Module 1: Polymer Physical Properties Overview of Polymer Property Models

Process Simulation with Polymers Plus Overview of Polymer Property Models
Module 1: Polymer Physical Properties

Overview of Polymer Property Models
Process Simulation with Polymers Plus
©2004 AspenTech. All Rights Reserved.
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
©2004 AspenTech. All Rights Reserved. 3– 1 Aspen Technology, Inc.

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
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

Background
• Polymer systems exhibit unique characteristics:
– The molecular weight and chemical composition of a polymer
may change during the process
– Because of the size difference between polymer and solvent
molecules, polymer-solvent systems exhibit large excess
entropy of mixing; this influences phase equilibrium and
physical properties (viscosity)
– Polymer can exist as a liquid-like melt, amorphous solid, or
semi-crystalline solid
– Industrially produced polymers are polydisperse in nature
• The models used must take into account the differences

between polymers and conventional systems
Importance of Thermodynamic Properties
Key Phenomena Thermophysical properties that

influence key phenomena
Mass balance Density (ρ), phase equilibrium
(binary interaction parameters)
Energy balance Heat capacity (Cp), heat of
formation (∆H f), heat of
vaporization (∆H vap)
Heat transfer ρ, Cp, thermal conductivity (k),
viscosity (η)
Pressure drop η, ρ

Design Philosophy: Polymer Property Models (1)

• Polymer models in Polymers Plus can be component-
based or segment-based:
– Component-based models treat the polymer on a molecular
basis, and have parameters for the polymer component. These
models are appropriate for homopolymers and have fewer
number of parameters to obtain
– Segment-based models treat the polymer as a collection of
repeat units (segments); the parameters are obtained for the
segments and not for the polymer component. These models
are more suitable for copolymers
• Many segment-based models allow the user to define pseudo-
homopolymer parameters; polymer parameters take priority over
segment parameters when both are defined

• The property models in Polymers Plus are designed to be flexible
– If data are available, models can be fit using simple polynomials
– If data are not available, parameters can be estimated using the
group contribution methodology of D.W. van Krevelen
• Polymers Plus has van Krevelen models for density, heat capacity,
enthalpy, entropy, melting point, glass point, Gibbs free energy,
thermal conductivity, and melt viscosity
• These models are segment based. The user may specify property
parameters for:
– The polymer component
– The segments
– If no parameters are entered, van Krevelen group contribution
techniques are used to estimate segment parameters
• These options are shown in priority order


• Property
H2
H2 C * parameters may be
C CH specified for the
* CH Polymer polymer component
CN
m
or for segments
Increasing Priority
n • Polymer
parameters take
H2 H2
C precedence over
C CH Segments
CH segment
CN parameters
• If parameters are
not specified, they
H2 are automatically
C Functional
CH CN Groups estimated using
group contributions

• Many of the property models in Polymers Plus use a branched
structure
– “Standard” models are used for conventional components
• Typically these are DIPPR correlations
– “Polymer” models are used for polymers and oligomers
• Mixture models use appropriate mixing rules

– Some solution properties, such as viscosity, are dominated by the
properties of the polymer, even when the polymer mass fraction is
very small
• Several models have been designed as corresponding-states
equations using reference conditions for temperature, molecular
weight, etc.

Transport Properties: Liquid Viscosity (1)

• The viscosity of a polymer is an extremely complex
phenomena. Observed viscosity may depend on:
– Temperature
– Polymer mass fraction in the solution
– Segmental composition of the polymer
– Pressure
– Shear rates
– Molecular size and structure:
• Weight average mole weight
• Polydispersity
• Degree of branching

• There is no unified theory capable of accounting for all of
these phenomena
• Our current models include terms for:
– Temperature
– Copolymer composition (segment fractions)
– Weight average molecular weight
– Solution composition
• We must often rely on correlations or user routines to

accurately predict the viscosity of real polymer solutions


• Most polymers exhibit a “critical molecular weight” with
respect to viscosity, above this point the viscosity
increases very rapidly with the weight-average molecular
weight
α1 • The slope α2, below the
critical mole weight, is
Mw,crit typically close to 1.0
• The slope α1, above the
ln(η 0) critical mole weight is often
much higher – e.g., 3.4
α2
ln( Mw )

