AspenPolymers ExsAppsV7 3 Ref

Aspen Polymers
Examples & Applications

Version Number: V7.3
March 2011
Copyright (c) 1981-2011 by Aspen Technology, Inc. All rights reserved.
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Contents
Introducing Aspen Polymers ...................................................................................1
About This Manual............................................................................................1
Related Documentation .....................................................................................3
Technical Support ............................................................................................3
A1 Creating a Simulation Model..............................................................................5

Creating a New Run..........................................................................................5
Creating the Process Flowsheet ..........................................................................6
Placing Blocks and Streams .....................................................................6
Renaming Blocks and Streams .................................................................7
Specifying Setup and Global Options...................................................................7
Entering a Simulation Title ......................................................................8
Defining Unit-Sets ..................................................................................8
Entering a Simulation Description.............................................................8
Defining Report Options ..........................................................................9
Specifying Other Simulation Options.........................................................9
Specifying Components.....................................................................................9
Characterizing Polymers.................................................................................. 10
Specifying Physical Properties .......................................................................... 11
Specifying Feed Streams ................................................................................. 11
Specifying Kinetics ......................................................................................... 12
Modifying Reactions.............................................................................. 13
Specifying Gel Effect............................................................................. 15
Defining the Unit Operation Block..................................................................... 15
Entering Block Specifications ................................................................. 15
Improving Convergence ........................................................................ 16
Overriding Global Values ....................................................................... 17
Entering Mixer Specifications ................................................................. 17
Running the Simulation................................................................................... 17
Examining Simulation Results .......................................................................... 18
Input Summary ................................................................................... 18
Plotting Distributions ...................................................................................... 21
Creating Live Distribution Plots ........................................................................ 22
Viewing Plots for Multiple Simulations ..................................................... 24
Pasting and Linking Between Aspen Polymers and Excel...................................... 26
Saving the Run and Exiting.............................................................................. 27
A2 Predicting Physical Properties.........................................................................28

Defining the Simulation................................................................................... 29
Creating a New Run.............................................................................. 29
Specifying Setup and Global Options....................................................... 30
Specifying and Characterizing Components.............................................. 30
Specifying Physical Properties ................................................................ 31
Contents iii
Defining Molecular Structure.................................................................. 32
Specifying Mass Fraction Crystallinity...................................................... 33
Creating Property Sets .......................................................................... 33
Creating Property Tables ....................................................................... 34
Running the Simulation and Examining the Results............................................. 35
Input Summary ................................................................................... 37
References .................................................................................................... 38
A3 Regressing Property Parameters.....................................................................39

Specifying Physical Property Method ....................................................... 42
Entering Experimental Data ................................................................... 42
Specifying a Regression Case................................................................. 45
Specifying Physical Property Parameters ................................................. 46
Input Summary ................................................................................... 48
References .................................................................................................... 50
A4 Fitting Kinetic Parameters...............................................................................51

Creating the Process Flowsheet .............................................................. 52
Specifying Polymerization Kinetics .......................................................... 57
Supplying Process Information ............................................................... 59
Specifying Data Regression ................................................................... 61
Input Summary ................................................................................... 66
A5 Fractionating Oligomers ..................................................................................69

Input Summary ................................................................................... 79
References .................................................................................................... 81
A6 Calculating End-Use Properties .......................................................................82

iv Contents
Creating a Sensitivity Table ................................................................... 87
Input Summary ................................................................................... 89
References .................................................................................................... 91
B1 Polystyrene Bulk Polymerization by Thermal Initiation...................................92

About This Process ......................................................................................... 92
Process Definition........................................................................................... 92
Process Conditions ............................................................................... 93
Physical Property Models and Data ......................................................... 94
Reactors / Kinetics ............................................................................... 94
Process Studies.................................................................................... 95
Selected Simulation Results............................................................................. 99
Simulation Stream Summary ............................................................... 101
References .................................................................................................. 103
B2 Polystyrene with Styrene Monomer Distillation.............................................104

About This Process ....................................................................................... 104
Process Definition......................................................................................... 104
Process Conditions ............................................................................. 105
Polymers and Segments...................................................................... 106
Physical Property Models and Data ....................................................... 106
Reactors / Kinetics ............................................................................. 107
Inhibitor............................................................................................ 107
Process Studies.................................................................................. 107
Selected Simulation Results........................................................................... 112
References .................................................................................................. 117
B3 Expanded Polystyrene Suspension Polymerization........................................118

Process Studies.................................................................................. 122
References .................................................................................................. 127
B4 Styrene Ethyl Acrylate Free-Radical Copolymerization Process .....................128

Parameter Regression ......................................................................... 131
Process Studies.................................................................................. 134
References .................................................................................................. 142
Contents v
B5 Styrene Butadiene Emulsion Copolymerization Process ................................143
Process Studies.................................................................................. 147
References .................................................................................................. 153
B6 Styrene Butadiene Ionic Polymerization Processes .......................................154

Kinetics............................................................................................. 156
Process Studies.................................................................................. 157
B7 High-Density Polyethylene High Temperature Solution Process ....................162

Process Studies.................................................................................. 164
References .................................................................................................. 180
B8 Low-Density Polyethylene High Pressure Process .........................................181

Process Studies.................................................................................. 185
References .................................................................................................. 198
B9 Nylon 6 Caprolactam Polymerization Process................................................200

Reaction Kinetics................................................................................ 203
Process Studies.................................................................................. 209
References .................................................................................................. 218
vi Contents
B10 Methyl Methacrylate Polymerization in Ethyl Acetate ..................................219
Process Studies.................................................................................. 221
References .................................................................................................. 228
B11 Polypropylene Gas Phase Polymerization Processes ...................................229

Process Studies.................................................................................. 234
References .................................................................................................. 247
Index ..................................................................................................................248
Contents vii
viii Contents
Introducing Aspen Polymers
Aspen Polymers (formerly known as Aspen Polymers Plus) is a general-

purpose process modeling system for the simulation of polymer
manufacturing processes. The modeling system includes modules for the
estimation of thermophysical properties, and for performing polymerization
kinetic calculations and associated mass and energy balances.
Also included in Aspen Polymers are modules for:
Characterizing polymer molecular structure
Calculating rheological and mechanical properties
Tracking these properties throughout a flowsheet
There are also many additional features that permit the simulation of the
entire manufacturing processes. This casebook is a compilation of simulation
examples, user models, and industrial application examples.
Note: Some of the simulations described in this book require Fortran files.
These are found in the same location as the simulation files (\xmp or \app
sub-directory of the GUI installation directory). You must compile the
accompanying Fortran before running the files.
About This Manual

The Aspen Polymers Examples & Applications Casebook is divided into two
sections:
Section A Simulation Examples provides step-by-step instructions for
using Aspen Polymers to build and use a polymer process simulation
model. Topics include:
o Creating a simulation model
o Predicting physical properties
o Regressing property parameters
o Fitting kinetic parameters
o Fractionating oligomers
o Calculating end-use properties
Section B Application Examples presents common industrial
processes and describes how to simulate the reactor section of specific
polymer production processes. A few of the application examples describe
Introducing Aspen Polymers 1

a complete plant flowsheet, and others focus on physical property
representation. Topics include:
o Polystyrene bulk polymerization by thermal initiation
o Polystyrene with styrene monomer distillation
o Expanded polystyrene suspension polymerization
o Styrene ethyl acrylate free-radical copolymerization process
o Styrene butadiene emulsion copolymerization process
o Styrene butadiene ionic polymerization processes
o High-density polyethylene high temperature solution process
o Low-density polyethylene high pressure process
o Nylon 6 caprolactam polymerization process
o Methyl methacrylate polymerization in ethyl acetate
o Polypropylene gas phase polymerization processes
Note: Dynamic process applications are available in the Aspen Dynamics

Examples documentation set.
2 Introducing Aspen Polymers

Related Documentation
In addition to this document, a number of other documents are provided to
help users learn and use Aspen Polymers applications. The documentation set
consists of the following:
Installation Guides
Aspen Engineering Suite Installation Guide
Aspen Polymers Guides

Aspen Polymers User Guide, Volume 1
Aspen Polymers User Guide, Volume 2
(Physical Property Methods & Models)
Aspen Plus Guides

Aspen Plus User Guide
Aspen Plus Getting Started Guides
Aspen Dynamics Guides

Aspen Dynamics Examples
Aspen Dynamics User Guide
Aspen Dynamics Reference Guide
Technical Support
AspenTech customers with a valid license and software maintenance
agreement can register to access the online AspenTech Support Center at:
http://support.aspentech.com
This Web support site allows you to:
Access current product documentation
Search for tech tips, solutions and frequently asked questions (FAQs)
Search for and download application examples
Search for and download service packs and product updates
Submit and track technical issues
Send suggestions
Report product defects
Review lists of known deficiencies and defects
Introducing Aspen Polymers 3

Registered users can also subscribe to our Technical Support e-Bulletins.
These e-Bulletins are used to alert users to important technical support
information such as:
Technical advisories
Product updates and releases
Customer support is also available by phone, fax, and email. The most up-to-
date contact information is available at the AspenTech Support Center at
http://support.aspentech.com.
4 Introducing Aspen Polymers

A1 Creating a Simulation
Model
This example describes how to construct a polymer simulation model. It

provides an overview of Aspen Polymers (formerly known as Aspen Polymers
Plus) features.
The steps covered include:
Creating a New Run
Creating the Process Flowsheet
Specifying Setup and Global Options
Specifying Components
Characterizing Polymers
Specifying Physical Properties
Specifying Feed Streams
Specifying Kinetics
Defining the Unit Operation Block
Running the Simulation
Examining Simulation Results
Plotting Distributions
Creating Live Distribution Plots
Pasting and Linking Between Aspen Polymers and Excel
Saving the Run and Exiting
The process in this example uses two CSTR reactors and a mixer. The free-
radical kinetics occur in the reactors.
Creating a New Run

To construct the simulation model you need to start Aspen Polymers
To start Aspen Polymers:
1 Start Aspen Plus from the Start Menu or by double clicking the Aspen Plus
icon on your desktop.
The Aspen Plus Startup dialog box appears.
A1 Creating a Simulation Model 5

2 On the Aspen Plus Startup dialog box, click the Template option. Click
OK.
The New dialog box appears. You use this dialog box to specify the
simulation template and Run Type for the new run. Aspen Plus uses the
Simulation Template you choose to automatically set various defaults
appropriate to your application.
3 For this example, click Polymers with Metric Units for your template.
The default Run type, Flowsheet, is appropriate. Click OK.
The Aspen Plus main window is now active.

In a flowsheet you can:
Place (or delete) blocks
Place (or delete) streams
Rename blocks and streams
The process flowsheet for this example is shown here.
Placing Blocks and Streams

Follow these instructions to
Place unit operation blocks
Place streams and connect blocks
To place unit operation blocks:
1 In the Model Library, click the Reactors tab, then the RCSTR icon.
2 Move the mouse to the Process Flowsheet window, then click to place
block B1.
3 In the Process Flowsheet window, click to place the second RCSTR block,
B2.
4 In the Model Library, click the Mixers/Splitters tab, then the Mixer icon.
6 A1 Creating a Simulation Model

If you want to select different Mixer model icons, click the down-arrow on
the icon.
To place streams:
1 Click the Material STREAMS icon on the left corner of the Model Library
and move the mouse to the Process Flowsheet window.
Red and blue arrows appear on the unit operation blocks. These arrows
indicate the location of the required (red) and optional (blue) stream
connection ports.
2 Place the + cursor on the red feed arrow of B1 and click to make the
connection. Move the mouse away from the block and click again to place
stream 1 (FEEDA).
3 Place the + cursor on the red product arrow of B1 and click to make the
connection. Move the mouse to the red feed arrow of B3 (M) and click
again to connect the two blocks. Refer to the process flowsheet for the
location of these streams.
4 Repeat these steps to create a feed stream for B2, connect B2 and B3
(M), and create a product stream for B3 (M).
5 After placing all streams, turn off the insert mode by clicking the Select
Mode button in the upper left corner of the Model Library.
Renaming Blocks and Streams

To rename blocks and streams:
1 Click the block to be renamed, such as B3, and click the right mouse
button to display the menu.
2 Click Rename Block.
3 Enter the Block ID as M and click OK.
4 Click the stream to be renamed, such as 1, and click the right mouse
5 Click Rename Stream.
6 Enter the Stream ID as FEEDA and click OK.
7 Repeat these steps to rename the other streams.
You are now ready to enter input data for your simulation.
Specifying Setup and Global

Options
To enter process and model specifications into Aspen Polymers, you can use
the Next button or the Data Browser Menu Tree. In this example, you
enter data using the Menu Tree.
Use the Setup folder to:
Enter a simulation title
Define unit-sets

Review and specify global options set by the simulation template you
selected
Entering a Simulation Title

To enter a title:
1 From the Data menu, click Setup.
The Setup Specifications - Data Browser appears.
2 On the Global sheet, type the title of your simulation run as:
Creating an Aspen Polymers Simulation Model
Defining Unit-Sets
This example requires a user defined unit-set for input data and output
results.
To define a unit-set:
1 From the Setup folder in the Menu Tree, double-click the Units-Sets sub-
folder.
2 Click New to create a new set.
3 Enter an ID (for example, SET1) and click OK.
A dialog box appears requesting approval to make SET1 the global unit
set, click Yes.
4 Confirm that SI is entered in the Copy from field. If it is not selected,
select SI from the pulldown list. This means the simulation will use SI
units as the basis for your new unit set.
5 Set the following options:
o Mass Flow = kg/hr
o Mole Flow = kmol/hr
o Temperature = C
o Pressure = atm
Entering a Simulation Description

A Description sheet is available to enter a more detailed description of the
simulation.
To enter the description for this example:
1 From the Setup folder in the Menu Tree, click the Specifications form.
2 Click the Description tab.
You can either retain or delete the default information displayed, but type
the following description:
This example describes how to put together a polymer simulation model.

Defining
g Re
Report Options
Since you chosee tthe Polymers with Metric Units simulation on template when
you started this
is e
example, Aspen Plus has set defaults for calcu
lculating and
reporting stream
m properties:
No mole flow
Mass flow
To enter a userr d
defined stream report format:
1 From the Setu
Setup folder in the Menu Tree, click the Report
ort Options
O form.
2 Click the Stre
Stream tab.
3 In addition to the default options, click Mole for the Flow
ow basis
b frame
and Mass for the Fraction basis frame.
Specifying
ing Other Simulation Option
ions
To enter other sim
simulation options for this example:
1 From the Setu
Setup folder in the Menu Tree, click the Simulat
lation Options
form.
2 Click the Limi
imits tab.
3 Enter 1000 in the Simulation time limit in CPU seconds
ds field.
4 Click the Syst
System tab, and click the Print Fortran traceba
ebacks when a
Fortran erro
rror occurs option.
Specifyi
ifying Components
You use Compon
ponents forms to select chemical components for
fo your
simulation and sp
specify component types (for example, convent
entional, solid,
assay, blend, poly
olymer, segment, oligomer, and pseudocompononent).
To select compon
onents:
1 From the Data menu, click Components.
2 On the Select
lection sheet, enter the components as shown:

Characterizing Polymers
You must enter additional characterization information for segments,
polymers, oligomers and site-based species. You must also define the type of
segments present. Segments can be repeat units, end groups, or branch
points attached to three or four branches.
To define the segments:
1 From the Components folder in the Menu Tree, double-click the
Polymers sub-folder.
2 From the Polymers sub-folder, click the Characterization form.
3 On the Segments sheet, from the Type pulldown list, click REPEAT for
segments STYSEG and ACNSEG.
For each polymer you must define the component attributes to be tracked. All
components specified as type Polymer in the Specifying Components
section require component attributes.
To specify component attributes for the polymers:
1 Click the Polymers tab.
2 Verify SAN appears in the Polymer ID pulldown list, or select it if it does
not appear.
3 In the Built-in attribute group field, click Free-radical selection from
the pulldown list.
The attribute summary table, Attribute list, is automatically filled in. You
can click the cells in the attribute list table or click Edit to change the
selections.
To track distributions in your simulation in order to generate plots or tables,

you need to specify the type of distribution, the polymer, and the display
characteristics for the generated distribution data.

To request a distribution:
1 From the Menu Tree, click the Distributions form.
2 On the Selection sheet, from the Polymer ID pulldown list, click SAN.

To define global physical property methods:
1 In the Menu Tree, double-click the Properties folder.
2 From the Properties folder, click Specifications.
3 On the Global sheet, in the Base method field, click POLYNRTL.
User defined property parameters such as molecular weight for polymers are
defined in the Properties folder:
1 From the Properties folder in the Menu Tree, double-click the
Parameters sub-folder.
2 In the Parameters sub-folder, click the Pure Component folder.
3 Click New.
The New Pure Component Parameters dialog box appears.
4 Verify Scalar is selected, and in the Enter new name or accept default
field enter DATA1 as new name for parameter. Click OK.
5 From the Parameters pulldown list, click MW.
6 Enter the molecular weights for the components: AIBN=164.0 and
SAN=104.150.
Specifying Feed Streams

To enter stream specifications, you either open input forms from the Data
Browser Menu Tree, or select a stream on the Process Flowsheet window and
use the right mouse button to open the stream menu, where you click Input
to open the input form. Here, you use the Menu Tree.
To enter feed stream specifications:
1 From the Menu Tree, double-click the Streams folder.
2 From the Streams folder, double-click the FEEDA sub-folder.
3 From the FEEDA sub-folder, click Input.
On the Specifications sheet, enter:
o Temperature =70C
o Pressure =2 atm
o Total Flow (Mass) = 24000 kg/hr
o Composition = Mass Frac
AIBN = 0.002
EB = 0.002
STY = 0.25
ACN = 0.25

XYLENE = 0.496
4 From the Menu Tree, double-click the FEEDB sub-folder. Click Input.
5 On the Specifications sheet, enter:
o Temperature =70 C
o Pressure =2 atm
o Total Flow (Mass) = 24000 kg/hr
o Composition = Mass Frac
AIBN = 0.004
STY = 0.1
ACN = 0.4
XYLENE = 0.496
Specifying Kinetics
Kinetic inputs are specified in the Reactions folder. This example uses the
free-radical kinetics model.
To specify the free-radical polymerization inputs:
1 From the Menu Tree, double-click the Reactions folder.
2 From the Reactions folder, click the Reactions sub-folder.
3 Click New to create a new reaction.
4 In the Enter ID field, type R1, in the Select type field, select FREE-
RAD. Click OK.
5 On the Species sheet, enter information as shown:

Be sure to click the Generate Reactions option to generate reactions
automatically from the list of reacting species.
6 Click the Comments button to add the description "Grade A SAN

polymerization kinetics." Click OK.
Modifying Reactions
To review and edit the reactions:
1 Click the Reactions tab.
An Auto Generation dialog box appears.
2 Click Yes to turn off reaction generation.
3 On the Reactions sheet, review the automatically generated reactions
and delete any unnecessary equations by selecting them in the table and
clicking the Delete button . For this example, you can delete all
reactions for:
o Chat-agent
o Chat-sol
o Term-dis
4 Click the Rate Constants tab and enter reaction rate constants as shown
for each reaction:

Note: You can also refer to the Input Summary REACTIONS paragraph for
R1 on page 20 for the rate constants of R1.
5 To verify you have entered data correctly, click the Reactions tab again,
then click the first reaction in the table, then click the Rate Constants
button.
The Rate Constant Parameters sheet for the first reaction should look
like this:
6 Click Close.

Specifying Gel Effect
To specify Gel effect:
1 Click the Gel Effect tab.
2 Click the Include gel effect checkbox.
3 From the Sentence ID pulldown list, click New.
Note: To enter data in the Sentence ID field you can also use the right
mouse button to click in the field, then click Create from the menu.
4 Click OK to accept the ID 1. Enter the information for the gel effect
correlation as shown:
Repeat the above procedures for Specifying Kinetics, Modifying Reactions, and
Specifying Gel Effect to specify the kinetics for R2. Refer to the Input
Summary REACTIONS paragraph for R2 on page 20 for the appropriate
comment, reactions, rate constants, and gel-effect correlations.
Defining the Unit Operation

Block
You must define the operating conditions for unit operations.
Entering Block Specifications

To enter block specifications for the CSTR reactors:
1 From the Menu Tree, double-click the Blocks folder.
2 From the Blocks folder, double-click the B1 sub-folder.

