): Activity

Coefficient Approach – Supercritical
Components
ϕ iv y i p = x i γ i* H i (
γ *i = γ i γ ∞i )
ϕ iv = Vapor fugacity coefficien t at system pressure (from EOS)
γ ∞i = Infinite dilution activity coefficient
b
H i = Henry coefficient of " i" = ai + i + ci ln T + d iT ...
T
• Supercritical components must be declared as “Henry-Comps”
• Typically used for light gasses such as N2, O2, etc.
• ai – ei are specified as the binary parameter “Henry”
• Mixing rules are applied to handle mixed solvents, see online help
• Aspen has Henry parameter database
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Phase Equilibrium Calculations (LLE)

xil1 γ il1 f i *,l = xil 2 γ il 2 f i *,l = ϕ iv yi p
• In practice, only polymer-NRTL option has been found
suitable for polymer LLE
• Polymer vapor pressure parameters usually need to be
reset (try setting PLXANT(1) = –10 to –20 in SI units)
– Aspen FLASH algorithm resolves the LLVE equations by
setting each liquid phase fugacity equal to the vapor phase
fugacity, if vapor pressure is too low vapor fugacityà0
– The optional POLYFRAC model may be more appropriate for
solving polymer liquid/liquid extractions

• We hope to resolve this issue in the future by making

alternate flash algorithms for systems with non-volatile
components
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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Activity Coefficient Models

Activity Coefficient Option Sets

– Model the non-idealities of the liquid phase as sum of
contributions from molecular size (excess entropy),
intermolecular interactions (excess enthalpy), and free volume:
ln γ = ln γ size + ln γinteractions+ ln γ FV
Model Size Interactions Free-Volume
(entropic) (enthalpic) (compressibility)
Flory-Huggins Flory Term χ = f(T) none

Polymer-NRTL Flory Term NRTL term none

τ = f( T, x )
UNIFAC Flory Term UNIFAC none

UNIFAC-FV Flory Term UNIFAC Flory EOS

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Flory-Huggins Model (POLYFH) (1)

• Flory-Huggins Activity Coefficient

– Size Term: Flory-Huggins excess entropy of mixing
– Interactions: Empirical χ binary interaction parameter. The χ
parameter represents the interactions between polymer and
solvent molecules; the larger its value, the less miscible the
two components. VLE and LLE data are fitted to obtain χ; χ is
symmetric

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Activity Coefficient Models

Flory-Huggins Model (POLYFH) (2)

FH MODEL
Output γ.
ln γ i = ln γ isize + ln γ iint eractions yi and P via
Input T, xi,
φi φ x i γ i Pi s = y iϕ iv P
and Pis at T ln γ i = ln + 1 − mi ∑ j +
xi j m j

   
mi  ∑ χ jk φiφ j  −  ∑φ j χ ij  
 k > j   j  

Binary interaction parameter (mean-field, symmetric)

χ12=χ21 bij
χ ij = aij +
T
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Flory-Huggins Model: Characteristic Size

Option Description Concentration Characteristic Size

1 Mass Basis:
wi = mass fraction n iM i
φi = = wi
M i = number average molecular weight ∑n
j
jM j
m i = si * Pi ε i
for polymer/oligomer; molecular weight
for conventional component
2 Segment mole fraction basis: ni Pi
ni = number of moles φi =
∑n j
Pj mi = s i * Pi ε i
Pi = number average chain length j

3 Volume basis:
Vi m 3 / kmol
ni Vi wi v i
= molar volume ( ) φi = =
vi m 3 / kg
= specific volume ( )
∑n V
j
j j ∑w v
j
j j
mi = s i * Pi ε i

wi
= mass fraction

• Note: the POLDP parameter can be used to set the characteristic

size Pi for a monomer or oligomer component. By default POLDP=1

• For polymers, Pi = attribute DPN

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Activity Coefficient Models

Parameters for the Flory Huggins Model

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

FHCHI/1 a ij 0.0 -100 100 X --- Binary,

Symmetric
FHCHI/2 bij 0.0 -1E6 1E6 X TEMP Binary,
Symmetric
FHSIZE/1 si 1.0 1E-15 1E15 X --- Unary
FHSIZE/2 εi 1.0 -1E10 1E10 X --- Unary
POLDP Pi 1.0 1.0 1E10 --- --- Unary

• The FHSIZE and POLDP parameters are also used in

the Flory term used by the polymer-NRTL model

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Polymer NRTL Model (POLYNRTL) (1)

2. Polymer NRTL Activity Coefficient

– Size Term: Flory Huggins excess entropy of mixing
– Interactions: Segment-based NRTL local composition model.
The τij NRTL binary parameters are used between segment
and solvent (model better suited for copolymers). VLE and
LLE data are fitted to obtain τij; τij is asymmetric
– Free volume: none

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Activity Coefficient Models

Polymer NRTL Model (POLYNRTL) (2)

φ  φ 
ln γ i = ln γ isize + ln γ iNRTL ln γ Isize = ln I  + 1− mI ∑  J 
 xI  J  mJ 

Σ X G τ X j G ji  Σ X G τ 
ln γ lNRTL = Σ iri , p  j j ji ji + Σ j  τ ij − k k kj ks 
=p  Σ k X k Gkj 
 Σ k X k Gki Σ k X kGki 
Σ XG τ X j G js  
ln γ lNRTL = j j js js + Σ j τ sj − Σ k X k Gksτ ks 
Input T, =S
Σ k X k Gks 
Σ k X k Gkj  Σk X k G kj 
x1 , x2,
and Pis
at T Gij = exp(− α ijτ ij ) αij = cij + d ij (T − 273.15)
Output γi
b yi and P via
τ ij = a ij + ij + eij ln T + f ijT
T

x i γ i Pi s = y iϕ iv P
τ1 2 ≠ τ 2 1
Binary interaction parameters (local, asymmetric)
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Parameters for Polymer-NRTL

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

NRTL/1 a ij 0 --- --- X --- Binary,

Asymmetric
NRTL/2 bij 0 --- --- X TEMP Binary,
Asymmetric
c ij
NRTL/3 0.3 --- --- X --- Binary,
Symmetric
dij
NRTL/4 0 --- --- X 1/TEMP Binary,
Symmetric
eij
NRTL/5 0 --- --- X --- Binary,
Asymmetric
fij
NRTL/6 0 --- --- X 1/TEMP Binary,
Asymmetric
min
NRTL/7 T 0 --- --- X TEMP Unary
max
NRTL/8 sT
i
1000 --- --- X TEMP Unary
FHSIZE/1 1.0 1E-15 1E15 X --- Unary
εi
FHSIZE/2 Pi 1.0 -1E10 1E10 X --- Unary
POLDP* 1.0 1.0 1E10 --- --- Unary

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Process Simulation with Polymers Plus Phase Equilibrium - Polymer Activity Coefficient Models

UNIFAC and UNIFAC-FV Models

3. UNIFAC, and

4. UNIFAC-FV methods
– Both use Flory term for size dependency
– Both models are based on group contribution; no parameters
to adjust
– UNIFAC-FV has a free-volume contribution
• Based on the Flory equation-of-state
• Uses predicted molar volumes of each species; polymer molar
volumes are calculated using the Tait model
• See user guide for detailed description
– These models are recommended for qualitative solution only

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