• A modified Mark-Houwink (MMH) equation is used for estimation of
the polymer melt viscosity
α β
 M   Tref  E  T 
η *, l
= η ref  w    exp  η 1 − 
i M   
 ref   T   RT  Tref 
• Where:
– Mw is the weight-average molecular weight of the polymer
– Mref is a reference mole weight; typically the critical MW
– ηref is the zero-shear viscosity at the reference conditions
– Eη, β, α additional model parameters (if not provided by the user
default values are used)
– Different α values are used above and below the critical MW

Transport Properties: Mixture Viscosity

• Polymers Plus includes two liquid mixture viscosity
models
– Aspen model (default in 12.1 and higher)
• A simple, flexible correlation
• Our research shows this model is able to fit real-world data very well
– Van-Krevelen model (default in 11.1 and lower)

• Uses “pseudo-binary” mixing rule for polymer and mixed solvent
– The new model is strongly recommended
Transport Properties: Aspen Polymer Solution

Viscosity Model
3
 
(
ln η l = ∑ wi ln η i*,l + ∑ kij wi w j ln η ij + ∑ wi ∑ w j lij ln η ij )
1/3

i j> i i  j ≠i 
• Where:
– ηl = Zero shear viscosity of the mixture
– ηi * ,l = Zero shear viscosity of component i
– wi = Weight fraction of component i
– k ij = Symmetric binary parameter, kji = k ij
– lij = Antisymmetric binary parameter, lji = -lij
– lnηij = Cross binary term from viscosities of pure components

Transport Properties: van Krevelen Thermal

Conductivity Model
σ
• For each phase, σ, thermal
λ*,i σ = λ*,i,σrefψ F conductivity, λ, is calculated
as:
crystalline  T − Trefσ     
ψ = 1 + Aσ   + B σ Trefσ  1 − 1  + C σ ln T 
 Tσ  T T σ  Tσ 
 ref   ref   ref 
Thermal Conductivity
σ σ σ
 P − P   T − T  P − P 
+ Dσ   + Eσ   
ref ref ref
 Pσ   T σ  Pσ 
 ref   ref  ref 
semi-crystalline
• Parameters A-F may be

adjusted by the user; if
parameters are not provided
they are estimated from
glassy
rubbery molecular structures
liquid
• This model uses complex
Tg Tm rules to handle crystallinity
and copolymer composition
Temperature
Thermal Properties: Transition Temperatures (1)

• Many of the property models in Polymers Plus use
different correlations for each polymer phase regime
– Phase regime is determined by calculating:
• The glass transition temperature, Tg,
• The melting point, Tm
• The mass crystallinity, Xc
– In reality, the phase transitions occur over a range of
temperatures
• The transition temperatures are considered point properties to simplify
the modeling
– The crystalline fraction can be tracked through the CISOLID
substream or specified through the property parameter
POLCRY

Thermal Properties: Transition Temperatures (2)

• The glass and the melt transition temperature of a polymer
component can be calculated by:
– Specifying them as pure-component parameters for the polymer
directly
– Specifying them as pure component parameters for the segments of
the polymer
– Estimating them from the van Krevelen groups
∑fMT j j g,j ∑f M T j j m, j
Tg = Tm =
segments segments
for polymers
∑fM j j ∑fM j j
segments segments
∑n k, j Yg , k ∑n Y
k , j m ,k
Tg , j = Tm , j =
groups groups
for segments
∑n k, j Mk ∑n k, j Mk
groups groups
Thermal Properties: Molar Volume / Density

• Most EOS option sets use the equation of state to
calculate liquid density
• Polymers Plus includes two density correlations for use
with activity coefficient option sets:
– van Krevelen molar volume model
• Based on group contributions
• Simple temperature function
• Applicable to liquid, glassy, or semi-crystalline polymer
– Tait molar volume model
• Correlation based on temperature and pressure
• Applicable only for liquid phase polymer
• Best for high-pressure systems with liquid phase compressibility
©2004 AspenTech. All Rights Reserved. 3 – 10 Aspen Technology, Inc.