3 Click Setup, and on the Specifications sheet enter:
o Pressure =2 atm
o Temperature =70 C
o Valid Phases = Liquid-Only
o Reactor Volume = 10 cum
5 Click R1, then the button to move it from the Available Reaction
Sets to the Selected Reaction Sets frame.
This defines R1 as the reaction set that describes the chemical reactions
occurring in B1.
6 Click the Component Attr. tab and set:
o Substream ID = MIXED
o Component ID = SAN
7 Enter a series of Attribute ID and Component Attribute values as
below:
o Attribute ID = LPFRAC
Component Attribute value = 1E-005
o Attribute ID = LEFRAC
Component Attribute values = 0.5, 0.5
o Attribute ID = LSFRAC
o Attribute ID = LDPN
Component Attribute value = 500
o Attribute ID = SFRAC
o Attribute ID = PDI
Component Attribute value = 1.5
o Attribute ID = DPN
Component Attribute value = 1000
Improving Convergence
Polymer reaction kinetics present very difficult convergence problems, so the
standard convergence options are frequently insufficient. To resolve this
problem, we use the RCSTR block Convergence form. To do this:
1 From Blocks folder, B1 sub-folder in the Menu Tree, click the
Convergence form.
2 Click the Parameters tab and change the Solver to Newton.
3 Click Newton Parameters and change the Stabilization Strategy to
Line-Search. Click Close.
Note: This combination of parameters (step 2 and step 3) is recommended

for all addition polymerization kinetics.
4 From the Parameters sheet, click Advanced Parameters and change
the Scaling method to Component-based. Click Close.

Note: Component-based scaling is recommended for all Aspen Polymers
simulations.
5 Click the Initialize using integration option.
When this option is selected, CSTR uses an integrator to provide an initial
guess to the simultaneous equation solver.
Overriding Global Values

Block Options forms can be used to override global values for physical
properties, simulation options, diagnostic message levels and report options.
For B1 the control panel diagnostic message level is set higher than the global
default value 4. To override values:
1 From Blocks folder, B1 sub-folder in the Menu Tree, click the Block
Options form.
2 Click the Diagnostics tab, and set the On Screen slider bar to level 7.
Repeat the above procedures for Entering Block Specifications, Improving
Convergence, and Overriding Global Values to define the unit operation block
B2. Refer to the Input Summary BLOCKS B2 paragraph on page 20. Note that
only the Convergence component values differ from Block B1.
Entering Mixer Specifications

To enter Mixer specifications:
1 From the Blocks folder in Menu Tree, double-click the M sub-folder.
2 From the M sub-folder, click Input.
3 On the Flash Options sheet enter:
o Pressure = 1 atm
o Valid phases = Liquid-Only
Running the Simulation

To run a simulation:
1 Click the button to confirm that you have finished entering all required
input.
The Required Input Complete dialog box appears.
2 Click OK.
A Control Panel appears, and shows the run progress.
Note: You can also open a control panel from the Aspen Plus toolbar, by
clicking the button, then the button.
As the run proceeds, status messages appear in the Control Panel. When
the calculations are complete, the message Results Available appears in the
status bar at the right corner of the Aspen Plus main window.

Examining Simulation Results
When the message Results Available appears in the status bar you can
examine your simulation results.
To examine the results:
1 From the Menu Tree, double-click the Results Summary folder.
2 In the Results Summary folder, click Run Status.
The Summary sheet appears.
The Aspen Plus version, run starting time and run status are summarized
on this sheet.
3 From the Results Summary folder, click Streams.
The Material sheet appears with the stream results.
Since you selected the Polymers with Metric Units Simulation Template,
POLY_M is used as the stream result format and reports stream Temperature,
Pressure, Average MW, and other results. Mass Flow, and Mass Fraction are
reported based on the selections made in the Specifying Setup and Global
Options section on page 7. You can click the scroll bar to review the stream
results that are off the screen.
You select Results from the pulldown list between the and buttons
and use the button to navigate to the next form with results.
1 After reviewing the Material sheet, and selecting Results from the
pulldown list, click the button.
The Poly. Curves sheet appears. You can review the polymer structural
property distribution results for the streams.
2 Click the button.
The Stream FEEDA Results form appears.
3 Use the button to review the remainder of the results.
Input Summary
The input summary for this example is shown here:

TITLE 'Creating an Aspen Polymers Simulation Model'
IN-UNITS SI MASS-FLOW='kg/hr' MOLE-FLOW='kmol/hr' PRESSURE=atm &

TEMPERATURE=C PDROP='N/sqm'
DEF-STREAMS CONVEN ALL
SYS-OPTIONS TRACE=YES
RUN-CONTROL MAX-TIME=1000.0
DESCRIPTION "
This example describes how to put together a polymer
simulation model.
"
DATABANKS POLYMER / SEGMENT / INITIATO / PC-SAFT / &

PURE22 / NOASPENPCD
PROP-SOURCES POLYMER / SEGMENT / INITIATO / PC-SAFT / &

PURE22
COMPONENTS
AIBN C8H12N4 /
EB C8H10-4 /
STY C8H8 /
ACN C3H3N /
XYLENE C8H10-3 /
STYSEG C8H8-R /
ACNSEG C3H3N-R /
SAN SAN
FLOWSHEET
BLOCK B1 IN=FEEDA OUT=GRADEA
BLOCK B2 IN=FEEDB OUT=GRADEB
BLOCK M IN=GRADEA GRADEB OUT=PRODUCT
PROPERTIES POLYNRTL
PROP-DATA DATA1
IN-UNITS SI MASS-FLOW='kg/hr' MOLE-FLOW='kmol/hr' &
PRESSURE=atm TEMPERATURE=C PDROP='N/sqm'
PROP-LIST MW
PVAL AIBN 164.0
PVAL SAN 104.150
POLYMERS
SEGMENTS STYSEG REPEAT / ACNSEG REPEAT
POLYMERS SAN
ATTRIBUTES SAN SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM &
FMOM SMOM LDPN LZMOM LFMOM LSFLOW LSFRAC LEFLOW &
LEFRAC LPFRAC
DISTRIBUTION SAN CHAIN-SIZE
STREAM FEEDA
SUBSTREAM MIXED TEMP=70.0 PRES=2.0 MASS-FLOW=24000.0

MASS-FRAC AIBN .0020 / EB .0020 / STY .250 / ACN .250 / &
XYLENE .4960
STREAM FEEDB
MASS-FRAC AIBN .0040 / STY .10 / ACN .40 / XYLENE &
.4960
BLOCK M MIXER
PARAM PRES=1.0 NPHASE=1 PHASE=L
BLOCK B1 RCSTR
PARAM VOL=10. TEMP=70.0 PRES=2.0 NPHASE=1 PHASE=L &
SCALING=COMPONENTS ALGORITHM=MIXED
CONVERGENCE SOLVER=NEWTON STAB-STRAT=LINE-SEARCH
BLOCK-OPTION TERM-LEVEL=7
REACTIONS RXN-IDS=R1
BLOCK B2 RCSTR
PARAM VOL=10. TEMP=70.0 PRES=2.0 NPHASE=1 PHASE=L &
SCALING=COMPONENTS ALGORITHM=MIXED
BLOCK-OPTION TERM-LEVEL=7
EO-CONV-OPTI
CONV-OPTIONS
PARAM CHECKSEQ=NO
STREAM-REPOR MOLEFLOW MASSFLOW MASSFRAC
REACTIONS R1 FREE-RAD
DESCRIPTION "Grade A SAN Polymerization Kinetics"
PARAM
SPECIES INITIATOR=AIBN MONOMER=STY ACN CHAINTAG=EB &
SOLVENT=XYLENE POLYMER=SAN
MON-RSEG STY STYSEG / ACN ACNSEG
INIT-DEC AIBN .00003710 0.0 0.0
CHAIN-INI STY 4820.0 0.0 0.0
CHAIN-INI ACN 225.0 0.0 0.0
PROPAGATION STY STY 4820. 0.0 0.0
PROPAGATION STY ACN 10277. 0.0 0.0
PROPAGATION ACN STY 7165.6 0.0 0.0
PROPAGATION ACN ACN 225. 0.0 0.0
CHAT-MON STY STY 0.289 0.0 0.0
CHAT-MON STY ACN 0.289 0.0 0.0
CHAT-MON ACN STY .0060 0.0 0.0
CHAT-MON ACN ACN .0060 0.0 0.0
TERM-COMB STY STY 13900000. 0.0 0.0
TERM-COMB STY ACN 358000000. 0.0 0.0
TERM-COMB ACN STY 358000000. 0.0 0.0
TERM-COMB ACN ACN 10200000. 0.0 0.0
GEL-EFFECT TERMINATION 2 MAX-PARAMS=10 GE-PARAMS=1.0 0.0 &
2.570 -.005050 9.560 -.01760 -3.030 .007850 0.0 2.0

DESCRIPTION "Grade B SAN Polymerization Kinetics"
PARAM
SPECIES INITIATOR=AIBN MONOMER=STY ACN CHAINTAG=EB &
SOLVENT=XYLENE POLYMER=SAN
MON-RSEG STY STYSEG / ACN ACNSEG
INIT-DEC AIBN 3.71E-005 0.0 0.0 EFFIC=1.0 NRADS=2
CHAIN-INI STY 4820.0 0.0 0.0
CHAIN-INI ACN 225.0 0.0 0.0
PROPAGATION STY STY 4820.0 0.0 0.0
PROPAGATION STY ACN 10277.0 0.0 0.0
PROPAGATION ACN STY 7165.60 0.0 0.0
PROPAGATION ACN ACN 225.0 0.0 0.0
CHAT-MON STY STY .2890 0.0 0.0
CHAT-MON STY ACN .2890 0.0 0.0
CHAT-MON ACN STY .0060 0.0 0.0
CHAT-MON ACN ACN .0060 0.0 0.0
TERM-COMB STY STY 1.3900E+08 0.0 0.0
TERM-COMB STY ACN 3.5800E+09 0.0 0.0
TERM-COMB ACN STY 3.5800E+09 0.0 0.0
TERM-COMB ACN ACN 1.0200E+08 0.0 0.0
2.570 -.005050 9.560 -.01760 -3.030 .007850 0.0 2.0
Plotting Distributions
Follow these instructions to:
Display and plot the distribution data for a polymerization reactor
Display a distribution table for a stream or an entire flowsheet
To display and plot the distribution data for a polymerization reactor:
1 From the Blocks folder B1 sub-folder in the Menu Tree, click the Results
form.
2 Click the Distributions tab.
3 From the Aspen Plus menu bar, click Plot, then Plot Wizard.
The Aspen Plus Plot Wizard appears.
4 Click Next, then the icon for Chain Size Distr. plot type.
5 Click Next. If you want to review further plot options, click Next, or
proceed directly to the next step.
6 Click Finish.
The plot is displayed.
Note: You can modify the plot by using the right mouse button to click the
objects in the plot window. From the menu, click Edit, Properties, or Modify
to make necessary changes.
To display a distribution table for a stream or for the entire flowsheet:
2 Click the Streams form.
3 Click the Poly. Curves tab. You may need to use the scroll arrows to
locate the tab.

6 Click Next.
7 Click the stream(s) you want to plot from the Available box and click the
button to move them to the Selected box. In this example, all
streams are selected. If you want to review further plot options, click
Next, or proceed directly to the next step.
8 Click Finish.
The plot appears.
Creating Live Distribution Plots

The distribution plotting capability lets you create live plots that are
automatically refreshed when you rerun the simulation.
To create a live distribution plot for a reactor:
form.
5 Click Next.
6 Verify the Show average properties option is selected. Click it if it is not
selected.
7 Click Next.

8 To update the plot when new results are available, click Yes in the bottom
left corner of the Plot Wizard.
Note: To activate this feature when the plot window is active, from the Aspen
Plus menu bar, click Edit, then Live Plot.
9 Click Finish.
The plot appears.
You are now ready to make another simulation and see the plot change.
To change the specifications for B1:
1 Keeping the plot window on your screen, from the Blocks folder B1 sub-
folder in the Menu Tree, click the Setup form.
2 On the Specifications sheet, change temperature to 5C and reactor
volume to 70 cum.
3 To rerun the simulation, click the button.
Watch the distribution curve and average properties change in the plot
window.

Viewing Plots for Multiple Simulations
To manually superimpose distribution plots for several simulations you need
to:
Prepare your current plot
Select axis values
Add the new data to plot
To clear the existing plot values:
1 Click to make the plot window active. From the Aspen Plus menu bar, click
Edit, then Live Plot. This turns off the feature.
2 Click the average property text (DPN, DPW, PDI) on the plot, click the
right mouse button, then Delete. Click OK.
3 From the Blocks folder B1 sub-folder in the Menu Tree, click the Setup
form.
4 On the Specifications sheet, change temperature back to 70C and
reactor volume to 10 cum.
5 To run the simulation, click the button. This time the plot does not
change.
To manually select x-axis and y-axis values for the plot:
form.
3 You are going to manually select the x-axis values and y-axis values for
the new plot. Click DPn to select the degree of polymerization column as
the x-axis.
4 From the Aspen Plus menu bar, click Plot, then X-Axis Variable. DPn is
set as the x-axis.

5 On the Distributions sheet, click Mass frac. to select the mass fraction
column as the y-axis.
6 From the Aspen Plus menu bar, click Plot, then Y-Axis Variable. Mass
fraction is set as the y-axis.
To superimpose the new data on the plot:
1 From the Aspen Plus menu bar, click Plot, then Add New Curve.
2 To choose the plot on which the new curve should be superimposed, in the
Plot Window List dialog box, click B1: Chain Length Distribution.
3 Click OK.
The plot window shows two superimposed curves, with separate y-axes.
To use a single y-axis, use the right mouse button to click a curve line,
then click Properties from the menu.
The Plot Control Properties dialog box appears.
4 Click the AxisMap tab.
5 Click the All in One button, then click Apply.
You can use the Legend tab to change the legend for the new plot and
define the reactor conditions.

Pasting and Linking Between
Aspen Polymers and Excel
You use OLE linking to establish connections between Aspen Plus and other
applications.
To paste and link the distribution table of B1 to an Excel application:
1 From the the Blocks folder B1 sub-folder in the Menu Tree, click Results.
2 Click the Distributions tab, then use the right mouse button to click
DPn.
The column of data is highlighted.
3 On the menu, click Copy.
4 Open an Excel work sheet and type DPn as the title of the first column.
With the mouse curse over the second row, use the right mouse button to
click in the cell. On the menu, click Paste Special.
5 On the Paste Special dialog box, click Paste Link, click Text, and click
OK.
6 Repeat the same steps for the Mass frac. column.
The distribution table is generated in Excel and is updated when the
simulation results change in Aspen Plus.
To obtain reaction rate constants from Excel:
1 Open an Excel file containing the reaction rate constant parameters.
2 Use the right mouse button to select a column of reaction constants, such
as Pre-Exp (ko), and from the menu, click Copy.
3 In Aspen Plus, from the Reactions folder in the Menu Tree, click R1.

5 Click Parameters and click the Summary tab on the Rate Constant
Parameters dialog box.
6 Place the cursor in the top cell use the right mouse button to click the
Pre-Exp column, click Paste Special.
7 Click the Paste Link option and click the Text option.
The reaction constants are copied to Aspen Plus and are updated when
changes are made in Excel.
Saving the Run and Exiting

Before you exit Aspen Plus, you may save the run as a Backup file (*.bkp) or
a Quick Restart file (*.apw). It is recommended that you use the backup file
format to save disk space and for future version compatibility.
To save an .apw and a .bkp file:
1 From the Aspen Plus menu bar, click File, then Save As.
2 Enter a file name, then click .apw or .bkp in the Save as type field. Click
Save to apply.
To exit Aspen Plus:
1 From the Aspen Plus menu bar, click File, then Exit.
2 A dialog box appears asking if you want to save the run, select Yes if you
have not saved the run.
Congratulations! You have just built and run a complete polymerization
example using Aspen Polymers.

A2 Predicting Physical
Properties
This example demonstrates how to use Aspen Polymers to predict pure

component properties of polymers using the Van Krevelen group contribution
method.
Defining the Simulation
Creating a New Run
Specifying and Characterizing Components
Defining Molecular Structure
Specifying Mass Fraction Crystallinity
Creating Property Sets
Creating Property Tables
Running the Simulation and Examining the Results
The Van Krevelen method is based on the chemical structure of the polymers
(Van Krevelen, 1990) . It uses additive molar functions based on group
contribution. Using this technique a variety of polymer properties can be
predicted. In Aspen Polymers, the Van Krevelen method is used to estimate
heat capacity of both liquid and solid polymers, liquid viscosity and thermal
conductivity for both polymer melt and polymer solution, and density. In this
example, heat capacity, thermal conductivity, and density are predicted at
atmospheric pressure in the temperature range of 20 to 500C for poly (2,6
dimethyl phenylene oxide). Since this temperature range crosses the glass
point and melting point of the polymer we will see predictions for liquid and
solid polymer.
In this example, we consider the polymer of 2,6 dimethyl phenol, which can
polymerize through an oxidative coupling reaction to form a type of
poly(phenylene oxide), an aromatic polyether.
The structure of the repeat unit of this polymer is:
28 A2 Predicting Physical Properties

* O *
The repeat segment considered in this example is not available in the Aspen
Polymers databanks. Therefore, the properties of the segment are estimated
using Van Krevelen group contribution methods, by providing the groups
constituting this segment.
Property tables and property sets are used to tabulate liquid heat capacity,
heat capacity and density of the polymer.

In this example, you apply the Property Analysis feature to estimate the
properties of a polymer over a range of temperatures. When using property
analaysis or physical property data regression, the polymer components must
be defined as oligomers. This provides a mechanism through which the
structure of the molecule can be defined without using polymer component
attributes.
In this example we consider purely amorphous polymer and a polymer with
40% mass crystallinity. These two types of polymer are defined as PPO-A and
PPO-40. The resulting component list for this simulation run is:
Component Type Name Alias
PPO-A OLIGOMER
PPO-40 OLIGOMER POLY(PHENYLENE-OXIDE) PPO
PPO-REP SEGMENT POLY(PHENYLENE-OXIDE) PPO
The feed stream consists of 1 kg/hr of styrene, 1 kg/hr of n-butyl-acrylate

and 1 kg/hr of the copolymer at one atmosphere pressure and 500 K. The
feed is flashed at 500 K and 1 atm.
Creating a New Run

OK.
simulation template and Run Type for the new run.
4 Change the Run type to Property Analysis.
5 Click OK.
A2 Predicting Physical Properties 29

Note: For convenience, you may wish to change the default units set to use
temperature in degree C.

enter data using button.
To enter a title and description for the simulation:
1 From the Aspen Plus toolbar, click the button.
Estimate properties of poly(2,6 dimethyl phenoxide)
Estimate properties of 2,6-DM PPO using Van Krevelen group contribution
methods.
4 Click .
A Component Specifications Selection sheet appears.

You use Components forms to select chemical components for your
simulation and specify component types (for example, conventional, solid,
assay, blend, polymer, segment, oligomer, and pseudocomponent).
To specify and characterize components:
1 On the Component Specifications Selection sheet, enter the
Component ID, Type, Component name, and Alias for monomers,
segments and copolymer as shown:

Note: For the segment PPO-REP, the name and alias slots are left empty
because as part of this exercise you will provide molecular structure for this
segment.
2 Click .
A Components Polymers Characterization form appears.
3 On the Segments sheet, from the Type pulldown list, click REPEAT to
define PPO-REP as a repeat segment.
4 Click the Oligomers tab.
5 From the Segment pulldown list, click PPO-REP.
6 For each oligomer component, enter the number of repeat segments in
the table:
Note: In this example, the number of segments in the oligomer is arbitrary

since none of the properties being evaluated depend on the chain length. In
general, however, the number of segments should be set equal to the
expected number average degree of polymerization of the polymer.
The weight average degree of polymerization can be specified indirectly by
entering the POLPDI unary property parameter for each oligomer component.
7 Click .
A Properties Specifications Global sheet appears.

To specify physical properties:
1 On the Properties Specifications Global sheet, from the Base method
pulldown list, click POLYNRTL.
2 Click .
A Required Properties Input Complete dialog box appears.
3 Click OK.

Defining Molecular Structure
To define the molecular structure for the segment PPO-REP:
1 From the Properties folder in the Menu Tree, click the Molecular
Structure sub-folder.
2 In the Object manager, click the name PPO-REP and click Edit.
3 Click the Functional Group tab.
4 From the Method pulldown list, click VANKREV (Van Krevelen) method.
5 Enter the Group number and Number of occurrences as shown:

Note: The structure of the repeat unit is divided into groups:
* O
Group 118 Group 149
Specifying Mass Fraction Crystallinity

The crystallinity of the polymer may be specified using the POLCRY pure
component property parameter. To do this:
1 From the Properties folder in the Menu Tree, double click the
2 Click the Pure Component sub-folder.
3 On the Object manager, click New.
A New Pure Component Parameters dialog box appears.
4 To enter a scalar parameter, click OK.
5 On the Input tab, enter the oligomer component, property parameter and
mass fraction crystallinity as shown:
Creating Property Sets

To list desired polymer properties, you need to create property sets and
property tables. To do this:
1 From the Properties folder in the Menu Tree, click the Prop-Sets sub-
folder.
2 In the Object manager, click New.
A Create new ID dialog box appears

3 To accept the name PS-1, click OK.
4 On the Properties sheet, from the Physical properties and Units
pulldown lists, enter:
o CP (heat capacity) in J/kg-K
o K (thermal conductivity) in W/m-K
o RHO (density) in kg/cum
o TM (melting point) in C
o TG (glass transition temperature) in C
Your form should look like this:
5 Click the Qualifiers tab.

6 From the Phase pulldown list, click Liquid
7 In the Component row, enter PPO-A and PPO-40 in the first two columns.
Note: In Aspen Polymers, the Liquid identifier is also used to refer to all
types of solid polymer in the mixed substream. The property models switch
equations (for liquid, glassy, crystalline, or amorphous polymer) depending on
the temperature and the predicted transition temperatures.
Creating Property Tables

To create property tables:
1 From the Properties folder in the Menu Tree, click the Analysis sub-
folder.
The Create new ID dialog box appears.
3 From the Select type pulldown list, click GENERIC and accept PT-1 as
the ID by clicking OK.
4 On the System sheet, click the Specify Component Flow option and
enter 1 for each oligomer component.
5 Click the Variable tab, and for Fixed State Variables, enter a pressure
of 1 atm.

6 From the Variable pulldown list, click Temperature.
7 Click the Range/List button.
The Adjusted Variable Range/List Options dialog box appears.
8 From the Variable range or list pulldown list, click Range and enter 25C to
500C with Increments of 25. Click Close.
9 Click the Tabulate tab, and click PS-1, then click the button to move
it to Selected Prop-Sets.
Your simulation is now complete.
Running the Simulation and

Examining the Results
Run the simulation
Examine the results
To run the simulation:
1 From the Aspen Plus toolbar, click .
The Control Panel appears.
2 To run the simulation, click .
2 From the pulldown list between the and buttons, click Results.
3 Click to navigate to the next form with results.
The following figures show selected results for heat capacity, thermal
conductivity and density. Note that the polymer goes through glass transition
at 210C and melts at 397C. Above the melting point, the crystallinity is
ignored so both components show the same predictions.

Heat Capacity
2750
2500
MASS-HEAT-CA J/kg-K
2000 2250
LIQUID CP PPO-A
1750
LIQUID CP PPO-40
1500
0 50 100 150 200 250 300 350 400 450 500

TEMP C
Thermal Conductivity
0.18 0.19 0.2 0.21 0.22 0.23 0.24 0.25 0.26 0.27 0.28 0.29 0.3
Semi-Crystalline
THERMAL-COND Watt/m-K
LIQUID K PPO-A
LIQUID K PPO-40
Liquid
Amorphous Solid
Glassy Solid
0 50 100 150 200 250 300 350 400 450 500

Temperature, deg C

Density
1100
LIQUID RHO PPO-A
1050
LIQUID RHO PPO-40
1000
MASS-DENSITY kg/cum
900 950850
0 50 100 150 200 250 300 350 400 450 500

TEMP C
Input Summary
The input language summary for this example is shown here:
TGS
DYNAPLUS
DPLUS RESULTS=ON
TITLE 'Estimate properties of poly( 2,6 dimethyl phenoxide ) '
IN-UNITS SI PRESSURE=atm TEMPERATURE=C PDROP='N/sqm'
DESCRIPTION "
Estimate properties of 2,6-DM PPO using Van Krevelen
group contribution methods.
"
DATABANKS POLYMER / SEGMENT / PURE12 / NOASPENPCD
PROP-SOURCES POLYMER / SEGMENT / PURE12
COMPONENTS
PPO-A PPO /
PPO-40 PPO /
PPO-REP
PROPERTIES POLYNRTL
STRUCTURES
VANKREV PPO-REP 118 1 / 149 1
PROP-DATA PURE-1
IN-UNITS SI PRESSURE=atm TEMPERATURE=C PDROP='N/sqm'

PROP-LIST POLCRY
PVAL PPO-40 0.4
POLYMERS
SEGMENTS PPO-REP REPEAT
OLIGOMERS PPO-A PPO-REP 100. / PPO-40 PPO-REP 100.
PROP-SET PS-1 CP K RHO TM TG UNITS='J/kg-K' 'Watt/m-K' &

'kg/cum' 'C' SUBSTREAM=MIXED PHASE=L
PROP-TABLE PT-1 FLASHCURVE

MASS-FLOW PPO-A 1. / PPO-40 1.
STATE PRES=1.
VARY TEMP
RANGE LOWER=25. UPPER=500. INCR=25.
TABULATE PROPERTIES=PS-1
References
Van Krevelen, D. W. (1990). Properties of Polymers, 3rd Ed. Amsterdam:
Elsevier.

A3 Regressing Property
Parameters
This example demonstrates how to use the data regression (DRS) capabilities
to fit the mixture parameters of an equation of state (EOS) model to binary
vapor-liquid equilibrium (VLE) data.
Creating a New Run
Specifying Physical Property Method
Entering Experimental Data
Specifying a Regression Case
Specifying Physical Property Parameters
Correlative models used to describe thermodynamic properties of mixtures
often contain binary interaction parameters. These parameters account for
mixture non-idealities, and are necessary for accurate representation of the
mixture behavior. For each constituent pair of a multicomponent mixture,
these parameters are obtained by regressing some form of binary
experimental information.
In this example, binary VLE data of ethylene-polyethylene mixture is
regressed to obtain the two binary interaction parameters of the Sanchez-
Lacombe EOS, k ij and ij . You can find the details of this model in Volume 2
of the Aspen Polymers User Guide. Ethylene-polyethylene binary mixture is
encountered in polyolefin production, and at high pressures the
thermodynamic behavior of this mixture can be described by an EOS such as
the Sanchez-Lacombe model.
A3 Regressing Property Parameters 39

In this example, you create an Aspen Polymers data regression (DRS)
session, run the DRS, and examine the results.
Creating a New Run

OK.
4 From the Run type pulldown list, click Data Regression
5 Click OK.

User the Setup folder to:
Enter simulation title and description
Define unit-sets
Entering a Simulation Title and Description

Regression of binary parameters for the POLYSL model
3 In the Units of measurement field, for Input data and Output results,
click SI.
The objective of this example is to demonstrate how to use the data
40 A3 Regressing Property Parameters

regression capabilities to fit the mixture parameters of an EOS model to
binary VLE data.
Defining Unit-Sets
1 From the Setup folder in the Menu Tree, click the Units-Sets sub-folder.
2 Click New.
3 To accept US-1 as the unit set ID, click OK.
A dialog box appears requesting approval to make US-1 the global unit set
4 Click No.
5 On the Standard sheet, from the Copy from pulldown list, click Eng.
o Temperature = K
o Pressure = bar
7 Click the Transport tab
8 From the Density pulldown list, click kg/cum.
9 Repeat these steps to create unit set US-3 (step 3) in which:
o Copy from=SI (step 5)
o Pressure=bar (step 6)
o Delta P=bar (step 6)
10 Click .

The component information necessary for this DRS run is:
Component Type Component Name Alias
ID
PE Oligomer POLY(ETHYLENE) PE
ETHYLENE Conventional ETHYLENE C2H4
C2H4-R Segment ETHYLENE-R C2H4-R
In this example, the polymer is identified as oligomer. This is required for

property data regresssion and property analysis runs. By defining the polymer
as an oligomer, the need to enter any attribute information is eliminated.
The composition (segment fractions) and the number-average chain length
and moleuclar weight of the polymer are determined from the structure
defined in the oligomer form. To avoid a warning message, you need to
supply the true molecular weight of the oligomer as described in the
Specifying Physical Property Parameters section on page 46. However, the
results of the DRS run are not affected by the reference molecular weight
specified in the property parameters section.
To supply the component information for this example:

Component ID, Component name, and Alias for ethylene,
polyethylene and ethylene segment as shown:
2 From the Components folder in the Menu Tree, click the Polymers sub-
folder.
3 On the Segments sheet, from the Type pulldown list, click REPEAT.
4 Click the Oligomers tab, select C2H4-R as the segment and enter 1132
for PE in the oligomer row.
5 Click .
The Properties Specifications Global sheet appears.
Specifying Physical Property Method

The Sanchez-Lacombe model physical property method (POLYSL) is used in
this example. To choose this method:
1 On the Properties Specifications Global sheet, from the Base method
pulldown list, click POLYSL.
2 Click .
An Information dialog box appears.
3 Click OK.
The Properties Data form appears.
Entering Experimental Data

The experimental data used in this DRS run is from Hao and coauthors, and is
provided in the appropriate steps of this procedure (Hao, Elbro, & Alessi,
1992).
To enter the experimental data:

2 Enter ID as C2PE399 (for data at 399K), and from the Select type
pulldown list, click MIXTURE.
3 Click OK.
A Properties Data Setup sheet for C2PE399 appears.
4 Enter:
o Category = Phase equilibrium
o Component basis = Mass Fraction
o Data type = TPXY
A Change Data Type dialog box appears, click OK.
5 From Available Components, click ETHYLENE and click to move it
to Selected Components.
6 Repeat step 5 for PE.
7 Click the Constraints tab. You need to delete PE from the Component
column since PE is considered involatile in this example. Use the right
mouse button to click PE, then click Clear.
8 Click the Data tab, enter:
o Temperature = K
o Pressure = kPa
o Overwrite standard deviation as:
Temperature = 0
Pressure = 1%
Mole fraction = .001
Enter the data at 399.15K from Hao et al. (1992).
Usage Temp., K Pressure, KPA X, Ethylene X, PE
STD-DEV 0 1% .001 0
DATA 399.15 455.8 .0018 0.9982
DATA 399.15 790.30 .0037 0.9963
DATA 399.15 1135 .0055 0.9945
DATA 399.15 1479 .0075 0.9925
DATA 399.15 1824 .0107 0.9893
DATA 399.15 2168 .0136 0.9864
DATA 399.15 2513 .0158 0.9842
DATA 399.15 2857 .0175 0.9825
DATA 399.15 3202 .0198 0.9802
DATA 399.15 3546 .0221 0.9779
DATA 399.15 3891 .0242 0.9758
DATA 399.15 4235 .0255 0.9745
DATA 399.15 4580 .0285 0.9715
DATA 399.15 4924 .0305 0.9695
DATA 399.15 5269 .0330 0.967
DATA 399.15 5613 .0359 0.9641
After the first four entries, your data sheet should look like this:

9 From the Properties folder in the Menu Tree, click the Data folder and
repeat the steps to enter the data from Hao et al. (1992) at 413.15K and
428.15K.
STD-DEV 0 1% .001 0
DATA 413.15 455.8 .0015 0.9985
DATA 413.15 790.30 .0034 0.9966
DATA 413.15 1135 .0048 0.9952
DATA 413.15 1479 .0068 0.9932
DATA 413.15 1824 .0087 0.9913
DATA 413.15 2168 .0112 0.9888
DATA 413.15 2513 .0131 0.9869
DATA 413.15 2857 .0151 0.9849
DATA 413.15 3202 .0166 0.9834
DATA 413.15 3546 .0189 0.9811
DATA 413.15 3891 .0208 0.9792
DATA 413.15 4235 .0235 0.9765
DATA 413.15 4580 .0250 0.975
DATA 413.15 4924 .0277 0.9723
DATA 413.15 5269 .0296 0.9704
DATA 413.15 5613 .0328 0.9672
DATA 428.15 455.8 .0013 0.9987
DATA 428.15 790.30 .0029 0.9971
DATA 428.15 1135 .0039 0.9961
DATA 428.15 1479 .0055 0.9945
DATA 428.15 1824 .0074 0.9926
DATA 428.15 2168 .0090 0.991
DATA 428.15 2513 .0105 0.9895
DATA 428.15 2857 .012 0.988
DATA 428.15 3202 .0146 0.9854
DATA 428.15 3546 .0164 0.9836
DATA 428.15 3891 .0178 0.9822

DATA 428.15 4235 .0207 0.9793

DATA 428.15 4580 .0222 0.9778
DATA 428.15 4924 .0242 0.9758
DATA 428.15 5269 .0265 0.9735
DATA 428.15 5613 .0286 0.9714
10 Click .
A Regression Cases Incomplete dialog box appears.
Specifying a Regression Case

To specify a regression case:
1 On the Regression Cases Incomplete dialog box, click Specify the data
regression cases.
2 Click OK.
3 Click New.
4 To accept R-1, click OK.
5 Click the Parameters tab, enter the Initial value, Lower bound, and
other options as shown:
Note: The binary parameters may be specified for the oligomer-conventional

species pair or for the segment-conventional species pair. For homopolymers
either approach is suitable. For copolymers, the segment approach offers
greater flexibility to account for the influence of polymer segmental
composition on phase equilibrium.
6 Click .

Specifying Physical Property Parameters
To specify physical property parameters:
1 On the Required Properties Input Complete dialog box, click Enter
property parameters option.
2 Click OK.
An Additional property parameters dialog box appears.
3 To accept the Pure Component Parameters option, click OK.
In the Sanchez-Lacombe model, for each component, three pure component
constants, T*, P*, and * are needed.
To enter these pure component constants:
1 In the Properties Parameters Pure Component form, click New.
2 In the lower right corner of New Pure Component Parameters dialog
box, enter PCES-1 as the new name.
3 To accept the Scalar option, click OK.
4 On the Input sheet, click US-1 from the toolbar units-set pulldown list,
enter the other information as shown:
Note: These constants are reported in Appendix E of the Aspen Polymers

User Guide, Volume 2. Unary parameters are entered for segment of the
polymer, rather than the polymer itself.
5 From the Properties folder Parameters sub-folder in the Menu Tree,
click the Pure-Component sub-folder.
box, enter MW as the new name.
9 On the Input sheet, click US-3 from the toolbar units-set pulldown list,
enter the other information as shown:

Note: It is necessary to identify a polymeric molecule when the oligomer
option is used.

Run the simulation
Examine the results
1 Click .
2 Click OK.
A Required Data Regression Input Complete dialog box appears.
3 Click OK.
A Data Regression Run Selection dialog box appears.
4 To accept R-1 as the run selection, click OK.
The Control Panel appears and the simulation starts running.
5 When the Parameter Values dialog box appears, click Yes to all to
replace the existing parameters with the regressed values.
When you see the message Data Regression completed, the results are
present.

Input Summary
TITLE 'Regression of binary parameters for the POLYSL model'
IN-UNITS SI
DESCRIPTION "
The objective of this example is to demonstrate how to
use the data regression capabilities to fit the mixture
parameters of an EOS model to binary VLE data. "
COMPONENTS
ETHYLENE C2H4 ETHYLENE /
PE PE PE /
C2H4-R C2H4-R C2H4-R
PROPERTIES POLYSL
PROP-DATA MW
IN-UNITS SI PRESSURE=bar PDROP=bar
PROP-LIST MW
PVAL PE 31756.8563
PROP-DATA PCES-1
IN-UNITS ENG DENSITY='kg/cum' PRESSURE=bar TEMPERATURE=K &
PDROP=psi
PROP-LIST SLPSTR / SLRSTR / SLTSTR
PVAL C2H4-R 4250 / 887 / 673
PVAL ETHYLENE 3339 / 660 / 291
PROP-DATA SLETIJ-1
IN-UNITS SI
PROP-LIST SLETIJ
BPVAL PE ETHYLENE -.4040175320
BPVAL ETHYLENE PE -.4040175320
PROP-DATA SLKIJ-1
IN-UNITS SI
PROP-LIST SLKIJ
BPVAL PE ETHYLENE -.0900000000
BPVAL ETHYLENE PE -.0900000000
PARAMETERS
BIPARAMETER 1 SLKIJ PE ETHYLENE 1 1.00000000E-02 &
-9.00000000E-02 1.10000000E-01 1.00000000E+00
BIPARAMETER 2 SLETIJ PE ETHYLENE 1 -9.00000000E-02 &
-9.90000000E-01 8.10000000E-01 1.00000000E+00
CASE R-1

DATA-GROUPS C2PE399 CONSISTENCY=YES / C2PE413 &
CONSISTENCY=YES / C2PE428 CONSISTENCY=YES
PARAMETERS BINARY=1 2
DATA-GROUP C2PE399
IN-UNITS SI PRESSURE=kPa PDROP='N/sqm'
SYSTEM-DEF TPXY ETHYLENE PE COMPOSITION=MASS-FRAC
PHASE-EQ VL ETHYLENE
DATA 1 399.15 455.8 .0018 1 /
2 399.15 790.30 .0037 1 /
3 399.15 1135 .0055 1 /
4 399.15 1479 .0075 1 /
5 399.15 1824 .0107 1 /
6 399.15 2168 .0136 1 /
7 399.15 2513 .0158 1 /
8 399.15 2857 .0175 1 /
9 399.15 3202 .0198 1 /
10 399.15 3546 .0221 1 /
11 399.15 3891 .0242 1 /
12 399.15 4235 .0255 1 /
13 399.15 4580 .0285 1 /
14 399.15 4924 .0305 1 /
15 399.15 5269 .0330 1 /
16 399.15 5613 .0359 1
STD-DEV 1 0 -1 .001 -1
DATA-GROUP C2PE413
DATA 1 413.15 455.8 .0015 1 /
2 413.15 790.30 .0034 1 /
3 413.15 1135 .0048 1 /
4 413.15 1479 .0068 1 /
5 413.15 1824 .0087 1 /
6 413.15 2168 .0112 1 /
7 413.15 2513 .0131 1 /
8 413.15 2857 .0151 1 /
9 413.15 3202 .0166 1 /
10 413.15 3546 .0189 1 /
11 413.15 3891 .0208 1 /
12 413.15 4235 .0235 1 /
13 413.15 4580 .0250 1 /
14 413.15 4924 .0277 1 /
15 413.15 5269 .0296 1 /
16 413.15 5613 .0328 1
STD-DEV 1 0 -1 .001 -1
DATA-GROUP C2PE428
DATA 1 428.15 455.8 .0013 1 /
2 428.15 790.30 .0029 1 /
3 428.15 1135 .0039 1 /
4 428.15 1479 .0055 1 /
5 428.15 1824 .0074 1 /

6 428.15 2168 .0090 1 /
7 428.15 2513 .0105 1 /
8 428.15 2857 .012 1 /
9 428.15 3202 .0146 1 /
10 428.15 3546 .0164 1 /
11 428.15 3891 .0178 1 /
12 428.15 4235 .0207 1 /
13 428.15 4580 .0222 1 /
14 428.15 4924 .0242 1 /
15 428.15 5269 .0265 1 /
16 428.15 5613 .0286 1
STD-DEV 1 0 -1 .001 -1
POLYMERS
SEGMENTS C2H4-R REPEAT
OLIGOMERS PE C2H4-R 1132
PROPERTY-REP NOPCES PROP-DATA DFMS
References
Hao, W., Elbro, H. S., & Alessi, P. (1992). Polymer Solution Data Collection.
Chemistry Data Series, XIV, Part 1, DECHEMA.

A4 Fitting Kinetic
Parameters
This example demonstrates how to fit kinetic rate constant parameters to

available data for a single reactor flowsheet. This example describes the basic
procedure for developing a simulation to fit kinetic parameters.
Creating a New Run
Specifying Polymerization Kinetics
Supplying Process Information
Specifying Data Regression
The Styrene Ethyl Acrylate Free-Radical Copolymerization Process application
example in Section C provides strategies for fitting parameters for complex
systems.
In this process, vinyl acetate is polymerized in solution in a batch reactor with
methanol as a solvent and methyl peroxide as the initiator. The reactor is
operated isothermally with the polymerization temperature maintained at the
boiling point of methanol, 64.7C, 1 atm.
The reactor is considered liquid filled. Therefore, vapor-liquid equilibrium
calculations are not accounted for in this simulation. In practice, there is
usually some vapor space in the reactor and reflux condenser. This has some
effect on the concentration in the liquid phase. However, the effect is not
considered significant for this homopolymerization example. The simulation
can be modified to include VLE calculations if necessary.
The component information is:
Component ID Type Component Name Alias
MPO Conventional VINYL-ACETATE C4H6O2-1
A4 Fitting Kinetic Parameters 51

VAC Conventional VINYL-ACETATE C4H6O2-1
MEOH Conventional METHANOL CH4O
POLY Polymer POLY(VINYL-ACETATE) PVAC
VAC-SEG Segment VINYL-ACETATE-R C4H6O2-R-3
The feed stream consists of 100 kg/hr of vinyl acetate, 80 kg/hr of methanol,
0.0258 kg/hr of initiator at one atmosphere and 64.7C. The initial charge is
determined by multiplying the flowrates by the cycle time needed to prepare
the charge.