Thermal Properties: van Krevelen Molar

Volume / Density Model (1)
Liquid Vl
Molar Volume
Amorphous
Glassy X c=0 Semi-Crystalline

Vg
Vc
X c=1
Crystalline
0 Tg Tm
Temperature

• User may provide polymer parameter information directly:
1 A
= ρ polymer = C<T<D
V polymer 1 + BT
• Or, the segment density ρ lj is calculated from:
1 A
= ρ seg = C<T<D
Vseg 1 + BT
• Where A,B, C and D are constants and T is temperature Similar
expressions exist for the crystalline and glassy solid regions


• Next, polymer volume is obtained from:
 Mn 
V polymer = ∑f seg
 
 M seg  × Vseg
segments  
• If segment parameters A, B, C,and D are not available,
then segment volume is obtained from group
contribution:
Vseg = ∑ n j (a + b × T + cTg )Vw j
j
– nj = number of group j in segment
– a,b,c = constants; Vwj = van der Waals volume
Thermal Properties: Tait Molar Volume /

Density Model
• Polymer molar volume may also be calculated using the
Tait model (default in UNIFAC-FV property method):
  P 
Vi = M n ×Vi (0, T )1 − C ln 1 +  
  Bi  
V(0, T ) = A 0 + A1 (T − 273.15) + A 2 (T − 273.15)

2
Bi = B 0 exp [− B1 (T − 273.15)]
• Ai and B i are empirical parameters

Thermal Properties: Mixture Density

• Polymers Plus relies on the Rackett mixture model to calculate the
molar volume of the polymer-free solvent mixture, Vsol
• The solvent-polymer mixture is assumed to mix ideally:
= ∑ x i V = x pol Vpol + x solVsol

L LL L
Vmix
• This model behaves like the standard molar volume model when the
polymer mass fraction is zero
• Note that this model does not account for non-ideal mixing such as
solvent-induced swelling of a gel
Thermal Properties: Enthalpy and Heat

Capacity (1)
• Polymers Plus uses two methods to calculate the
enthalpy of polymer components
– EOS based option sets solve for enthalpy using the ideal gas
law and the enthalpy departure term, which is derived from the
equation of state
– Activity based option sets calculate the polymer enthalpy using
the heat capacity of the condensed-state polymer
• Both methods are referenced to ideal gas conditions at a

temperature of 25 C

Thermal Properties: Enthalpy and Heat Enthalpy

Capacity (2) ∆ H dep i
*,v
departure
Heat of
Gas Hi*,v (T)
DHFORM formation Ideal
DHFVK Real G
as Heat of
H *,ig
(T ) ref vaporization
∆ vap H *i (T )
i
∆ sub H *i T ref ( ) ( )
∆ con H *i T ref
DHSUB Hi*,l(T)
DHCON
Enthalpy
Liquid
s
Amorphou Heat of
Solid (
H i*, l T melt )
H i
*, l
(T ) ref
∆ fus H i* (T melt )
fusion
Semi-
Crystalline
Solid (
H i*, c T melt ) EOS Path
( )
H i*,c T ref Crystalline VK path
Solid
Tref T melt T
298K
Temperature

Capacity – van Krevelen Enthalpy Model
• Pure liquid-phase polymer:
T
H = H ( IG ,298 K ) + H
L 0
f
0
cond
(298 K ) + ∫ Cp liquid (T ) dT
298
Cpliquid (T ) = A + BT + CT + DT ( 2 3
)
• Similar relations exist for amorphous and semi-crystalline polymers
• The heat of formation (parameter DHFVK), head of condensation

(DHCON) and liquid heat capacity parameters (CPLVK) are
estimated by group contribution techniques if values are not
provided


• The heat of formation (DHFVK), heat of condensation
(DHCON), heat of sublimation (DHSUB), and liquid heat
capacity (CPLVK) may be specified for the polymer
components or segments
– If segment values are specified, the polymer properties are
calculated by segmental contributions
Ppolymer"i " = ∑P f j ij
segments" j "
P = any molar additive property
fij = molar fraction of segment “j” in “i”
– Missing segment parameters are estimated by group

contributions:
Psegment" j" = ∑P n
P = any molar additive property
k jk njk = number of occurrences of group “k” in “j”
groups"k "

• Pure liquid-phase polymer:
∫ ( A + BT + CT + DT 3 ) dT
T
H = H ( IG , 298 K ) + H
L 0
f
0
cond ( 298 K ) + 2
298
• Similar relations exist for crystalline polymers. When calculating

mixture properties, additional enthalpy of mixing due to solution
nonideality must be accounted for:
ideal nonideal
H Lm = ∑ x i HLi − RT 2 ∑ x i (∂ ln γ i / ∂T )
i i
• γ is the activity coefficient that accounts for solution nonideality.