This example demonstrates how to fit kinetic rate constant parameters to
available data for a single reactor flowsheet.
Creating a New Run

OK.
The default Run type, Flowsheet, is appropriate for this example.
4 Click OK.

The process flowsheet for this example is shown here:
52 A4 Fitting Kinetic Parameters

1 In the Model Library, click the Reactors tab, then the RBatch icon.
If you want to select different RBatch model icons, click the down-arrow
on the icon.
the block (BATCH).
To place streams:
connection ports.
2 Place the + cursor on the red feed arrow and click to make the
stream 1 (FEED).
3 Repeat step 2 to create the product stream.
Renaming Blocks and Streams

To rename blocks and streams:
1 Click the block to be renamed, B1, and click the right mouse button to
display the menu.
2 Click Rename Block.
3 Enter the Block ID as BATCH and click OK.

4 Click the stream to be renamed, such as 1 (FEED), and click the right
mouse button to display the menu.
6 Enter the Stream ID as FEED and click OK.
7 Repeat steps 4-6 to rename the PRODUCT stream.

User the Setup folder to:
Enter simulation title and description
Define unit-sets
Review and specify other global simulation options

Free-Radical Kinetics Parameter Fitting
This example illustrates how to fit kinetic rate constant parameters in
Aspen Polymers.
Defining Unit-Sets
2 Click New.
3 To accept US-1 as the unit set ID, click OK.
A dialog box appears requesting approval to make US-1 the global unit set
4 Click Yes.
5 On the Standard sheet, from the Copy from pulldown list, click SI.
Mass Flow = kg/hr
Mole Flow = kmol/hr
Pressure = atm

Temperature = C
7 Click .

Component ID, Component name, and Alias for monomers, segments
and copolymer as shown:
2 Click .
3 On the Segments sheet, from the Type pulldown list, click REPEAT to
define VAC-SEG as a repeat segment.
4 Click the Polymers tab, from the Built-in attribute group pulldown list,
click Free-radical selection.
5 To modify the attribute group, click Edit.
6 On the Polymer Attributes dialog box, click to clear the attributes that
do not appear below.

7 Click Close.
8 Click .
A Properties Specifications Global form appears.

Specify physical properties
Enter pure component parameters
Enter a Prop-Set
Display a Prop-Set in a stream report
On the Properties Specifications Global form, from the Base method
pulldown list, click POLYNRTL.
Defining Pure Component Parameters

To enter pure component parameters:
1 From the Properties folder in the Menu Tree, double-click the
2 Click the Pure Component sub-folder.
box, enter DATA-1 as the new name.
6 On the Input sheet, in the Parameters cell, click to select MW from the
pulldown list.
For Component, enter:
Component MW

MPO 76.050
Defining a Prop-Set
To enter a Prop-Set:
folder.
2 In the Object Manager, click New.
3 Enter DENSITY as the new name of the property set. Click OK.
4 On the Properties tab, click in the Physical properties cell to select
RHO, click the Units cell to select kg/cum. Repeat this step to select
RHOMX, with units of kg/cum.
5 Click the Qualifiers tab from the Phase pulldown list, click and Liquid.
6 From the pulldown lists in the Component row, click to select VAC,
POLY, and MEOH.
Defining the Stream Report

To display the Prop-Set in the stream report:
1 From the Setup folder in the Menu Tree, click the Report Options form.
2 Click the Stream tab.
3 Click the Property Sets button, click DENSITY, and click to move it
to Selected Property Sets.
4 Click Close.
Specifying Polymerization Kinetics

To specify polymerization kinetics:
1 From the Menu Tree, double-click the Reactions.
2 From the Reactions folder, click the Reactions sub-folder.
4 In the Enter ID field, type REAC-1, and from the Select Type pulldown
list click FREE-RAD. Click OK.
5 On the Species sheet, enter the data as shown:

6 Click the Reactions tab, enter the data as shown:
To do this for the first reaction:

o Click New.
On the Add Reaction dialog box, enter:
Reaction type = INIT-DEC
Initiator = MPO for the
o Click Done.
o Repeat these steps for the other 6 reactions using the information
shown.
7 On the Reactions form, click the Rate Constants button. Click the
Summary tab and enter the following rate information:
Type Pre-Exponential Activation Energy
(1/s) (J/kmol)
Initiator Decomposition 5.0E-6 0

Type Pre-Exponential Activation Energy
(1/s) (J/kmol)
Chain Initiation 9500 0

Propagation 1000 0
Chain Transfer to Monomer 2.337 0
Chain Transfer to Polymer 1.235 0
Chain Transfer to Solvent 0.323 0
Termination by disproportionation 1.645E8 0
8 Click Close.
Specifying Gel-Effect
To specify gel effect:
1 Click the Options tab, and click the Gel Effect option.
2 Click the Gel Effect tab.
3 From the No. pulldown list, click New.
Note: To enter data in the No. field you can also use the right mouse button
to click in the field, then click Create from the menu.
4 Enter the information for the gel effect correlation as shown:

Enter feed stream information
Enter block information
Set block convergence and user information

Specifying Stream Conditions
To enter feed stream information:
2 From the Streams folder, click the FEED sub-folder.
3 On the Specifications sheet, enter the stream conditions as:
o Temperature = 64.7C
o Pressure = 1 atm
o MPO = 0.028 kg/hr
o VAC = 100 kg/hr
o MEOH = 80 kg/hr
4 Click .
Specifying Block Conditions

To enter block information:
1 On the Specifications sheet, from the Reactor operating specification
pulldown list, click Constant temperature.
2 Enter:
o Pressure = 1 atm
The Reactor field already displays Liquid-only.
3 Click the Reactions tab, click REAC-1, and click to move it to the
Selected reaction sets frame.
4 Click the Stop Criteria tab, enter:
o Criterion No. =1
o Location = Reactor
o Variable type = Time
o Stop value = 5
5 Click the Operation Times tab, enter:
o Total cycle time =1 hr
o Maximum calculation time = 5 hr.
o Time interval between profile points = 0.5 hr
o Maximum number of profile points = 52
Defining Block Convergence

To set convergence and user information for the block:
1 From the Menu Tree Blocks folder BATCH sub-folder, click the
Convergence form.
2 Click the Integration Loop tab, enter:
o Integration convergence tolerance = 1E-6
o Initial step size of integration variable = 1E-7
o Maximum step size of integration variable = 0.1 hr.

3 From the Menu Tree Blocks folder BATCH sub-folder, click the User
Subroutine form.
4 In the Values for parameters frame, enter:
o Integer = 100
o Real = 21000
5 Click the User Variables tab, and in the Number of user variables
field, enter 1.
Specifying Data Regression

Specify data regression
Create multiple data sets
Define the regression cases
Define the block convergence sequence
To specify data regression:
1 From the Menu Tree, double-click the Model Analysis Tools folder.
2 Double-click the Data Fit folder.
3 Click the Data Set sub-folder.
You will need to create two data sets: one named D-INITIA and one
named D-PROPAG.
Creating Data Sets

To create the first data set:
2 In the Enter ID field, enter D-INITIA, and in the Select Type field, click
to select PROFILE-DATA. Click OK.
3 On the Define sheet, enter the data as shown (where MFINIT is the mass
fraction of the initiator):

4 Click the Data tab, enter a Std-Dev of 1.0 and from the Time pulldown
list, click hr.
5 Enter the time and mass fraction data as shown:
Data Time (hr) Mass Fraction of Initiator
Point
1 0.0 1.554E-4
2 0.5 1.551E-4
3 1.0 1.546E-4
4 1.5 1.542E-4
5 2.0 1.538E-4
6 2.5 1.532E-4
7 3.0 1.526E-4
8 3.5 1.522E-4
9 4.0 1.518E-4
10 4.5 1.513E-4
11 5.0 1.509E-4
6 Click the Initial Conditions tab, enter:
o Temperature = 65C
o Pressure = 1 atm
The Reactor type and Block name fields already display RBATCH and
BATCH respectively.
To create the second data set:
1 From the Menu Tree Model Analysis Tools folder Data Fit sub-folder,
click the Data Set sub-folder.
3 In the Enter ID field, enter D-PROPAG, and in the Select Type field,
click to select PROFILE-DATA. Click OK.
4 On the Define sheet, enter:
o Variable name = DUTY
o Variable = DUTY
o Model and block name = BATCH
RBATCH is already selected as the Block name.
5 Click the Data tab, enter a Std-Dev of 5.0.
Enter the time and heat release data shown:
Data Time (hr) Instantaneous Heat Release
Point (Watt)
2 0.5 -3750.0
3 1.0 -3700.0
4 1.5 -3300.0
5 2.0 -3250.0
6 2.5 -3100.0
7 3.0 -3000.0
8 3.5 -2800.0
9 4.0 -2650.0

10 4.5 -2350.0
11 5.0 -2150.0
6 Click the Initial Conditions tab, enter:
o Pressure = 1 atm
The Reactor type and Block name fields already display RBATCH and
BATCH respectively.
7 Click .
Defining Regression Cases

To define the first regression case:
1 On the Data-Fit Regression Cases Incomplete dialog box, click to
select Specify Data-Fit Regression Cases. Click OK.
2 From the Menu Tree, click the Regression folder.
3 In the Object manager, click New
4 In the Enter ID field, enter INITA. Click OK.
5 On the Specifications sheet, from the Data set pulldown list, click D-
INITIA.
The Weight is entered as 1.
6 Click the Vary tab, enter:
To define the second regression case:

1 From the Menu Tree Model Analysis Tools folder Data Fit sub-folder,
click the Regression sub-folder.
3 In the Enter ID field, enter PROPAGA. Click OK.
4 On the Specifications sheet, from the Data set pulldown list, click D-
PROPAGA.
The Weight is entered as 1.

6 Click the Convergence tab, in the Absolute function tolerance field,
enter 1.0.
Defining Block Convergence Sequence

To define the block convergence sequence:
1 From the Menu Tree, double-click the Convergence folder.
2 From the Convergence folder, click the Sequence sub-folder.
3 In the Object manager, Click New.
4 To accept S-1 as the sequence name, click OK.

Run the simulation
Examine the results
The results for initiation are:
The results for propagation are:

Input Summary
TITLE 'Free-Radical Kinetics Parameter Fitting'

TEMPERATURE=C TIME=hr PDROP='N/sqm'
DESCRIPTION "
This example illustrates how to fit kinetic rate constant
parameters in Aspen Polymers. "
DATABANKS PURE11 / POLYMER / SEGMENT / NOASPENPCD
PROP-SOURCES PURE11 / POLYMER / SEGMENT
COMPONENTS
MPO C4H6O2-1 /
VAC C4H6O2-1 /
MEOH CH4O /
POLY PVAC /
VAC-SEG C4H6O2-R-3
FLOWSHEET
BLOCK BATCH IN=FEED OUT=PRODUCT
PROPERTIES POLYNRTL
PROP-DATA DATA1
IN-UNITS SI
PROP-LIST MW

PVAL MPO 76.050
POLYMERS
SEGMENTS VAC-SEG REPEAT
POLYMERS POLY
ATTRIBUTES POLY SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM &
FMOM SMOM LSFLOW LEFLOW
PROP-SET DENSITY RHO RHOMX UNITS='kg/cum' SUBSTREAM=MIXED &

COMPS=VAC POLY MEOH PHASE=L
STREAM FEED
SUBSTREAM MIXED TEMP=64.70 PRES=1.0
MASS-FLOW MPO .028 / VAC 100 / MEOH 80
BLOCK BATCH RBATCH

USER-VECS NUSER-PROF=1
INT VALUE-LIST=100
REAL VALUE-LIST=21000.0
PARAM TYPE=T-SPEC PRINT-TIME=.5 CYCLE-TIME=1.0 MAX-TIME=5.0 &
MAX-NPOINT=52 PRES=1.0 TEMP=64.70 NPHASE=1 PHASE=L &
INT-TOL=1.000E-06 HINIT=1.000E-07
INTEG-PARAMS MAXSTEP=.1
STOP 1 REACTOR TIME 5.0
REACTIONS RXN-IDS=REAC-1
REGR-POINTS 1 D-INITIA VALUE-LIST= 0.0 1800.000 3600.000 &
5400.000 7200.000 9000.000 10800.00 12600.00 14400.00 &
16200.00 18000.00 / 2 D-PROPAG VALUE-LIST= 1800.000 &
3600.000 5400.000 7200.000 9000.000 10800.00 12600.00 &
14400.00 16200.00 18000.00
REGR-PARAM MAXPOINT= 11
EO-CONV-OPTI
SEQUENCE S-1 BATCH INITIA BATCH (RETURN INITIA) PROPAGA BATCH &
(RETURN PROPAGA)
STREAM-REPOR NOZEROFLOW NOMOLEFLOW MASSFLOW PROPERTIES=DENSITY
REACTIONS REAC-1 FREE-RAD

DESCRIPTION "EXAMPLE FREE-RADICAL INPUT"
PARAM
SPECIES INITIATOR=MPO MONOMER=VAC SOLVENT=MEOH POLYMER=POLY
MON-RSEG VAC VAC-SEG
INIT-DEC MPO 5E-6 .0 .0
CHAIN-INI VAC 9500.0 .0 .0
PROPAGATION VAC VAC 1000.0 .0 .0
CHAT-MON VAC VAC 2.3370 .0 .0
CHAT-POL VAC VAC 1.2350 .0 .0
CHAT-SOL VAC MEOH .3230 .0 .0
TERM-DIS VAC VAC 1.645E+08 .0 .0
GEL-EFFECT TERMINATION 2 MAX-PARAMS=10 GE-PARAMS=1.0 .0 &
.44070 .0 6.7530 .0 .34950 .0 .0 1.0
REGRESSION INITIA
DATA D-INITIA
VARY REACT-VAR REACTION=REAC-1 VARIABLE=IDPRE-EXP &

SENTENCE=INIT-DEC ID1=MPO
LIMITS 1E-7 1E-5
ALGORITHM AFCTOL=1.0 INIRIN=0
REGRESSION PROPAGA
DATA D-PROPAG
VARY REACT-VAR REACTION=REAC-1 VARIABLE=PRPRE-EXP &
SENTENCE=PROPAGATION ID1=VAC ID2=VAC
LIMITS 1E3 5E4
ALGORITHM AFCTOL=1.0 INIRIN=0
PROFILE-DATA D-INITIA
PARAM BLOCK=BATCH TEMP=65.0 PRES=1 UNITS=hr
DEFINE ZZTEMP BLOCK-VAR BLOCK=BATCH SENTENCE=PARAM &
VARIABLE=TEMP
DEFINE ZZPRES BLOCK-VAR BLOCK=BATCH SENTENCE=PARAM &
VARIABLE=PRES
VECTOR-DEF MFINIT BLOCK-VEC BLOCK=BATCH SENTENCE= &
REGR-C-PROF VARIABLE=MASSFRAC-L ID2=MPO
USE STD-DEV * -1.0 / DATA 0.0 1.554E-4 / DATA 0.5 &

1.551E-4 / DATA 1.0 1.546E-4 / DATA 1.5 1.542E-4 / &
DATA 2.0 1.538E-4 / DATA 2.5 1.532E-4 / DATA 3.0 &
1.526E-4 / DATA 3.5 1.522E-4 / DATA 4.0 1.518E-4 / &
DATA 4.5 1.513E-4 / DATA 5.0 1.509E-4
PROFILE-DATA D-PROPAG
PARAM BLOCK=BATCH TEMP=64.5 PRES=1 UNITS=hr

DEFINE ZZTEMP BLOCK-VAR BLOCK=BATCH SENTENCE=PARAM &
VARIABLE=TEMP
DEFINE ZZPRES BLOCK-VAR BLOCK=BATCH SENTENCE=PARAM &
VARIABLE=PRES
VECTOR-DEF DUTY BLOCK-VEC BLOCK=BATCH SENTENCE= REGR-PROF &
VARIABLE=DUTY
USE STD-DEV * 5.0 / DATA 0.5 -3750.0 / DATA 1.0 &
-3700.0 / DATA 1.5 -3300.0 / DATA 2.0 -3250.0 / &
DATA 2.5 -3100.0 / DATA 3.0 -3000.0 / DATA 3.5 &
-2800.0 / DATA 4.0 -2650.0 / DATA 4.5 -2350.0 / &
DATA 5.0 -2150.0

A5 Fractionating Oligomers
This example illustrates the use of Aspen Polymers for modeling a

polymer/oligomer fractionation process.
Creating a New Run
One typical fractionation method is to dissolve the polymer in a good solvent
and then add small amounts of antisolvent to it. At the phase equilibria, the
high-molecular weight polymer precipitates in the solvent phase, while the
lower-molecular weight polymer dissolves in the antisolvent phase. By
continuing addition of antisolvent, progressively lower molecular-weight
polymer precipitates.
The system in this example contains benzene (1, solvent), ethanol (2,
antisolvent) and polystyrene (3, polymer). A pseudo-component approach is
used to represent the polydispersity of polystyrene. In the pseudo-component
approach, a series of oligomers with different degree of polymerization (DP) is
defined. The mass distribution of the oligomers in the feed is approximately a
Gamma distribution. The Flory-Huggins model of polymer solution is used to
calculate the liquid-liquid phase equilibria in this quasi-ternary mixture. The
Flory-Huggins binary interaction parameters are obtained from Wu and
Prausnitz (Wu & Prausnitz, 1990).

In this example you create an Aspen Polymers process model to fractionate
polystyrene using benzene and ethanol, run the simulation, and examine the
results.
A5 Fractionating Oligomers 69
Creating a New Run
OK.
3 For this example, click Polymers with English Units for your template.
4 Click OK.


1 In the Model Library, click the Separators tab, then the Flash3 icon.
If you want to select different Flash3 model icons, click the down-arrow on
the icon.
70 A5 Fractionating Oligomers
the block (B1).
To place streams:
connection ports.
stream 1.
3 Repeat step 2 to create the other streams.
Renaming Streams
To rename streams:
1 Click the stream to be renamed, such as 5, and click the right mouse
3 Enter the Stream ID as 1P and click OK.

enter data using the Menu Tree.
Use the Setup folder to:
Enter a simulation title
Define unit-sets
Specify report options

1 From the Data menu, click Setup.
Polystyrene Oligomer Fractionation
This example illustrates the use of Aspen Polymers for modeling
polymer/oligomer fractionation process.
Defining Unit-Sets
2 Click New.
3 In the Enter ID field, enter SET1, then click OK.
A dialog box appears requesting approval to make SET1 the global unit set
4 Click No.
5 On the Standard sheet, from the Copy from pulldown list, click Eng.
o Pressure = atm
o Temperature = K
Specifying Report Options

To specify report options:
2 Click the Stream tab, in the Flow basis frame, click Mole, and in the
Fraction basis frame, click Mole and Mass.

To specify components:
1 From the Menu Tree, double click the Components folder.
2 From the Components folder, click Specifications.
3 On the Selection sheet, define benzene, ethanol and ten oligomer
components (from OL2 to OL11) as shown:
Note: Styrene segment is needed to define the structure of oligomers.
To characterize components:
1 From the Menu Tree Components folder, double-click the Polymers sub-
folder.
2 In the Polymers sub-folder, click Characterization.
3 On the Segments sheet, in the Type field for segment STY-SEG, click
REPEAT.
4 Click the Oligomers tab.
You need to provide the number of segments for each oligomer. Enter
these as shown below using even numbers from 2-20.