More on it later

Enthalpy of Conventional Components: For

Activity – Coefficient Based Option Sets
∆ dep H i
*, v
Enthalpy
Heat of
Gas
departure
DHFORM formation Ideal H i*,v(T )
Gas
DHFVK R al
e
(
H i*, ig T ref )
∆ vap H i (T )
*
∆ vap H T
i
*
( ref
) Heat of
vaporization
H i*,l(T )
Enthalpy
Liquid
H *,i l (T ref ) Vapor reference

(default)
Liquid reference
(optional)
Tref T melt T
298K
©2004 AspenTech. All Rights Reserved. Temperature

Capacity – Standard Components
• Pure monomers using vapor state reference (default):
T
H L = H 0f (IG ,298 K ) + ∫ Cp IG (T ) dT + H dep (T ) − ∆HVap (T )
298
• Pure monomers using liquid state reference (more accurate):
T
H L = H 0f (IG ,298 K ) − ∆H Vap ( 298 K ) + ∫ Cp L (T ) dT
298
To use liquid reference state, change routes:
HLMX à HLMXDVK
HL àHLDVKD
Uses CPLDIP parameters for liquid heat capacity
Not valid for Henry Components!


Thermal Properties: Entropy and Gibbs Energy

– van Krevelen Models
• Gibbs energy is calculated in a similar manner
– The Gibbs free energy of formation, DGFVK, condensation,
DGCON, and sublimation, DGSUB may be specified for the
polymer component or segment
– Missing segment parameters are estimated by group
contributions
• Entropy is calculated by the relationship:

H L −GL
SL =
T

Capacity – EOS Models (1)
• The equations of state require the ideal-gas enthalpy of the polymer.
This is calculated from the heat of formation and the ideal gas heat
capacity:
( )
Enthalpy departure
*,l
H *, ig
=H *,l
(T ) + H
*,ig
−H
T
from EOS model
(T ) = H )+ ∫ Cp
*,ig *,ig ref *, ig
H (T dT
ref
T
• If DHFVK or CPIG are not specified for the polymer, they are
calculated from segment contributions
(T ref ) = ∑f
*,ig
Hi i, j H i*,,igj (T ref )
segment" j "
(T ) = ∑f
*,ig
Cpi i, j Cp *,j ig (T )
segment" j "


Capacity – EOS Models (2)
• If DHFVK is not specified for a segment, it is estimated by group
contributions:
(T ref ) = ∑n
*,ig
Hj k, j H k*,ig (T ref )
group"k"
• CPIG parameters must be specified for either the polymer or the

segment; these can be estimated during a property estimation run
• When estimating CPIG parameters for segments specify the

structure using the “UNIFAC” functional groups
• The CPIG equation is a polynomial as with standard Aspen:

Cp *,ig (T ) = C1 + C 2T + C 3T 2 + C4 T 3 + C5 T 4 + C 6 T 5
C7 ≤ T ≤ C8
Thermal Properties: Heat of Polymerization

• Heat of polymerization (∆Hpol) is the heat required to convert one mole of monomers
to one mole of segments of a polymer chain
• Heat of polymerization is related to the enthalpies of formation of the monomer and

the segment in the liquid phase according to:
∆Hpol = ∆H0f,seg + ∆Hcond,seg - ∆H0 f,mon - ∆H0 cond,mon
• Where
∆H0 f,mon is the heat of formation of monomer at the ideal-gas state
∆H0f,seg is the heat of formation of segment at the ideal-gas state
∆Hpol can be used to calculate the heat of formation of the segment

(∆H0f,seg). If ∆H0f,seg is not provided, the van Krevelen method is
used to estimate its value

Estimating Polymer Properties

• When experimental data are available for the polymer, the model
parameters should be regressed to match the existing data
• If data are not available, most properties can be estimated using

group contribution techniques
– Van-Krevelen estimations are performed “on the fly”, you do not need
to run “property estimation”
– A “property estimation” run is required or the estimation option must
be activated to estimate CPIG parameters for segments
• Most van Krevelen models have only temperature dependence; they
ignore pressure effects on density and heat capacity
Estimating Polymer Properties: Specifying van-

Krevelen Structure
• Example: specify the structure of a neopentyl-glycol repeat unit
CH3
OCH2CCH2O
Specify
CH3 VANKREV
2 x 100 ~CH2~
(last in list)
2 x 149 ~O~
Specify
1 x 106 ~C(CH2)2~
number of
occurrences
Note help of each group.
message at Entry order is
bottom not important
A complete list of groups is available in Appendix of Polymers Plus User Guide Vol
2 or through online help under topic “van Krevelen Functional Group Parameters”

Estimating Polymer Properties: Specifying van-

Krevelen Structure (Help Screen)
Estimating Polymer Properties: Estimating

CPIG Using UNIFAC
UNIFAC method is preferred

over the “general” method
because the general method will
fill in missing hydrogen atoms
which do not exist for segments

Regressing Polymer Properties: Pure

Component Properties (1)
1. Set run type to “Data Regression”

2. Specify an oligomer component with the same segmental
composition as the polymer (or polymers) for which data are
available
User has data for pure

polystyrene and SAN
copolymer with 90 mole %
styrene and 10 mole % AN


3. Specify the following property parameters for each oligomer:
– MW use polymer reference molecular weight
– POLDP number average chain length (Pn)
– POLPDI polydispersity index of the polymer (used to get Mw)
– POLCRY mass-fraction crystallinity (if polymer is semicrystalline)

4. a. Create data sets


4. b. Specify the property type and oligomer component name
Specify property; keep

in mind that solid
polymers are
considered “liquid” in
this context
Specify name of
oligomer component;
one data set is required
for each oligomer

4. c. Specify the data – remember that molar quantities must be
consistent with the specified reference mole weight
Specify data and

standard deviations
Feature to “ignore”
bad data points


5. Set up regression or evaluation case
Evaluation
compares
prediction to data
without any fitting
Data sets can be weighted

Component Properties (8) Specify parameter
6. Specify parameters to be fitted name and element
number where
applicable
Options: regress, fix, or exclude


7. Run the regression
– You can run a series of regressions sequentially to fit
parameters in a step-by-step manner
• Set up all regression cases as shown in previous slides
• When you run, you will be prompted to set the sequence order
– Each regression case uses fitted parameters from the
previous regression case
– After regression is finished Aspen will prompt you with the
option of replacing specified parameters with new fitted
parameters
Regressing Polymer Properties: Evaluate

Results (1)
Standard deviation of parameter

should be small compared to
fitted parameter value

Regressing Polymer Properties: Evaluate

Results (2)
• From the PROFILES tab, you can view data and predictions in a table
or use the plot wizard to make plots such as these:
Look for random scatter When all the points are near
around the zero line the line you have a good fit
Residual vs. Property Estimated vs. Experimental
910 920 930 940 950 960 970 980

4
Estimated RHOL REPEAT, KG/CUM

3
Residual RHOL REPEAT, KG/CUM
2
D-1 REPEAT FIT
D-1 FIT
-2 -1 0 1-3
900 910 920 930 940 950 960 970 980 900 910 920 930 940 950 960 970 980
Experimental RHOL REPEAT, KG/CUM Experimental RHOL REPEAT, KG/CUM
Regressing Polymer Properties:

Troubleshooting
• Convergence failure or high standard deviations of fitted parameters
may indicate:
– Too many fitted parameters for a small data set
• Get more data or use fewer manipulated parameters
– Predictions are not sensitive to the manipulated parameters
• Perhaps you listed the wrong parameters or you selected a temperature-
dependent parameter when fitting isothermal data
• Verify predicted melt and glass transition temperatures – model parameter for
liquid phase (DNLVK, etc.,) are used only in the appropriate temperature range
- You may need to specify TGVK and TMVK to avoid this problem
– Bad data points or inconsistent data sets
• Locate the bad data points and use “ignore” to remove them from the fitting
• Using weighing factors for data sets based on your relative conf idence in each
set