A physical property option set is needed for this simulation.
Specify physical property method
Enter pure component constants
Enter binary interaction parameters
Select properties to be calculated
Display a property sets in a stream report
To specify the global physical property method:
1 From the Menu Tree, double-click the Properties folder.
2 From the Properties folder, click Specifications.
3 On the Global sheet, from the Base method pulldown list, click POLYFH.
Defining Pure Component Parameters
You enter three pure component properties in this example. To enter the first
pure component constant:
1 From the Menu Tree Properties folder, double-click the Parameters sub-
folder.
2 From the Parameters sub-folder, click the Pure Component sub-folder.
4 Click to select T-dependent Correlation and expand Liquid vapor
pressure to select PLXANT-1. Click OK.
5 On the Input sheet, enter data shown in the Input Summary PROP-DATA
PLXANT-1 paragraph on page 80. A partial example is shown here:
To enter the second pure component constant:

1 From the Menu Tree Properties folder Parameters sub-folder, click the
Pure Component folder.
3 In the lower right corner of the New Pure component Parameters
dialog box, enter the new name as U-3. Click OK.
4 On the Input sheet, enter the critical constants for oligomers data as
shown. Refer to the Input Summary PROP-DATA U-3 paragraph on page
79 for the values of these constants. A partial example is shown here:
5 From the unit field pulldown list on menu bar, click SET1.
Defining Binary Interaction Parameters

To enter binary interaction parameters:
1 From the Menu Tree Properties folder Parameters sub-folder, double-
click the Binary Interaction sub-folder.
2 From the Binary Interaction sub-folder, click FHCHI-1.
3 Enter values as shown below.
Refer to the Input Summary PROP-DATA FHCHI-1 paragraph on page 80
for the complete list of parameter values. A partial example is shown
here:
Defining Properties to be Calculated
To select the properties to be calculated:
1 From the Menu Tree Properties folder, click the Prop-Sets sub-folder.
3 To accept PS-1 as the new name, Click OK.
4 On the Properties sheet, in the Physical properties field, click GAMMA.
5 Click the Qualifiers tab, from the Phase pulldown list, click Liquid.
Defining the Stream Report

To display the property set in the stream report:
2 Click the Stream tab, and click the Property Sets button.
3 Click PS-1, then click to move it to the Selected property sets
frame. Click Close.

Follow these instructions to specify:
Stream conditions
Block specifications
Specifying Stream Conditions

To specify the stream condition for the oligomer and non-solvent streams:
2 From the Streams folder, click the 1 folder.
3 On the Specifications sheet, enter the mass flow and feed condition as
follows:
o Temperature = 101.5 F
o Pressure = 14.7 psi
o Total flow (Mass) = 2.1 lb/hr
o Solvent 2 = 2.1 lb/hr
4 From Streams folder in the Menu Tree, click the 1P sub-folder.
5 On the Specifications sheet, enter the data as shown:
Specifying Block Conditions
To specify the Flash3 block:
1 From the Menu Tree, double-click the Blocks folder.
2 From the Blocks folder, doubl-click the B1 sub-folder.
3 From the B1 sub-folder, click Input.
o Temperature = 101.48 F
o Pressure = 14.7 psi
5 Click the Key Components tab, from the Key component in the 2nd
liquid phase pulldown list, click SOLVENT2.

Run the simulation
Examine the results
After flashing, the quasi-ternary mixture separates into two liquid phases, a
solvent rich phase and an antisolvent rich phase. Using the Flory-Huggins
model, the equilibria compositions in solvent and antisolvent phases are
computed. The Flory-Huggins predictions for liquid-liquid equilibria of
polystyrene-Benzene-Ethanol system are shown here:
The solid line is the mass distribution of polystyrene oligomer for the feed
stream 1P, dashed lines are for the product streams.
When ethanol is added to the polystyrene/benzene mixture, the majority of
high molecular weight PS remains in the solvent rich stream while most of the
low molecular weight ones dissolve into the antisolvent stream.
Input Summary
TITLE 'Polystyrene Oligomer Fractionation'
IN-UNITS ENG
DESCRIPTION "
This example illustrates the use of Aspen Polymers
for modeling polymer/oligomer fractionation process. "
COMPONENTS
SOLVENT1 C6H6 /
SOLVENT2 C2H6O-2 /
STY-SEG C8H8-R /
OL2
OL3
OL4
OL5
OL6
OL7
OL8
OL9
OL10
OL11
FLOWSHEET
BLOCK B1 IN=1 1P OUT=2 3 4
PROPERTIES POLYFH
PROP-DATA U-3
IN-UNITS ENG PRESSURE=atm TEMPERATURE=K PDROP=psi
PROP-LIST TC / PC / ZC
PVAL OL2 500.0 / 20.0 / .20
PVAL OL3 500.0 / 20.0 / .20
PVAL OL4 500.0 / 20.0 / .20
PVAL OL5 600.0 / 20.0 / .20
PVAL OL6 700.0 / 20.0 / .20
PVAL OL7 800.0 / 20.0 / .20
PVAL OL8 850.0 / 20.0 / .20
PVAL OL9 900.0 / 20.0 / .20
PVAL OL10 1000.0 / 20.0 / .20
PVAL OL11 1100.0 / 20.0 / .20
PROP-DATA PLXANT-1
IN-UNITS ENG
PROP-LIST PLXANT
PVAL OL2 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL3 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL4 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL5 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL6 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL7 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL8 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL9 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL10 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL OL11 -10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PROP-DATA FHCHI-1
IN-UNITS ENG
PROP-LIST FHCHI
BPVAL SOLVENT1 SOLVENT2 1.7390 0.0
BPVAL SOLVENT1 OL2 .2210 0.0
BPVAL SOLVENT2 OL2 1.4510 0.0
POLYMERS
SEGMENTS STY-SEG REPEAT
OLIGOMERS OL2 STY-SEG 2 / OL3 STY-SEG 4 / OL4 STY-SEG &
6 / OL5 STY-SEG 8 / OL6 STY-SEG 10 / OL7 STY-SEG &
12 / OL8 STY-SEG 14 / OL9 STY-SEG 16 / OL10 &
STY-SEG 18 / OL11 STY-SEG 20
PROP-SET PS-1 GAMMA SUBSTREAM=MIXED PHASE=L
STREAM 1
SUBSTREAM MIXED TEMP=101.480003 PRES=14.6959488 &
MASS-FLOW=2.10
MASS-FLOW SOLVENT2 2.10
STREAM 1P
MASS-FRAC SOLVENT1 .708990 / OL2 .020 / OL3 .060 / OL4 &
.080 / OL5 .060 / OL6 .040 / OL7 .020 / OL8 .010 &
/ OL9 .0010 / OL10 .00010 / OL11 .000010
BLOCK B1 FLASH3
PARAM TEMP=101.480003 PRES=14.6959488 L2-COMP=SOLVENT2
STREAM-REPOR MOLEFLOW MASSFLOW MOLEFRAC MASSFRAC PROPERTIES=PS-1
References
Wu, A. H., & Prausnitz, J. M. (1990). J. Appl. Pol. Sci., 39, pp. 629-637.
A6 Calculating End-Use
Properties
This example demonstrates how to use Aspen Polymers to predict important

end-use properties including melt-index, intrinsic viscosity and zero-shear
viscosity for high-density polyethylene and other polyolefins using user-
defined Prop-Set.
Creating a New Run
Creating a Sensitivity Table
The industry uses a number of empirical correlative models to predict melt
index of polyethylene product. End-use properties such as melt index are best
implemented as a property set (Prop-Set). A number of built-in Prop-Sets are
available in Aspen Plus. In addition, Prop-Sets let you specify a property set
with add-on user correlations. When doing this, a user-supplied Fortran
subroutine is required to perform the calculations.
Aspen Polymers supplies a user Prop-Set and the corresponding Fortran
subroutine for melt index based on the correlations of Karol, Sinclair, and
colleagues, (See the End-Use Properties section in Chapter 2 of the Aspen
Polymers User Guide, Volume 1) as well as the intrinsic and zero-shear
viscosities (Karol, Brown, & Davison, 1973; Sinclair, 1983).

In this example you create an Aspen Polymers process model to predict end-
use properties, run the simulation, and examine the results.
82 A6 Calculating End-Use Properties

Creating a New Run
OK.
4 Click OK.


1 In the Model Library, click the Heat Exchangers tab, then the Heater
icon.
A6 Calculating End-Use Properties 83

If you want to select different Heater model icons, click the down-arrow
on the icon.
the block (B1).
To place streams:
connection ports.
stream 1.
3 Repeat step 2 to create the stream 2.

An example illustrating end-use property calculations
4 You can either retain or delete the default information displayed, but type
The objective of this example is to demonstrate how to use Aspen
Polymers to predict important end-use properties including melt-index,
intrinsic viscosity, and zero-shear viscosity for high-density polyethylene
and other polyolefins using user-defined Prop-Sets. This example requires
a user Fortran subroutine USRPRP.F. Please copy USRPRP.F from the
example directory and compile it in your local directory.
5 Click .

Component ID, Component name, and Alias for the segment and
polymer as shown:

2 Click .
3 On the Segments sheet, from the Type pulldown list, click REPEAT.
4 Click the Polymers tab, from the Built-in attribute group pulldown list,
click Properties selection.
5 To modify the attribute group, click Edit.
6 On the Polymer Attributes dialog box, click to select:
o MWW
o DPW
o PDI
o SMOM
7 Click Close.
8 Click .
A Properties Specifications Global form appears.

Specify physical properties
Enter a Prop-Set
1 On the Properties Specifications Global form, from the Base method
pulldown list, click POLYFH.
2 From Properties folder in the Menu Tree, double-click the Advanced
sub-folder.
3 From the Advanced sub-folder, click User Properties.
5 In the Enter ID field, enter IV as the new name, click OK.
6 On the Specifications sheet, in the User subroutine name field, enter
USRPRP.

7 Repeat steps 3-6 to enter properties as shown:
Defining a Prop-Set
To be able to list desired polymer properties, you need to create property sets
and property tables, to do this:
To enter a Prop-Set:
folder.
2 In the Object Manager, click New.
3 In the Enter ID field, enter IV as the new name of the property set. Click
OK.
4 On the Properties sheet, click in the Physical properties cell to select
IV.
5 Repeat steps 1-4 to create Prop-Sets named MI-K, MI-S and ZVIS (step
3). In step 4, select the corresponding user property name from the
Physical properties cell.
6 Click .

To supply process information:
1 On the Required Properties Input Complete dialog box, click OK.
The Stream 1 Input Specifications sheet appears.
2 Enter the process information as shown:

3 Click .
The Component Attr. Sheet appears.
4 From the Attribute ID pulldown menu, click DPN, in the Value cell,
enter 1000.
5 From the Attribute ID pulldown menu, click SFRAC, in the Value cell,
enter 1.
6 From the Attribute ID pulldown menu, click PDI, in the Value cell, enter
3.61
7 Click .
The BLOCK B1 Input Specifications sheet appears.
8 Enter:
o Temperature = 420K
o Pressure = 1 atm
Creating a Sensitivity Table

To create a sensitivity table:
1 In the Menu Tree, double-click the Model Analysis Tools folder.
2 Click the Sensitivity sub-folder.
4 In the Enter ID field, enter END-USE as the ID. Click OK.
5 On the Define sheet, click New.
6 In the Enter Variable name field, enter IV. Click OK.
7 In the Variable Definition dialog box, select:
o Category = Streams
o Reference Type = Stream-Prop
o Stream = 2
o Prop-Set = IV
8 Click Close.

9 Repeat steps 5-8 to create variables named MIK, MIS and ZVIS (step 6).
In step 7, select the corresponding user property name in the Prop-Set
field.
11 Click the Tabulate tab, in Column numbers 1-4, enter IV, MI-K, MI-S,
and ZVIS respectively.
12 Click the Table Format button, enter:

Note: This example requires a user subroutine, USRPRP.f. You need to copy
the Fortran subroutine USRPRP.F from the Aspen Polymers application folder
to your working directory. You then need to compile the subroutine before
running this example.
Alternately, you can copy the files USERFORT.DLL and USERFORT.DLOPT from
the Aspen Polymers application folder (app) to your working directory. Then,
from the Aspen Plus menu bar, chose Run | Settings | Engine Files and
enter USERFORT.DLOPT in the Linker Options box before running the
simulation.
Run the simulation
Examine the results
Input Summary
TITLE 'An example illustrating end-use property calculations'
IN-UNITS MET
DESCRIPTION "The objective of this example is to demonstrate how

to use Aspen Polymers to predict important end-use
properties including melt-index, intrinsic viscosity,
and zero-shear viscosity for high-density polyethylene
and other polyolefins using user-defined PROP-SETS.
This example requires a user Fortran subroutine USRPRP.F.

Please copy USRPRP.F from the example directory and
compile it in your local directory."
COMPONENTS
HDPE PE /
C2H4-R C2H4-R
FLOWSHEET
BLOCK B1 IN=1 OUT=2
PROPERTIES POLYFH
POLYMERS
POLYMERS HDPE
ATTRIBUTES HDPE SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM &
FMOM SMOM
USER-PROPERT IV SUBROUTINE=USRPRP
USER-PROPERT MI-K SUBROUTINE=USRPRP
USER-PROPERT MI-S SUBROUTINE=USRPRP
USER-PROPERT ZVIS SUBROUTINE=USRPRP
PROP-SET IV IV SUBSTREAM=MIXED
PROP-SET MI-K MI-K SUBSTREAM=MIXED
PROP-SET MI-S MI-S SUBSTREAM=MIXED
PROP-SET ZVIS ZVIS SUBSTREAM=MIXED
STREAM 1
SUBSTREAM MIXED TEMP=420. <K> PRES=1.
MASS-FLOW HDPE 1000.
COMP-ATTR HDPE SFRAC ( 1. )
COMP-ATTR HDPE DPN ( 1000. )
COMP-ATTR HDPE PDI ( 3.61 )
BLOCK B1 HEATER
PARAM TEMP=420. <K> PRES=1.
EO-CONV-OPTI
SENSITIVITY END-USE
DEFINE IV STREAM-PROP STREAM=2 PROPERTY=IV
DEFINE MIK STREAM-PROP STREAM=2 PROPERTY=MI-K
DEFINE MIS STREAM-PROP STREAM=2 PROPERTY=MI-S
DEFINE ZVIS STREAM-PROP STREAM=2 PROPERTY=ZVIS
TABULATE 1 "IV" COL-LABEL="IV"
TABULATE 2 "MI-K" COL-LABEL="MI-K"

TABULATE 3 "MI-S" COL-LABEL="MI-S"
TABULATE 4 "ZVIS" COL-LABEL="ZVIS"
VARY BLOCK-VAR BLOCK=B1 VARIABLE=TEMP SENTENCE=PARAM
RANGE LOWER="400" UPPER="500" INCR="10"
STREAM-REPOR NOMOLEFLOW MASSFLOW
References
Karol, F. J., Brown, G. L., & Davison, J. M. (1973). Chromocene-Based
Catalysts for Ethylene Polymerization: Kinetic Parameters. J. of Polymer
Science: Polymer Chemistry Edition, 11, pp. 413-424.
Sinclair, K. B. (1983). Characteristics of Linear LPPE and Description of UCC
Gas Phase Process. Process Economics Report. Menlo Park, CA: SRI
International.

B1 Polystyrene Bulk
Polymerization by Thermal
Initiation
The polystyrene bulk polymerization by thermal initiation model illustrates the

use of Aspen Polymers (formerly known as Aspen Polymers Plus) for modeling
free-radical bulk polymerization of styrene with thermal and peroxide
initiation. The part of the process modeled is the polymerization stage and
subsequent devolatilization. This model is used to study the effect of feed flow
rate on styrene conversion, polymer properties, and recycle flowrate.
About This Process

Typically in free-radical polymerization, an initiator decomposes to form free
radicals that initiate chain growth. Propagation reactions add successive
monomer molecules to a growing polymer chain to increase its chain length.
A growing polymer chain terminates by either chain transfer or termination
reactions to form dead polymer chains.
Styrene monomer, when heated to polymerization temperatures above 120C,
can generate enough free-radicals to produce high conversion and high
molecular weight polymer. Styrene reacts via a Diels-Alder-type mechanism
to form dimers that react with an additional styrene molecule to produce free-
radicals. The thermal initiation rate has been reported to be third-order in
styrene concentration (Hui & Hamielec, 1972).
Process Definition
Styrene is polymerized in a reactor train consisting of two CSTRs followed by
a plug flow reactor. All of the reactors are considered liquid filled, and are
therefore modeled without taking into account vapor-liquid equilibrium.
Unreacted monomer is flashed in a devolatilizer to be modeled as an ideal
flash unit.
92 B1 Polystyrene Bulk Polymerization by Thermal Initiation

The flowsheet consists of two RCSTR in series, one RPlug, a Heater, and two
Flash2 blocks:
Process Conditions
The first CSTR operates at 120C, 1 atm, and the second operates at 160C, 1
atm. Both have a volume of 20 m3. The plug flow reactor operates at 1 atm,
with a temperature range of 160-200C from the inlet to the outlet.
The process conditions are:
Components Name Databank Description
Styrene STY PURE12 Monomer

Polystyrene PS POLYMER Polymer component
STY-SEG SEGMENT Styrene segment
Di-tert-butyl TBP PURE12 Initiator (Mw=216.32)
peroxide
Coinitiator CINI PURE12 Coinitiator
Ethylbenzene EB PURE12 Chain transfer agent
Dodecyl mercaptan DDM PURE12 Chain transfer agent (Mw=330.0)
Water H2O PURE12 Stripping agent
Physical POLYNRTL property method
Properties
Feeds
Temperature (C) 25
Pressure (atm) 1
Mass Flow (kg/hr) 7000
B1 Polystyrene Bulk Polymerization by Thermal Initiation 93

Mass fraction of .98
styrene
Mass fraction of 0.0
polystyrene
coinitiator
ethylbenzene
Mass fraction of DDM 0.0007
Mass fraction of TBP 0.0003
Kinetics FREE-RAD model
Operating Block Temp (C) Pres (atm) Size

Conditions
CSTR-1 120 1 20 m3
CSTR-2 160 1 20 m3
PLUG 160-200 1 80 m length by
0.40 m diam
DV-H1 220 1
FLASH-1 220 1
FLASH-2 220 1
Physical Property Models and Data

The Polymer Non-Random Two Liquid activity coefficient model physical
property method (POLYNRTL) is used. As no parameters are provided, the
thermophysical properties (density, heat capacity, etc.) of styrene,
ethylbenzene, dodecyl mercaptan, di-tert-butyl peroxide, and water are
calculated using parameters from the Pure Component Databank. Note that
the coinitiator is given the properties of styrene. However, as this component
is used only as a dummy component for the thermal initiation reaction,
results are not affected. The polymer thermophysical properties are calculated
using the van Krevelen group contribution method.
Reactors / Kinetics
The kinetics of bulk and solution polymerization of styrene have been studied
extensively. It has been reported (Albright, 1985) that chain transfer to the
monomer and the Diels-Alder dimers primarily controls the molecular weight
of polystyrene. Furthermore, based on chemical evidence and kinetic
modeling, it has been reported that termination of the growing chains occurs
principally by combination over disproportionation.
The reactions included from the built-in free-radical kinetics are:
Description Reaction
Initiator decomposition I R
Thermal initiation M C P1

Chain initiation R M P1
Propagation Pn M Pn 1
Chain transfer to monomer Pn M Dn P1
Chain transfer to EB Pn EB Dn R
Chain transfer to DDM Pn DDM Dn R
Termination by combination Pn Pm Dn m
6 2
The unit for the rate constant for the thermal initiation reaction is m /kmol /s
while the unit for the rate constant for initiator decomposition reaction is 1/s.
3 2
The units for the rate constants for the other reactions are m /kmol /s .
The induced initiation reaction is configured for thermal initiation by setting
the power to be third-order with respect to monomer. A coinitiator, which is
required for the induced initiation reaction, is included in the list of
components, but its power and feed rate are set to zero so that it will not
influence the rate for the thermal initiation reaction.
Process Studies
The model is used to study the effect of feed flow rate on styrene conversion,
polymer properties, and recycle styrene flowrate. In order to determine the
effect of feed flowrate on styrene conversion, polymer properties, and recycle
flowrate, a sensitivity study is carried out with feed mass flow as the varied
parameter.
Input Summary
An input language summary for this example is shown here:
; Free radical bulk polymerization of styrene by thermal and chemical
; initiation
; QSSA case
;
DYNAPLUS
DPLUS RESULTS=ON
TITLE &
'Bulk Polymerization of Styrene by Thermal & Chemical Initiation'
IN-UNITS MET ENTHALPY-FLO='kcal/hr' PRESSURE=bar TEMPERATURE=C &

DELTA-T=C MOLE-ENTHALP='kcal/kmol' MASS-ENTHALP='kcal/kg' &
HEAT=kcal PDROP=bar INVERSE-PRES='1/bar'