Using Property Analysis

• The “Property Analysis” tool allows you to make plots and tables
showing pure component or mixture properties as a function of
temperature, pressure, or composition
• To get properties of a polymer in a simulation run, you can use the
Property Analysis tool and either:
– Reference an existing stream in the simulation which already contains
the polymer
• Polymer attributes in the referenced stream are used for property calculations
– Use an oligomer component to represent the polymer
• Use property parameters POLDP, POLPDI, and POLCRY to specify the degree
of polymerization, polydispersity, and mass crystallinity of the oligomer
(remember Mn = Msegx Pn and Mw=MnxPDI, where Mseg is the average molecular
weight of a segment in the oligomer)
• For Property Analysis runs you must define an oligomer
Using Property Analysis: Polymer Pure-

1. From the pull-down menu, select Tools, Analysis, Properties, Pure
2. Specify temperature
range, pressure,
phase, and property,
then hit “go”
Thermodynamic (H, Cp, ρ, …)
or Transport (k, viscosity)
Suggestion: when possible, use

mass units to avoid confusion
Here “NYLON” is defined as an

oligomer with one repeat unit
Use “Save as form” to save the analysis

under Properties \ Analysis; the table will be
generated each time the simulation is run

Using Property Analysis: Polymer Pure-

960 970 980 990 1000 1010 1020 1030

RHO vs Temperature
LIQUID NYLON
RHO kg/cum
940 950
930
150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
Temperature C
End of Section: Polymer Property Models

• Workshop 1: Fitting polymer properties
• Objective
– This workshop illustrates the following concepts:
• Using oligomers to characterize polymer components
• Using Property Analysis to report the estimated properties of a polymer
• Using Data Regression to fit polymer property models against
measured data

Workshop 1: van Krevelen Properties (1)

• Objective: Estimate van Krevelen density parameters
• Problem:
– A copolymer contains two types of segments
• Ethylene segment
• New segment that has the following structure:
(CH 2)2 CO NH C C
– Your aim is to estimate the density of this copolymer using
• Group contribution
• Experimental data

• Create a new simulation (Run type: Property Analysis)
• Define segments and polymer. Define polymer as oligomer to

estimate the properties. The polymer has a total of 1000 repeat units
and the mole percent of ethylene segment is 50%. Note that the new
segment is not in the data bank
• Use POLYNRTL as the physical property method
• Under Molecular Structure enter the van Krevelen group structure

for the new segment
• Create a Prop-Set to tabulate the liquid density of the copolymer in
gm/cc (Phase=Liquid; Component=PE)


• Create an Analysis (type: Generic) to calculate the copolymer
density at 300, 350, 400, 450, and 500 K, and at atmospheric
pressure
• Density measurements for this polymer gave the following data:

T (K) ρ (gm/cc)
300 0.9570
350 0.9310
400 0.9066
450 0.8835
500 0.8618
• Compare the simulations results with the experimental data

• Under Setup, Specifications, change the Run type to
Data Regression
• Enter the experimental data in the Data folder, and
create a regression case to regress the van Krevelen
density parameters for the new segment (DNLVK 1 and
2)
• Hint: Provide starting values for the parameters to be
regressed
• Compare again the calculated density values with the
experimental data