DESCRIPTION "Styrene polymerization in two CSTR's followed by a plug flow
reactor and two stage devolitization"
COMPONENTS
TBP C8H18O2 /
CINI C8H8 /
STY C8H8 /
PS PS-1 /
STY-SEG C8H8-R /
EB C8H10-4 /
DDM C12H26S /
H2O H2O
FLOWSHEET
BLOCK CSTR-1 IN=FEED OUT=R1-P
BLOCK CSTR-2 IN=R1-P OUT=R2-P
BLOCK PLUG IN=R2-P OUT=R3-P
BLOCK FLASH-1 IN=R3-PH2 OUT=REC-STY R3-OLI
BLOCK FLASH-2 IN=R3-OLI STRIP-AG OUT=VAPOR PRODUCT
BLOCK DV-H1 IN=R3-P OUT=R3-PH2
PROPERTIES POLYNRTL
PROP-DATA MW
IN-UNITS MET ENTHALPY-FLO='kcal/hr' PRESSURE=bar &
TEMPERATURE=C DELTA-T=C MOLE-ENTHALP='kcal/kmol' &
MASS-ENTHALP='kcal/kg' HEAT=kcal PDROP=bar &
INVERSE-PRES='1/bar'
PROP-LIST MW
PVAL TBP 216.320
POLYMERS
POLYMERS PS
ATTRIBUTES PS SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM FMOM &
SMOM LDPN LZMOM LFMOM LSFLOW LSFRAC LEFLOW LEFRAC &
LPFRAC
DISTRIBUTION PS
STREAM FEED
SUBSTREAM MIXED TEMP=25.00000 PRES=1.013250 MASS-FLOW=7000. &
NPHASE=1 PHASE=L
MASS-FRAC TBP 0.0003 / STY .980 / EB 0.019 / DDM &
0.0007
STREAM STRIP-AG
SUBSTREAM MIXED TEMP=25.00000 PRES=2.026500 &
MASS-FLOW=144.0000 NPHASE=1 PHASE=L
MASS-FLOW H2O 144.0000
BLOCK DV-H1 HEATER

PARAM TEMP=220.0000 PRES=1.013250

BLOCK FLASH-1 FLASH2
PARAM TEMP=220.0000 PRES=1.013250 MAXIT=200
BLOCK FLASH-2 FLASH2

PARAM TEMP=220.0000 PRES=1.013250 MAXIT=200
BLOCK CSTR-1 RCSTR

PARAM VOL=20. <cum> TEMP=120.0000 PRES=1.013250 NPHASE=1 &
PHASE=L MB-MAXIT=200 MB-TOL=.000010
BLOCK CSTR-2 RCSTR

PHASE=L MB-MAXIT=400 MB-TOL=.000010
BLOCK PLUG RPLUG

PARAM TYPE=T-SPEC LENGTH=80.00000 DIAM=.4000000 PHASE=L &
PRES=1.013250 HINIT=1.0000E-07 INT-TOL=.0010 &
CORR-METHOD=DIRECT
T-SPEC 0.0 160.0000 / 1.0 200.0000
EO-CONV-OPTI
SENSITIVITY S1
IN-UNITS SI
DEFINE R3MWN COMP-ATTR-VAR STREAM=R3-P SUBSTREAM=MIXED &
COMPONENT=PS ATTRIBUTE=MWN ELEMENT=1
DEFINE R3MWW COMP-ATTR-VAR STREAM=R3-P SUBSTREAM=MIXED &
COMPONENT=PS ATTRIBUTE=MWW ELEMENT=1
DEFINE R3PDI COMP-ATTR-VAR STREAM=R3-P SUBSTREAM=MIXED &
COMPONENT=PS ATTRIBUTE=PDI ELEMENT=1
DEFINE R3STY MASS-FRAC STREAM=R3-P SUBSTREAM=MIXED &
COMPONENT=STY
DEFINE R3PS MASS-FRAC STREAM=R3-P SUBSTREAM=MIXED &
COMPONENT=PS
COMPONENT=STY
COMPONENT=PS
COMPONENT=STY

COMPONENT=PS
DEFINE RECY STREAM-VAR STREAM=REC-STY SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
F R3CONV = R3PS/(R3STY + R3PS)
TABULATE 1 "R1CONV" COL-LABEL="R1CONV"
TABULATE 4 "R1MWN" COL-LABEL="R1MWN"
TABULATE 5 "R1MWW" COL-LABEL="R1MWW"
TABULATE 10 "R1PDI" COL-LABEL="R1PDI"
TABULATE 13 "RECY" COL-LABEL="RECYCLE"
VARY STREAM-VAR STREAM=FEED SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
RANGE LOWER="1.0" UPPER="2.5" INCR="0.2"
REINIT BLOCKS=ALL STREAMS=ALL
CONV-OPTIONS
PARAM CHECKSEQ=NO
SEQUENCE S-1 CSTR-1 CSTR-2 PLUG S1 CSTR-1 CSTR-2 PLUG DV-H1 &
FLASH-1 FLASH-2 (RETURN S1)
IN-UNITS SI
DESCRIPTION "Free-Radical Kinetic Scheme"
PARAM QSSA=YES
SPECIES INITIATOR=TBP COINITIATOR=CINI MONOMER=STY &
CHAINTAG=EB DDM POLYMER=PS
MON-RSEG STY STY-SEG
INIT-DEC TBP 1.6220E+11 1.1530E+08 0.0 EFFIC=.80 NRADS=2
INIT-SP STY CINI 438000.0 1.1480E+08 0.0
CHAIN-INI STY 1.0510E+07 2.9570E+07 0.0
PROPAGATION STY STY 1.0510E+07 2.9570E+07 0.0
CHAT-MON STY STY 3310000.0 5.3020E+07 0.0
CHAT-AGENT STY EB 1051.0 2.9590E+07 0.0
CHAT-AGENT STY DDM 1051.0 2.9590E+07 0.0
INIT-SP-EFF STY COEFFA=0.0 COEFFB=3.0 COEFFC=0.0
;

Selected Simulation Results
Results of the sensitivity studies carried out are shown in the figures that
follow. As shown, since the overall residence time decreases when feed flow
increases, conversion and polymer molecular weight decrease as well.
Typically, for free-radical polymerization systems with chain transfer to
monomer controlling the MWD, the polydispersity index should be close to 2.
However, with termination by combination controlling the molecular weight,
the polydispersity index should be close to 1.5.
For this simulation the polydispersity increases to about 1.924, indicating that
for the specified kinetics, the molecular weight becomes increasingly
controlled by chain transfer to monomer at high conversion. Finally, since the
monomer conversion decreases in the plug flow reactor, unreacted monomer
recycle increases. Note, however, that the increase in styrene recycle flow is
less than the increase in the overall feed flow rate.
The effect of feed flow rate on styrene conversion is shown here:
1
0.9
Styrene Conversion
0.8
0.7
0.6 CSTR-1
0.5 CSTR-2
0.4 PLUG
0.3
0.2
0.1
0
3000 4000 5000 6000 7000 8000 9000
Feed Flow Rate, kg/hr
The effect of feed flow rate on the number average molecular weight is shown
here:

200000
Number Average MW
180000
CSTR-1
CSTR-2
160000
PLUG
140000
120000
3000 4000 5000 6000 7000 8000 9000
The effect of flow rate on the weight average molecular weight is shown here:
350000
Weight Average MW
300000 CSTR-1
CSTR-2
PLUG
250000
200000
3000 4000 5000 6000 7000 8000 9000
The effect of feed flow rate on the polydispersity index is shown here:

2
Polydispersity Index
1.9
CSTR-1
CSTR-2
1.8
PLUG
1.7
1.6
3000 4000 5000 6000 7000 8000 9000
The effect of feed flow rate on the recycle flow rate is shown here:
1500
Recycle Flow Rate, kg/hr
1000
500
0
3000 4000 5000 6000 7000 8000 9000
Simulation Stream Summary

A partial stream table for the intermediate process flowstreams is shown
here:
FEED PRODUCT R1-P R2-P R3-OLI
-----------------------------
STREAM ID FEED PRODUCT R1-P R2-P R3-OLI

FROM : ---- FLASH-2 CSTR-1 CSTR-2 FLASH-1
TO : CSTR-1 ---- CSTR-2 PLUG FLASH-2
SUBSTREAM: MIXED
PHASE: LIQUID LIQUID LIQUID LIQUID LIQUID
COMPONENTS: KG/HR
TBP 2.1000 0.0 1.2516 6.5145-02 0.0
CINI 0.0 0.0 0.0 0.0 0.0
STY 6860.0000 147.1938 5147.1336 2515.9679 485.4496
PS 0.0 5645.3447 1713.7193 4346.0858 5645.3446
EB 133.0000 12.7095 132.9956 132.9818 47.5461
DDM 4.9000 3.9310 4.8998 4.8993 4.4821
H2O 0.0 12.4952 0.0 0.0 0.0
COMPONENTS: MASS FRAC
TBP 3.0000-04 0.0 1.7881-04 9.3065-06 0.0
CINI 0.0 0.0 0.0 0.0 0.0
STY 0.9800 2.5284-02 0.7353 0.3594 7.8516-02
PS 0.0 0.9697 0.2448 0.6209 0.9131
EB 1.9000-02 2.1831-03 1.8999-02 1.8997-02 7.6900-03
DDM 7.0000-04 6.7523-04 6.9998-04 6.9990-04 7.2493-04
H2O 0.0 2.1463-03 0.0 0.0 0.0
TOTAL FLOW:
KMOL/HR 67.1522 56.4492 67.1565 67.1624 59.3342
KG/HR 7000.0000 5821.6741 7000.0000 7000.0000 6182.8225
L/MIN 129.9401 105.8946 137.8228 133.2545 114.6276
STATE VARIABLES:
TEMP C 25.0000 220.0000 120.0000 160.0000 220.0000
PRES BAR 1.0133 1.0133 1.0133 1.0133 1.0133
VFRAC 0.0 0.0 0.0 0.0 0.0
LFRAC 1.0000 1.0000 1.0000 1.0000 1.0000
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
KCAL/KMOL 2.4055+04 2.1462+04 2.5663+04 2.3270+04 2.3116+04
KCAL/KG 230.7652 208.1063 246.2074 223.2675 221.8392
KCAL/HR 1.6154+06 1.2115+06 1.7235+06 1.5629+06 1.3716+06
ENTROPY:
CAL/MOL-K -79.6026 -72.0269 -70.9953 -72.6021 -71.3946
CAL/GM-K -0.7636 -0.6984 -0.6811 -0.6966 -0.6851
DENSITY:
MOL/CC 8.6132-03 8.8845-03 8.1211-03 8.4003-03 8.6271-03
GM/CC 0.8978 0.9163 0.8465 0.8755 0.8990
AVG MW 104.2408 103.1312 104.2342 104.2250 104.2034
COMPONENT ATTRIBUTES:
PS SFRAC
STY-SEG MISSING 1.0000 1.0000 1.0000 1.0000
SFLOW
STY-SEG MISSING 54.1828 16.4459 41.7088 54.1828
DPN
DPN MISSING 1212.4496 1821.7072 1320.3382 1212.4496
DPW
DPW MISSING 2309.3927 3177.1815 2469.6733 2309.3927
PDI
PDI MISSING 1.9047 1.7441 1.8705 1.9047
MWN
MWN MISSING 1.2628+05 1.8973+05 1.3752+05 1.2628+05
MWW

MWW MISSING 2.4053+05 3.3091+05 2.5722+05 2.4053+05
ZMOM
ZMOM MISSING 4.4689-02 9.0277-03 3.1589-02 4.4689-02
FMOM
FMOM MISSING 54.1828 16.4459 41.7088 54.1828
SMOM
SMOM MISSING 1.2513+05 5.2252+04 1.0301+05 1.2513+05
LDPN
LDPN MISSING 568.1677 1170.7394 761.3834 568.1677
LZMOM
LZMOM MISSING 2.9792-07 2.5496-07 3.2470-07 2.9792-07
LFMOM
LFMOM MISSING 1.6927-04 2.9850-04 2.4722-04 1.6927-04
LSFLOW
STY-SEG MISSING 1.6927-04 2.9850-04 2.4722-04 1.6927-04
LSFRAC
STY-SEG MISSING 1.0000 1.0000 1.0000 1.0000
LEFLOW
STY-SEG MISSING 2.9792-07 2.5496-07 3.2470-07 2.9792-07
LEFRAC
STY-SEG MISSING 1.0000 1.0000 1.0000 1.0000
LPFRAC
LPFRAC MISSING 6.6666-06 2.8242-05 1.0279-05 6.6666-06
References
Albright, L.F. (1985). Processes for Major Addition-Type Plastics and Their
Monomers. Krieger Publishing Co.
Brandrup, J., & Immergut, E. H. (1989). Polymer Handbook, 3rd Ed. Wiley
Intersciences, 57-82.
Friis, N., & Hamielec, A. E. (1976). Gel-Effect in Emulsion Polymerization of
Vinyl Monomers. ACS Symp. Ser., 24.
Gaur, U., & Wunderlich, B. (1982). J. Phys. Chem. Ref. Data, 11, (2), p. 313.
Hui, A. W., & Hamielec, A. E. (1972). Thermal Polymerization of Styrene at
High Conversions and Temperatures. An Experimental Study. J. of Applied
Polymer Science, 16, pp. 9-769.
Van Krevelen, D. W. (1990). Properties of Polymers, Their Correlation With
Chemical Structure; Their Numerical Estimation and Prediction from Additive
Group Contributions. New York: Elsevier.
Van Krevelen, D. W. (1990). Properties of Polymers, 3rd Ed., Amsterdam:
Elsevier.

B2 Polystyrene with Styrene
Monomer Distillation
The polystyrene with styrene monomer distillation model illustrates the use of
Aspen Polymers to model and predict the extent of polymer formation during
styrene distillation. The model examines the optimum level of inhibitor to
minimize polymer formation.
About This Process

Product from a styrene plant consists of 63% styrene, 32% ethyl benzene and
small amounts of toluene and benzene. Styrene is purified in a series of
distillation columns. During distillation styrene polymerization occurs and the
extent of polymerization depends on the time and temperature. To reduce
polymer formation inhibitor is commonly used in the feed. The amount of
inhibitor needs to be optimized since too little will produce more polymer
waste and too high concentration of inhibitor will be expensive. The purpose
of this example is to find an optimum level of inhibitor needed to minimize
polymer formation and to maximize the process profitability.
Process Definition
The process consists of three columns in series:
104 B2 Polystyrene with Styrene Monomer Distillation

The first column, known as the BT column, removes benzene and toluene
from the feed stream. The heavy cut flows to the EB (ethylbenzene) column,
which takes off an ethylbenzene cut, which is recycled to the upstream
styrene process. The third column separates the styrene monomer from
residual polystyrene formed as a by-product in the columns.
The reboiler of each column is represented using an RCSTR block (we assume
that most of the polymer is formed in the column reboilers). We must use the
RCSTR block because the current version of RadFrac does not support
polymer reaction kinetics.
Process Conditions
Component Name Databank Description

Etylbenzene EB PURE12 Chain transfer agent
Benzene BEN PURE12 Solvent
Toluene TOL PURE12 Solvent
Inhibitor INHIBIT PURE12 Inhibitor
Coinitiator CINI -- Coinitiator
PS PS POLYMER Polymer
Feed Stream
Temperature 80 C
Pressure 4.5 Bar
Mass Flow 18000 Kg/hr
styrene
B2 Polystyrene with Styrene Monomer Distillation 105

ethyl benzene
toluene
benzene
inhibitor
Operating Block Temp Pres (Bar) Specifications
Conditions (C) Top/Bottom
BT-COL 0.24 / 0.4 30 ideal stages +

condenser
RR = 6.5
Feed - stage 20
BT-REB 109 0.4 Liquid holdup 22.5 m3
EB-COL 0.055 / 0.36 60 ideal stages +

condenser
RR = 10
Feed - stage 33
EB-REB 113 0.36 Liquid holdup 18.5 m3
STY-COL 0.05 / 0.092 10 ideal stages +

condenser
RR = 2.7
Feed - stage 2
STY-REB 100 0.092 Liquid holup 15 m3
Polymers and Segments

Polystyrene is a homopolymer and the styrene segment is the only repeat
unit. The set of component attributes required for free-radical polymerization
is used for PS.

The Polymer Non-Random Two Liquid activity coefficient model (POLYNRTL) is
used as the physical property method. Binary parameters for
monomer/monomer pairs are drawn from Aspens binary databases. The
monomer/styrene segment parameters are set equal to the equivalent
parameters for monomer/sytrene pairs.
The thermophysical properties (density, heat capacity, etc.) of styrene, ethyl
benzene, benzene, toluene and inhibitor are obtained from the Aspen Plus
Pure Component Databank. Note that inhibitors are given the properties of
styrene with the exception of molecular weight. The polymer thermophysical
properties are calculated using the Van Krevelen group contribution method.

Reactors / Kinetics
The specific reactions included from the built-in kinetics are:
Thermal initiation 3M R*
Chain initiation R* + M P1
Propagation Pn + M Pn+1
Chain transfer to monomer Pn + M Dn + P1
Chain thansfer to EB Pn + EB Dn + P1
Termination by combination Pn + Pm Dn+m
Termination by inhibition Pn + X Dn
The induced initiation reaction is configured for thermal initiation by setting

third-order thermal initiation with respect to monomer. A coinitiator, which is
required for the induced initiation reaction, is included in the list of
components, but its feed rate is set to zero so that it will not influence the
rate for the thermal initation reaction.
Inhibitor
Common inhibitors used in this process are nitrobenzene, dinitro-o-bencene,
dinitro-m-bencene, dinitro-p-bencene, 4,6 dinitro-o-cresol, etc. In this
example 4,6 dinitro-o-cresol is used as inhibitor. (Mw = 198.135)
Process Studies
Input Summary
TITLE 'STYRENE DISTILLATION'
IN-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='MMkcal/hr' &

HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=C &
VOLUME=cum DELTA-T=C HEAD=meter MOLE-DENSITY='kmol/cum' &
MASS-DENSITY='kg/cum' MOLE-ENTHALP='kcal/mol' &
MASS-ENTHALP='kcal/kg' HEAT=MMkcal MOLE-CONC='mol/l' &
PDROP=bar
SIM-OPTIONS
VOLUME-FLOW='cum/hr' PRESSURE=bar TEMPERATURE=C DELTA-T=C
&
PDROP-PER-HT='mbar/m' PDROP=bar
SIM-OPTIONS FLASH-TOL=1.0000E-06
DESCRIPTION POLYSTYRENE IS FORMED IN THE REBOILER DURING THE

DISTILLATION OF STYRENE. THIS EXAMPLE SHOWS HOW TO OPTIMIZE

THE AMOUNT OF INHIBITOR REQUIRED TO SUPRESS THE FORMATION
OF POLYSTYRENE."
DATABANKS POLYMER / SEGMENT / PURE12 / AQUEOUS / SOLIDS &

/ INORGANIC / PURE93 / NOASPENPCD
PROP-SOURCES POLYMER / SEGMENT / PURE12 / AQUEOUS / &

SOLIDS / INORGANIC / PURE93
COMPONENTS
STY C8H8 /
PS PS-1 /
STY-SEG C8H8-R /
EB C8H10-4 /
BEN C6H6 /
TOL C7H8 /
INHIBIT C8H8 /
CINI C8H8
FLOWSHEET
BLOCK BT-COL IN=BT-FEED BT-V1 OUT=BT-TOP BT-L1
BLOCK BT-REB IN=BT-L1 OUT=BT-V1 BT-BOT
BLOCK EB-COL IN=EB-V1 EB-FEED OUT=EB-TOP EB-L1
BLOCK EB-REB IN=EB-L1 OUT=EB-V1 EB-BOT
BLOCK PUMP-1 IN=BT-BOT OUT=EB-FEED
BLOCK PUMP-2 IN=EB-BOT OUT=STY-FEED
BLOCK STY-COL IN=STY-FEED STY-V1 OUT=STY-TOP STY-L1
BLOCK STY-REB IN=STY-L1 OUT=STY-V1 RESIDUE
PROPERTIES POLYNRTL
USER-PROPS GMRENA 1 2 1 / GMRENB 1 2 1 / GMRENC 1 2 1 / &