Workshop 1: Input File

DRS CASE DNVLK
DATA-GROUPS DENSITY
TITLE 'WORKSHOP: POLYMER DENSITY' PARAMETERS PURE=1 2
IN-UNITS SI DATA-GROUP DENSITY

IN-UNITS SI MASS-DENSITY='GM/CC'
DATABANKS PURECOMP / POLYMER / SEGMENT / NOASPENPCD SYSTEM-DEF TP POLYMER PROP-LIST=RHOL
DATA 1 300.0 1.0 .9570 /
PROP-SOURCES PURECOMP / POLYMER / SEGMENT 2 350.0 1.0 .9310 /
3 400.0 1.0 .90660 /
COMPONENTS 4 450.0 1.0 .88350 /
POLYMER POLYMER POLYMER / 5 500.0 1.0 .86180
C2H4-SEG C2H4-R C2H4-SEG / STD-DEV 1 .10 -.10 -1.0
NEW-SEG * NEW-SEG
POLYMERS
PROPERTIES POLYNRTL SEGMENTS C2H4-SEG REPEAT / NEW-SEG REPEAT
OLIGOMERS POLYMER C2H4-SEG 500 / POLYMER NEW-SEG 500
STRUCTURES
VANKREV NEW-SEG 100 2 / 150 1 / 115 1 / 164 1 / & PROP-SET RHO RHO UNITS='GM/CC' SUBSTREAM=MIXED
112 1 COMPS=POLYMER &
PHASE=L
;PROP-DATA T-1
; IN-UNITS SI PROPERTY-REP NOPCES PROP-DATA DFMS
; PROP-LIST DNLVK
; PVAL NEW-SEG 6.796590550 6.42831655E-4 0.0 PROP-TABLE DENSITY PROPS
1000.000000 MOLE-FLOW POLYMER 1
STATE PRES=1 <ATM>
PARAMETERS VARY TEMP
PARAMETER 1 DNLVK NEW-SEG 1 1.0 -9.0 11.0 1.0 RANGE LOWER=300 UPPER=500 INCR=50
PARAMETER 2 DNLVK NEW-SEG 2 1.0 -9.0 11.0 1.0 TABULATE PROPERTIES=RHO
Workshop 1: Results
-------------------------------------------------- !
! TEMP ! LIQUID DENSITY OF POLYMER (GM/CC) !
! ! !
! !------------------------------------ !
! ! EXPERIM. ! VAN ! !
! K ! DATA ! KREVELEN ! REGRESSION !
! ! ! PREDICTION! !
!============!============!===========!=========== !
! 300.0000 ! 0.9570 ! 1.0367 ! 0.9568 !
! 350.0000 ! 0.9310 ! 1.0053 ! 0.9311 !
! 400.0000 ! 0.9066 ! 0.9757 ! 0.9067 !
! 450.0000 ! 0.8835 ! 0.9478 ! 0.8836 !
! 500.0000 ! 0.8618 ! 0.9215 ! 0.8616 !
-------------------------------------------------- !

Module 1: Polymer Physical Properties Overview of Polymer Property Models

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Module 1: Polymer Physical Properties Overview of Polymer Property Models

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Process Simulation with Polymers Plus Overview of Polymer Property Models

Module 1: Polymer Physical Properties

©2004 AspenTech. All Rights Reserved.

Course Agenda – Day 1

2. Polymers Plus Property Option Sets

4. Polymer Phase Equilibrium

5. User Prop-Set Properties

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Course Agenda – Day 2 and 3

8. Reactor and Flowsheet Convergence

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Workflow of a Typical Simulation Project

Identify and Select Fit / Verify Pure Fit / Verify

Develop User Prop-Set

Determine Customize Verify Model

Close Recycle Add Details Test Model

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• The models used must take into account the differences

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Importance of Thermodynamic Properties

Key Phenomena Thermophysical properties that

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Design Philosophy: Polymer Property Models (1)

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Design Philosophy: Polymer Property Models (2)

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Design Philosophy: Polymer Property Models (3)

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Design Philosophy: Polymer Property Models (4)

• Mixture models use appropriate mixing rules

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Transport Properties: Liquid Viscosity (1)

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Transport Properties: Liquid Viscosity (2)

• We must often rely on correlations or user routines to

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Transport Properties: Liquid Viscosity (3)

Transport Properties: Liquid Viscosity (4)

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Transport Properties: Mixture Viscosity

– Van-Krevelen model (default in 11.1 and lower)

– The new model is strongly recommended

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Transport Properties: Aspen Polymer Solution

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Transport Properties: van Krevelen Thermal

• Parameters A-F may be

Thermal Properties: Transition Temperatures (1)

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Thermal Properties: Transition Temperatures (2)

Thermal Properties: Molar Volume / Density

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Thermal Properties: van Krevelen Molar