GMREND 1 2 1
PROP-DATA MW
PDROP=bar
PROP-LIST MW
PVAL INHIBIT 198.1350
PROP-DATA PLXANT-1
IN-UNITS SI PRESSURE=bar TEMPERATURE=C PDROP='N/sqm'
PROP-LIST PLXANT
PVAL INHIBIT -30.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PROP-DATA NRTL-1
IN-UNITS ENG
PROP-LIST NRTL
BPVAL STY EB -.93850 48.950099610 .30 0.0 0.0 0.0 &
135.80600290 206.60000230
BPVAL EB STY 1.31730 -66.017519470 .30 0.0 0.0 0.0 &

135.80600290 206.60000230
BPVAL STY BEN 0.0 879.0049730 .3110 0.0 0.0 0.0 &
68.000003460 131.0000030
BPVAL BEN STY 0.0 -582.96797530 .3110 0.0 0.0 0.0 &
68.000003460 131.0000030
BPVAL EB BEN 0.0 51.711839590 .30340 0.0 0.0 0.0 &
176.00000260 275.00000180
BPVAL BEN EB 0.0 -64.163879490 .30340 0.0 0.0 0.0 &
176.00000260 275.00000180
BPVAL EB TOL 0.0 975.87575220 .30 0.0 0.0 0.0 &
212.00000230 273.20000180
BPVAL TOL EB 0.0 -654.62471480 .30 0.0 0.0 0.0 &
212.00000230 273.20000180
BPVAL BEN TOL 0.0 100.64771920 .30330 0.0 0.0 0.0 &
176.00000260 230.00000220
BPVAL TOL BEN 0.0 -109.82159910 .30330 0.0 0.0 0.0 &
176.00000260 230.00000220
POLYMERS
POLYMERS PS
ATTRIBUTES PS SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM FMOM &
LPFRAC
STREAM BT-FEED
VOLUME-FLOW='cum/hr' PRESSURE=bar TEMPERATURE=C &
DELTA-T=C PDROP-PER-HT='mbar/m' PDROP=bar
MASS-FRAC STY .630 / EB .3180 / BEN .020 / TOL .0320
STREAM BT-L1
SUBSTREAM MIXED TEMP=107.746962 PRES=.40 &
MASS-FLOW=25896.6115
MASS-FRAC STY .616547893 / EB .365240172 / BEN &
.008181312 / TOL .010030622
STREAM BT-V1
IN-UNITS MET MASS-FLOW='kg/sec' MOLE-FLOW='kmol/sec' &
VOLUME-FLOW='cum/hr' ENTHALPY-FLO='MMkcal/hr' &
TIME=sec VOLUME=cum DELTA-T=C HEAD=meter &
MOLE-DENSITY='kmol/cum' MASS-DENSITY='kg/cum' &
MOLE-ENTHALP='kcal/mol' MASS-ENTHALP='kcal/kg' &
HEAT=MMkcal MOLE-CONC='mol/l' PDROP=bar
SUBSTREAM MIXED TEMP=109 PRES=0.4 MASS-FLOW=2.15351197
MASS-FRAC STY 0.560602271 / EB 0.390454005 / BEN &
0.00198335909 / TOL 0.0469603649
STREAM EB-L1
1.0888E-10 / TOL .000287885
STREAM EB-V1

SUBSTREAM MIXED PRES=0.36 VFRAC=1 MASS-FLOW=53891.635
MASS-FRAC STY 0.844267227 / EB 0.155732773 / TOL &
1.934753E-011
STREAM STY-L1
1.0782E-29 / TOL 1.9846E-14
STREAM STY-V1
SUBSTREAM MIXED PRES=0.092 VFRAC=1 MOLE-FLOW=341.040394
MASS-FRAC STY 0.994096437 / EB 0.00590356315
BLOCK BT-COL RADFRAC

VOLUME-FLOW='cum/hr' PRESSURE=bar TEMPERATURE=C &
DELTA-T=C PDROP-PER-HT='mbar/m' PDROP=bar
PARAM NSTAGE=30 ALGORITHM=STANDARD ABSORBER=NO
COL-CONFIG CONDENSER=TOTAL REBOILER=NONE
DIAGNOSTICS TERM=4
FEEDS BT-FEED 20 / BT-V1 31
PRODUCTS BT-TOP 1 L / BT-L1 30 L
P-SPEC 1 .240 / 30 .40
COL-SPECS MOLE-RR=6.5
SC-REFLUX TEMP=40.0 OPTION=0
T-EST 1 43.0 / 2 57.0 / 22 113.0
BLOCK EB-COL RADFRAC

PARAM NSTAGE=60 EFF=VAPOR
FEEDS EB-V1 61 / EB-FEED 33
PRODUCTS EB-TOP 1 L / EB-L1 60 L
P-SPEC 2 .0650 / 60 .360
SC-REFLUX TEMP=40.0 OPTION=0
BLOCK STY-COL RADFRAC

PARAM NSTAGE=10
COL-CONFIG CONDENSER=PARTIAL-V REBOILER=NONE
FEEDS STY-FEED 2 / STY-V1 11
PRODUCTS STY-TOP 1 V / STY-L1 10 L
P-SPEC 1 .050 / 10 0.092
BLOCK BT-REB RCSTR

PARAM VOL=50.0 TEMP=109.0 PRES=0.0 NPHASE=2 PHASE=L &
PHASE-VOL=22.50 SCALING=COMPONENTS
PRODUCTS BT-V1 V / BT-BOT L
CONVERGENCE SOLVER=NEWTON
REACTIONS RXN-IDS=R-1
BLOCK EB-REB RCSTR

PARAM VOL=50.0 TEMP=113. PRES=0.0 NPHASE=2 PHASE=L &
PHASE-VOL=18.50 SCALING=COMPONENTS
PRODUCTS EB-V1 V / EB-BOT L

BLOCK STY-REB RCSTR

PHASE-VOL=15.0 SCALING=COMPONENTS ALGORITHM=INTEGRATOR &
MAX-NSTEP=100
PRODUCTS STY-V1 V / RESIDUE L
BLOCK PUMP-1 PUMP

PARAM PRES=4.130
BLOCK PUMP-2 PUMP

PARAM PRES=6.20
EO-CONV-OPTI
SENSITIVITY S-1
PARAM BASE-CASE=FIRST
DEFINE INHI MASS-FRAC STREAM=BT-FEED SUBSTREAM=MIXED &
COMPONENT=INHIBIT
DEFINE R1PS MASS-FLOW STREAM=BT-BOT SUBSTREAM=MIXED &
COMPONENT=PS
DEFINE R2PS MASS-FLOW STREAM=EB-BOT SUBSTREAM=MIXED &
COMPONENT=PS
DEFINE R3PS MASS-FLOW STREAM=RESIDUE SUBSTREAM=MIXED &
COMPONENT=PS
DEFINE STY MASS-FLOW STREAM=BT-FEED SUBSTREAM=MIXED &
COMPONENT=STY
DEFINE FEEDI MASS-FLOW STREAM=BT-FEED SUBSTREAM=MIXED &
COMPONENT=INHIBIT
C
F PS1 = R1PS / STY
F PS2 = (R2PS - R1PS )/ STY
F PS3 = (R3PS - R2PS )/ STY
F PSTOT =R3PS/STY
F PS0 = 731 / STY
C
F PPMIN = INHI * 1.0E6
C
F P = PS0 - PSTOT
C
F PROFIT = P - 100 * FEEDI/STY
TABULATE 1 "PPMIN" COL-LABEL="INHIBIT" "PPM"
TABULATE 2 "PS1" COL-LABEL="PS1" "POLYMER" "BT-COL"
TABULATE 3 "PS2" COL-LABEL="PS2" "POLYMER" "EB-COL"
TABULATE 4 "PS3" COL-LABEL="PS3" "POLYMER" "STY-COL"
TABULATE 5 "PSTOT" COL-LABEL="PSTOT" "TOTAL" "POLYMER"
TABULATE 6 "PROFIT" COL-LABEL="PROFIT"
VARY MASS-FLOW STREAM=BT-FEED SUBSTREAM=MIXED &
COMPONENT=INHIBIT
RANGE LIST=0.0 0.2 0.4 0.5 0.55 .60 0.65 0.7 0.75 1. &
2.0 3.0
CONV-OPTIONS
PARAM TEAR-METHOD=BROYDEN CHECKSEQ=YES

PROPERTY-REP PARAMS
REACTIONS R-1 FREE-RAD

IN-UNITS SI
DESCRIPTION "FREE-RADICAL KINETIC SCHEME"
PARAM QSSA=YES
SPECIES COINITIATOR=CINI MONOMER=STY CHAINTAG=EB &
SOLVENT=TOL BEN INHIBITOR=INHIBIT POLYMER=PS
INIT-SP STY CINI 438000.0 1.1480E+08
CHAIN-INI STY 1.0510E+07 2.9570E+07
PROPAGATION STY STY 1.0510E+07 2.9570E+07
CHAT-MON STY STY 3310000.0 5.3020E+07
CHAT-AGENT STY EB 1051.0 2.9590E+07
TERM-COMB STY STY 1.2550E+09 7017000.0
INHIBITION STY INHIBIT 1.0500E+09 2.9570E+07

This example includes a sensitivity study in which the inhibitor feed rate is
adjusted over a wide range. The purpose of this sensitivity is to find an
optimum level of inhibitor needed to minimize polymer formation and to
maximize the process profitability.
Process profitability is calculated as follows with the assumption that inhibitor
is 100 times more expensive than styrene monomer:
PROFIT = PS0 - PSTOT - 100 * FEEDI / STY
Where:
PS0 = Mass flow of polymer produced without inhibitor in
the feed / Mass flow of styrene in the feed
PSTOT = Mass flow of polymer produced with inhibitor in the
feed / Mass flow of styrene in the feed
FEEDI = Mass flow of inhibitor in the feed
STY = Mass flow of styrene in the feed
Results of the sensitivity studies are shown in the table and figures that
follow.
Effect of Inhibitor Feed Mass Fraction on the Polymer Formation and Process Profitability
VARY 1 INHIBIT PS1 PS2 PS3 PSTOT PROFIT

BT-FEED PPM POLYMER POLYMER POLYMER TOTAL
MIXED BT-COL EB-COL STY-COL POLYMER
INHIBIT
MASS-
FLOW
KG/HR

1 0.00 0.00 3.08E-02 3.89E-02 3.20E-04 0.07003 -0.0056
2 0.20 11.11 1.70E-02 3.28E-02 3.72E-05 0.04987 0.0128
3 0.40 22.22 7.52E-03 1.26E-02 2.98E-06 0.02017 0.0408
4 0.50 27.78 5.50E-03 3.77E-04 1.80E-07 0.00588 0.0542
5 0.55 30.55 4.83E-03 2.13E-04 1.51E-07 0.00505 0.0546
6 0.60 33.33 4.30E-03 1.47E-04 1.40E-07 0.00445 0.0547
7 0.65 36.11 3.87E-03 1.13E-04 1.35E-07 0.00398 0.0547
8 0.70 38.89 3.52E-03 9.34E-05 1.32E-07 0.00361 0.0547
9 0.75 41.66 3.22E-03 8.05E-05 1.30E-07 0.00330 0.0545
10 1.00 55.55 2.27E-03 5.44E-05 1.28E-07 0.00232 0.0533
11 2.00 111.10 1.04E-03 4.49E-05 1.46E-07 0.00109 0.0457
12 3.00 166.64 6.82E-04 5.06E-05 1.80E-07 0.00073 0.0373
The effect of the inhibitor feed mass fraction on polymer production is shown
here:
0.01 0.02 0.03 0.04 0.05 0.06 0.07
PS Generated in BT Column, kg/hr

PS Generated in EB Column, kg/hr
PS Generated in Styrene Column, kg/hr
Total PS Residue, kg/hr
0 15 30 45 60 75 90 105 120 135 150 165

Inhibitor Concentration in feed, PPM
The effect of the inhibitor feed mass fraction on process profitability is shown
here:

0.015 0.03 0.045
Profit
0
0 10 20 30 40 50 60 70 80 90 100 110
Concentration of Inhibitor in Feed, PPM

The stream summary report (for selected streams) for the base case results
without inhibitor is shown here:
STREAM ID BT-FEED BT-TOP BT-BOT EB-TOP EB-BOT

FROM : ---- BT-COL BT-REB EB-COL EB-REB
TO : BT-COL ---- PUMP-1 ---- PUMP-2
SUBSTREAM: MIXED
COMPONENTS: KMOL/HR
STY 108.8798 4.1382-07 105.5295 88.5771 12.7131
PS 0.0 0.0 3.3508 0.0 7.5900
EB 53.9149 9.0635-05 53.9148 53.9138 9.7391-04
BEN 4.6087 4.5123 9.6354-02 9.6354-02 0.0
TOL 6.2513 2.5789 3.6725 3.6725 0.0
INHIBIT 0.0 0.0 0.0 0.0 0.0
CINI 0.0 0.0 0.0 0.0 0.0
COMPONENTS: KG/HR
STY 1.1340+04 4.3100-05 1.0991+04 9225.4371 1324.0935
PS 0.0 0.0 348.9875 0.0 790.5152
EB 5724.0000 9.6225-03 5723.9916 5723.8877 0.1034
BEN 360.0000 352.4725 7.5265 7.5265 0.0
TOL 576.0000 237.6205 338.3835 338.3835 0.0
INHIBIT 0.0 0.0 0.0 0.0 0.0
CINI 0.0 0.0 0.0 0.0 0.0
STY 0.6300 7.3038-08 0.6313 0.6032 0.6261
PS 0.0 0.0 2.0045-02 0.0 0.3738
EB 0.3180 1.6306-05 0.3288 0.3742 4.8894-05
BEN 2.0000-02 0.5973 4.3231-04 4.9208-04 0.0
TOL 3.2000-02 0.4027 1.9436-02 2.2123-02 0.0
INHIBIT 0.0 0.0 0.0 0.0 0.0
CINI 0.0 0.0 0.0 0.0 0.0

TOTAL FLOW:
KMOL/HR 173.6547 7.0913 166.5639 146.2597 20.3042
KG/HR 1.8000+04 590.1027 1.7410+04 1.5295+04 2114.7121
CUM/HR 21.5234 0.6919 21.4214 17.5462 2.4217
STATE VARIABLES:
TEMP C 80.0000 40.0000 109.0000 40.0000 113.0000
PRES BAR 4.5000 0.2400 0.4000 6.5000-02 0.3600
VFRAC 0.0 0.0 0.0 0.0 0.0
LFRAC 1.0000 1.0000 1.0000 1.0000 1.0000
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
KCAL/MOL 17.3942 9.0202 18.9151 14.5519 24.3632
KCAL/KG 167.8099 108.3966 180.9639 139.1518 233.9206
MMKCAL/HR 3.0206 6.3966-02 3.1506 2.1284 0.4947
ENTROPY:
CAL/MOL-K -77.8169 -65.1477 -75.2613 -85.4707 -73.7515
CAL/GM-K -0.7507 -0.7829 -0.7200 -0.8173 -0.7081
DENSITY:
KMOL/CUM 8.0682 10.2491 7.7756 8.3357 8.3842
KG/CUM 836.3005 852.8781 812.7352 871.7124 873.2279
AVG MW 103.6540 83.2152 104.5242 104.5759 104.1516
PS SFRAC
STY-SEG MISSING MISSING 1.0000 MISSING 1.0000
SFLOW
DPN
DPN MISSING MISSING 2661.1066 MISSING 2728.7708
DPW
DPW MISSING MISSING 4974.3601 MISSING 5043.0428
PDI
PDI MISSING MISSING 1.8693 MISSING 1.8481
MWN
MWN MISSING MISSING 2.7716+05 MISSING 2.8421+05
MWW
MWW MISSING MISSING 5.1809+05 MISSING 5.2524+05
ZMOM
ZMOM MISSING MISSING 1.2591-03 MISSING 2.7814-03
FMOM
FMOM MISSING MISSING 3.3506 MISSING 7.5899
SMOM
SMOM MISSING MISSING 1.6667+04 MISSING 3.8276+04
LDPN
LDPN MISSING MISSING 1981.7638 MISSING 1974.7946
LZMOM
LZMOM MISSING MISSING 1.8832-07 MISSING 2.7918-08
LFMOM
LFMOM MISSING MISSING 3.7321-04 MISSING 5.5133-05
LSFLOW
STY-SEG MISSING MISSING 3.7321-04 MISSING 5.5133-05
LSFRAC
LEFLOW
STY-SEG MISSING MISSING 1.8832-07 MISSING 2.7918-08
LEFRAC
LPFRAC

LPFRAC MISSING MISSING 1.4957-04 MISSING 1.0037-05
RESIDUE STY-TOP
---------------
STREAM ID RESIDUE STY-TOP

FROM : STY-REB STY-COL
TO : ---- ----
SUBSTREAM: MIXED
PHASE: LIQUID VAPOR
COMPONENTS: KMOL/HR
STY 0.6196 12.0586
PS 7.6249 0.0
EB 2.2485-06 9.7166-04
BEN 0.0 0.0
TOL 0.0 0.0
INHIBIT 0.0 0.0
CINI 0.0 0.0
COMPONENTS: KG/HR
STY 64.5362 1255.9241
PS 794.1484 0.0
EB 2.3872-04 0.1032
BEN 0.0 0.0
TOL 0.0 0.0
INHIBIT 0.0 0.0
CINI 0.0 0.0
STY 7.5157-02 0.9999
PS 0.9248 0.0
EB 2.7801-07 8.2131-05
BEN 0.0 0.0
TOL 0.0 0.0
INHIBIT 0.0 0.0
CINI 0.0 0.0
TOTAL FLOW:
KMOL/HR 8.2446 12.0596
KG/HR 858.6848 1256.0273
CUM/HR 0.8909 6647.3689
STATE VARIABLES:
TEMP C 120.0000 59.1993
PRES BAR 9.2000-02 5.0000-02
VFRAC 0.0 1.0000
LFRAC 1.0000 0.0
SFRAC 0.0 0.0
ENTHALPY:
KCAL/MOL 18.2651 36.2480
KCAL/KG 175.3702 348.0308
MMKCAL/HR 0.1506 0.4371
ENTROPY:
CAL/MOL-K -82.6169 -43.9790
CAL/GM-K -0.7932 -0.4223
DENSITY:
KMOL/CUM 9.2543 1.8142-03
KG/CUM 963.8521 0.1890
AVG MW 104.1515 104.1517

PS SFRAC
STY-SEG 1.0000 MISSING
SFLOW
DPN
DPN 2730.8645 MISSING
DPW
DPW 5049.0638 MISSING
PDI
PDI 1.8489 MISSING
MWN
MWN 2.8442+05 MISSING
MWW
MWW 5.2587+05 MISSING
ZMOM
ZMOM 2.7921-03 MISSING
FMOM
FMOM 7.6248 MISSING
SMOM
SMOM 3.8498+04 MISSING
LDPN
LDPN 2711.1368 MISSING
LZMOM
LZMOM 6.6782-10 MISSING
LFMOM
LFMOM 1.8106-06 MISSING
LSFLOW
STY-SEG 1.8106-06 MISSING
LSFRAC
LEFLOW
STY-SEG 6.6782-10 MISSING
LEFRAC
LPFRAC
LPFRAC 2.3919-07 MISSING
References
Scheeline, H. W., & Pons, J. I. (1977). Styrene, Supplement B (Process
Economics Program Report No. 33B). Menlo Park: Stanford Research
Institute.

B3 Expanded Polystyrene
Suspension Polymerization
The expanded polystyrene (EPS) suspension polymerization model illustrates

the use of Aspen Polymers for modeling free-radical suspension
polymerization of styrene in a batch reactor. The batch reactor model,
RBatch, rigorously accounts for two liquid phases and one vapor phase. The
reactions take place in the organic (monomer/polymer droplets) phase.
The first polymerization stage of the EPS process and the effect of n-pentane
on the conversion and molecular weight profiles are studied. The results
reproduce the published work of Villalobos and coworkers (1993). This
application example also compares the use of monofunctional and bifunctional
initiators. Note that Aspen Polymers currently does not support bifunctional
initiators.
About This Process

The manufacture of expandable polystyrene involves two stages. During the
first stage, suspension polymerization of styrene is carried out in a stirred
batch reactor at temperatures between 80 and 90C with a dispersed phase
hold-up (volume of monomer phase over total liquid volume) in the range of
0.4 to 0.6.
Styrene monomer is suspended in the form of droplets in water phase.
Polymerization occurs in these droplets until the mixture reaches its glass
transition temperature. The mean particle size is determined by the droplet
coalescence and the droplet breakage caused by the agitation system. The
particle growth is controlled with the aid of suspending agents, which are
usually inorganic powders such as tricalcium phosphate.
In the second stage, also known as the impregnation stage, a blowing agent,
such as n-pentane, is loaded into the reactor and diffuses into the beads. The
residual monomer is polymerized using an initiator with a half-life higher than
the one used in the polymerization process. The batch reactor is operated at
elevated pressures during this second, impregnation, stage.
A main manufacturing objective is to minimize the long batch times necessary
to complete the polymerization. Polymerization at higher temperatures as a
means to increase productivity is not successful due to lower molecular
118 B3 Expanded Polystyrene Suspension Polymerization

weight of the polymer and the enhanced particle coalescence, which is due to
the higher temperature. Addition of a blowing agent influences the
polymerization rate and the molecular weight. The objective of plant
engineers is to optimize the time of the blowing agent addition and the extent
of initiator needed to improve the overall productivity.
The Aspen Plus RBatch reactor model is used to simulate the batch
polymerization. The EPS process involves two liquid phases (monomer and
water) and one vapor phase, which is rigorously handled inside RBatch. All
polymerization reactions (initiation, propagation, termination, and chain
transfer) occur in the monomer rich phase. This is specified using a phase
identifier in the free-radical kinetic model.
Initiator decomposition and thermal initiation in the monomer droplets
generate radicals that polymerize the monomer. The polymer is soluble in the
monomer phase. As the monomer concentration drops, the onset of diffusion
controlled termination leads to an auto-acceleration or gel effect, which
increases the reaction rate. At high conversion, the polymer monomer
mixture becomes glassy, and the propagation reaction becomes diffusion
limited. This effect is known as the glass effect.
The model is used to study the effect of adding n-pentane at the beginning of
the polymerization. N-pentane is a stronger electron donor than styrene, and
addition of n-pentane leads to a reduction in chain transfer to monomer. By
using user-gel effect correlations, the model captures the effect of n-pentane
on chain transfer, gel effect, and glass effect.
Process Definition
The first stage of the EPS suspension polymerization process is modeled using
the batch reactor model, RBatch. The recipe is defined in terms of
concentrations at 25C in the monomer phase. Therefore, the charge stream,
which is specified in overall concentrations, is fed to a three-phase block at
25C.
The charge of individual components is adjusted until the equilibrium
concentrations in the monomer phase match the required recipe and the
dispersed phase volume fraction equals 0.4. All streams from the Flash3 block
are then passed to a heater that heats the charge stream to the initial
reaction temperature.
B3 Expanded Polystyrene Suspension Polymerization 119

Process Conditions
The batch reactor feed time is specified at one hour so that the charge flow
rate on an hourly basis is equivalent to the actual charge. After the execution
of the Flash3 block, a calculator block computes phi (the dispersed phase
holdup) and initator and pentane concentrations. The reaction occurs at
constant temperature (90C) and pressure (275 Kpa for pentane=0 case, and
825 Kpa for pentane cases).
Note: In the delivered model, the calculator block is hidden. If the calculator
block is revealed, a Fortran compiler is required to run the example.

Polystyrene PS POLYMER Polymer component
Benzoyl peroxide BPO --- Initiator (Mw=242.23)
Coinitiator CINI --- Coinitiator (zero concentration,
required for thermal initiation)
n-pentane NPENTANE PURE11 Blowing agent
Water H2O PURE11 Suspension medium
Physical Properties POLYNRTL property method with supplied parameters
Recipe
Initial volume at 25C (cc) 3200

Dispersed phase volume 0.4
fraction at 25C
Inititiator concentration 0.01
(kmol/m3)
n-Pentane concentration 0.0, 7.5, 15
(wt%, with regard to
styrene)
Charge
Temperature (C) 90
Pressure (KPa) 275 (n-pentane=0), 825 (n-pentane>0)
Volume Flow (m3/hr) 3.2E-3
Mass parts of initiator .27
Mass parts of polystyrene 0.0
Mass parts of coinitiator 0.0
Mass parts of monomer 100, 92.5, 85
Mass parts of water 170.1
Mass parts of n-pentane 0.0, 7.5, 15
Kinetics FREE-RAD model (options specify reactions in L1 phase only)
Operating Conditions Block Temp Pres

(C)

FLASH3 25 = Charge
HEATER 90 = Charge
BATCH 90 = Charge

The Polymer Non-Random Two Liquid activity coefficient model physical
property method (POLYNRTL) is used. The thermophysical properties (density,
heat capacity, etc.) of styrene, n-pentane, and water are obtained from the
Aspen Plus Pure Component Databank. Note that initiator and coinitiator are
given the properties of styrene with the exception of molecular weight. The
polymer thermophysical properties are calculated using the van Krevelen
group contribution method.
Reactors / Kinetics
The kinetics of suspension EPS are similar to those of the bulk polystyrene
(See B1 Polystyrene Bulk Polymerization by Thermal Initiation application
example).
The reactions included from the free-radical built-in kinetics are:
Thermal initiation 3M 2 R
Initiator decomposition I 2R
Chain initiation R M P1
Propagation Pn M Pn 1
Chain transfer to monomer Pn M Dn P1
Termination by combination Pn Pm Dn m
The units for the rate constants for the thermal initiation reaction are
m6/kmol2/s. For initiator decomposition the units are /s. The units for the rate
constants for the other reactions are m3/kmol2/s.
Thermal initiation is defined using the special initiation reaction and by setting
third-order thermal initiation with respect to monomer. A coinitiator, which is
required for the special initiation reaction, is included in the list of
components, but its feed rate is set to zero so that it will not influence the
rate for the thermal initiation reaction.
As mentioned previously, the gel and glass effects are modeled using a user
gel effect correlation:
Description Correlation Number
Termination (gel effect) 4

Propagation (glass effect) 5
Chain transfer to monomer 3

(effect of n-pentane on)
The correlations contained within the user Fortran routine, usrgel.f, calculate
the gel factor for each of these reactions using the free volume theory
described by Villalobos (1993). The gel factor is multiplied with the rate
constant calculated from the pre-exponental and activation energy to give the
diffusion limited rate constant.
Process Studies
The model is used to study the effect of initial n-pentane concentration on
conversion and molecular weight profiles.
Input Summary
TITLE 'SUSPENSION EXPANDED POLYTSTYRENE BATCH PROCESS'
IN-UNITS SI
OUT-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='MMkcal/hr' &

PDROP=bar
DIAGNOSTICS
HISTORY SIM-LEVEL=4
;
; THE COMPONENT SYSTEM DEFINITION FOLLOWS
;
DESCRIPTION "
EXPANDED POLYSTYRENE SUSPENSION POLYMERIZATION BATCH
PROCESS. THIS EXAMPLE USES THE KINETIC MODEL AND RATE
CONSTANTS DESCRIBED IN VILLALOBOS,M.A.,HAMIELEC,A.E,AND
WOOD, P.E.,BULK AND SUSPENSION POLYMER IZATION OF STYRENE
IN THE PRESENCE OF N-PENTANE. AN EVALUATION OF MONO
FUNCTIONAL AND BIFUNCTIONAL INITIATION,
J.APPL.POLYM.SCI,50,327-343 (19 93)
"
DATABANKS PURE12 / POLYMER / SEGMENT / ASPENPCD
PROP-SOURCES PURE12 / POLYMER / SEGMENT / ASPENPCD
COMPONENTS

BPO C8H8 /
CINI C8H8 /
STY C8H8 /
PS PS-1 /
STY-SEG C8H8-R /
WATER H2O /
NPENTANE C5H12-1
FLOWSHEET
BLOCK BATCH IN=4 OUT=PRODUCT
BLOCK FLASH3 IN=CHARGE OUT=1 2 3
BLOCK HEATER IN=1 2 3 OUT=4
PROPERTIES POLYNRTL
PROP-DATA DATA1
IN-UNITS SI
PROP-LIST MW
PVAL BPO 242.230
PROP-DATA PLXANT-1
IN-UNITS SI
PROP-LIST PLXANT
PVAL PS -10.0
PROP-DATA NRTL-1
HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=K &
PDROP=bar
PROP-LIST NRTL
BPVAL BPO WATER -176.71520 10542.57030 .20 0.0 25.52320 &
0.0 279.150 338.150
BPVAL WATER BPO 150.57740 -5675.06590 .20 0.0 -21.68180 &
0.0 279.150 338.150
BPVAL CINI WATER -176.71520 10542.57030 .20 0.0 25.52320 &
0.0 279.150 338.150
BPVAL WATER CINI 150.57740 -5675.06590 .20 0.0 -21.68180 &
0.0 279.150 338.150
BPVAL STY WATER -176.71520 10542.57030 .20 0.0 25.52320 &
0.0 279.150 338.150
BPVAL WATER STY 150.57740 -5675.06590 .20 0.0 -21.68180 &
0.0 279.150 338.150
BPVAL STY-SEG WATER 0.0 500.0 .30 0.0 0.0 0.0 0.0 &
1000.0
BPVAL WATER STY-SEG 0.0 500.0 .30 0.0 0.0 0.0 0.0 &
1000.0
BPVAL WATER NPENTANE 12.38660 -791.79130 .20 0.0 0.0 0.0 &
273.150 303.150
BPVAL NPENTANE WATER -10.68920 5051.72750 .20 0.0 0.0 0.0 &
273.150 303.150
POLYMERS
POLYMERS PS

ATTRIBUTES PS DPN DPW PDI MWN MWW ZMOM FMOM SMOM SFLOW &
SFRAC
PROP-SET PS-1 MASSFRAC SUBSTREAM=MIXED COMPS=PS PHASE=L1
PROP-SET VOLFLOW VOLFLMX UNITS='cum/hr' SUBSTREAM=MIXED PHASE=T
STREAM CHARGE
PDROP=bar
SUBSTREAM MIXED TEMP=25.0 PRES=8.250 VOLUME-FLOW=.00320 &
FREE-WATER=NO NPHASE=3 PHASE=V
MASS-FRAC BPO .2780 / STY 100.0 / WATER 170.10
BLOCK HEATER HEATER

PDROP=bar
PARAM TEMP=90.0 PRES=0.0 NPHASE=3
BLOCK-OPTION FREE-WATER=NO
BLOCK FLASH3 FLASH3

PDROP=bar
PARAM TEMP=25.0 PRES=0.0
BLOCK BATCH RBATCH

PDROP=bar
PARAM TYPE=T-SPEC PRINT-TIME=.166666667 FEED-TIME=1.0 &
MAX-TIME=8.0 MAX-NPOINT=50 PRES=2.750 TEMP=90.0 &
NPHASE=3 FLASH=YES
PROP-REACTOR PS-1
BLOCK-OPTION TERM-LEVEL=6 FREE-WATER=NO
L2-COMPS COMP-LIST=WATER
EO-CONV-OPTI
CALCULATOR PHI

PDROP=bar
DEFINE VL1 STREAM-PROP STREAM=2 PROPERTY=VOLFLOW
DEFINE VLTOT STREAM-PROP STREAM=CHARGE PROPERTY=VOLFLOW
DEFINE BPO MOLE-FLOW STREAM=2 SUBSTREAM=MIXED COMPONENT=BPO
DEFINE NC5 MASS-FRAC STREAM=2 SUBSTREAM=MIXED &
COMPONENT=NPENTANE
F WRITE(*,*) 'PHI =',VL1/VLTOT
F WRITE(*,*) '[I]O =',BPO/VL1,' MOL/L-STYRENE'
F WRITE(*,*) '[C5]O =',NC5*100,' WT%(WRT STYRENE)'
EXECUTE AFTER BLOCK FLASH3
CONV-OPTIONS
PARAM CHECKSEQ=NO
STREAM-REPOR MOLEFLOW MASSFLOW MASSFRAC PROPERTIES=PS-1 VOLFLOW
IN-UNITS MET
DESCRIPTION "EXAMPLE FREE-RADICAL INPUT"
PARAM QSSA=YES
SPECIES INITIATOR=BPO COINITIATOR=CINI MONOMER=STY &
POLYMER=PS
INIT-DEC BPO 3.8160E+12 27233.0 0.0 EFFIC=.60 NRADS=2
INIT-SP STY CINI 219000.0 27440.0 0.0
CHAIN-INI STY 1.0213E+07 7068.0 0.0
PROPAGATION STY STY 1.0213E+07 7068.0 0.0
CHAT-MON STY STY 1.0213E+07 13450.0 0.0
GEL-EFFECT TERMINATION 4 MAX-PARAMS=3 GE-PARAMS=.50 .3480 &
1.750
GEL-EFFECT PROPAGATION 5 MAX-PARAMS=2 GE-PARAMS=1.0 .04650
GEL-EFFECT CHAT-MON 3 MAX-PARAMS=1 GE-PARAMS=1.750
SUBROUTINE GEL-EFFECT=USRGEL
OPTIONS PHASE=L1;

The effect of initial n-pentane concentration on conversion is shown hereT:

1
0.9
0.8
0.7
Conversion
0.6
0.5
0.4
0.3
0.2
0.1
0 1 2 3 4 5 6 7 8
Time(hours)
n-pentane=0 n-pentane=7.5% n-pentane=15%
As shown, the auto-accleration (gel) effect is apparent in the case with no n-

pentane: the slope of the conversion curve increases at about 6 hours. The
glass effect, which results in a flattening of the curve as the propagation rate
constant is decreased when the polymer mixture becomes glassy, is also
shown.
The other two curves show that neither the gel effect nor the glass effect is
reached due to the plasticizing effect of the n-pentane.
The number and weight average molecular weights for the three n-pentane
cases are shown here:
300
275
(Thousands)
250
225
200
175
150
Mn,Mw
125
100
75
50
25
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Conversion
npentane=0 npentane=0 npentane=7.5%
npentane=7.5% n-pentane=15% n-pentane=15%
One would expect the addition of a solvent to reduce the molecular weight.
However, the n-pentance reduces this effect by lowering the chain transfer to
monomer rate. Additionally, because it is a stronger electron donor than
styrene, n-pentane can obstruct the hydrogen abstraction necessary for chain
transfer to solvent to occur. Therefore, n-pentane addition leads to a
molecular weight build-up in the system.

References
Villalobos, M. A., Hamielec,A. E., & Wood, P. E. (1993). Bulk and Suspension
Polymerization of Styrene in the Presence of n-Pentane. An Evaluation of
Monofunctional and Bifunctional Initiation. J. Appl. Polym. Sci., 50, 327-343.

B4 Styrene Ethyl Acrylate
Free-Radical
Copolymerization Process
The styrene ethyl acrylate free-radical copolymerization model illustrates the

use of Aspen Polymers to model a styrene ethyl acrylate free-radical process.
The process modeled is an experimental system developed by McManus and
Penlidis at the University of Waterloo. The model is then used along with the
experimental data generated at the University of Waterloo to estimate
reaction rate constant parameters.
About This Process

The copolymerization of styrene with ethyl acrylate is of considerable interest
to the polymer industry. In 1996, McManus and Penlidis from the University of
Waterloo reported a detailed study of the copolymerization of styrene and
ethyl acrylate, and generated extensive data by varying the initiator
concentration, feed composition, and the reactor temperature (McManus &
Penlidis, 1996). Similar studies have been done for this system (Fehervari et
al., 1981). A number of investigators estimated the kinetic parameters, but
there are many discrepancies between kinetic rate constants and the
reactivity ratios reported in the literature. McManus and Penlidis reviewed the
information available on the kinetic data and estimated the reactivity ratios.
Process Definition
The copolymerization of styrene and ethyl acrylate is carried out in a batch
reactor. The batch reactor is charged with a pre-mixed stream of styrene,
ethyl acrylate, and the initiator azo-bis-isobutyronitrile. The reactor is
operated at a constant temperature and pressure. The flowsheet is shown
here:
128 B4 Styrene Ethyl Acrylate Free-Radical Copolymerization Process

Process Conditions
Initiator AIBN PURE12 Initiator

Ethyl Acrylate EA PURE12 Monomer
Polymer POLYMER POLYMER Polymer
EA-SEG SEGMENT Ethyl Acrylate
segment
Physical Properties POLYNRTL property method
Stream Monomer Initiator
Temperature (C) 60 60
Pressure (atm) 1 1
Mass flow kg/h 1000
Mole flow of AIBN 0.05 MR/L in reaction mixture
Mole fraction of styrene 0.762
Mole fraction of ethyl acrylate 0.238
Operating Conditions
BATCH reactor
Temperature (C) 60
Pressure (atm) 1
Reaction time (hr) 25
Cycle time (hr) 1
Reactors / Kinetics
The reaction set used in this process and the initial rate constant parameters
are:
Description k0 Ea V EFFIC
(m3/kmol) (J/kmol) (m3/kmol)
B4 Styrene Ethyl Acrylate Free-Radical Copolymerization Process 129

INIT-DEC AIBN 1.82E15 1.288E8 E 0.0 0.5080
8
CHAIN-INI STY 4.5E6 2.6E7 0.0
CHAIN-INI EA 3.0E6 2.24E7 0.0
PROPAGATION STY 2.3438E6 2.6E7 0.0
STY
PROPAGATION STY 3.26562E6 2.6E7 0.0
EA
PROPAGATION EA 1.49182E7 2.24E7 0.0
STY
PROPAGATION EA EA 3.000E6 2.24E7 0.0
CHAT-MON STY STY 117.190 2.6000E+0 0.0
7
CHAT-MON STY EA 163.30 2.6000E+0 0.0
7
CHAT-MON EA STY 746.0 2.2400E+0 0.0
7
CHAT-MON EA EA 95.50 2.2400E+0 0.0
7
TERM-COMB STY STY 1.4592E9 7E6 0.0
TERM-COMB STY EA 6.63E10 14.6E6 0.0
TERM-COMB EA STY 6.63E10 14.6E6 0.0
TERM-COMB EA EA 3.00E10 22.2E6 0.0
Gel effect is applied to the initiator efficiency and termination reaction using
correlation No. 2.
Reaction Correlation Parameters
INIT-EFF 2 -17.40
0.05528
17.8240
-05090
0.0
0.0
0.0
0.0
0.0
2.0
TERMINATION 2 1.0
0.0
2.570
-.005050
9.560
-.01760
-3.030
.007850
0.0
2.0

Parameter Regression
The experimental data reported by McManus and Penlidis includes conversion,
polymer composition, and number and weight average molecular weights as a
function of time. This data was generated by varying: (1) the initial mole
ratio of styrene to EA, (2) the initiator concentration, and (3) the reactor
temperature. The DATA-FIT capability is used to fit the reaction rate constant
parameters.
Monomer conversion and number average molecular weights were used to
regress the kinetic parameters. The experimental data obtained at 50 and
60C is provided in the following two tables. To indicate the accuracy of the
experiments, data obtained with a replicate experiment are also included in
the tables.
T=50C, Styrene Mole Fraction in the feed=0.762, and AIBN=0.05 mol/L
Data used in Data-Fit Replicate Experiment Simulation Results
Time Conversion Molecular Conversion Molecular Conversion Molecular

(min) (mass %) Weight (mass %) Weight (mass %) Weight
(Mn) (Mn) (Mn)
0 0 9.61E+04 0 0.00E+00 0 92990

120 5.68 9.61E+04 5.62 98204 5.36 92990
240 10.79 9.69E+04 11.58 84913 10.6 95576.3
360 16.09 9.85E+04 16.48 89791 15.82 98699.5
480 21.06 1.02E+05 21.86 99669 21.11 1.02E+05
600 26.16 1.02E+05 26.82 99269 26.55 1.07E+05
660 28.63 101179
720 37.55 1.04E+05 32.3 97121 32.25 1.12E+05
840 36.6 1.05E+05 37.08 105809 38.33 1.18E+05
900 41.8 106172
930 39.36 1.12E+05
960 1.12E+05 42.82 101569 44.98 1.26E+05
1020 45.97
1080 52.44 1.35E+05
1110 54.68 1.12E+05 56.22 99967
1200 61.44 1.15E+05 61.08 1.46E+05
1290 68.66 1.35E+05 70.71 108848
1320 71.37 1.60E+05
1410 77.46 1.34E+05 79.37 142398
1440 83.38 1.78E+05
1560 94.04 1.92E+05
1620 97.44 1.21E+05
1680 98.37 1.94E+05
1760 99.5 201441
T=60C, Styrene Mole Fraction in the feed=0.762, and AIBN=0.05 mol/L

Data used in Data-Fit Replicate Experiment Simulation Results
Time Conversion Molecular Conversion Molecular Conversion Molecular

(min) (mass %) Weight (mass %) Weight (mass %) Weight
(Mn) (Mn) (Mn)
0 0 6.13E+04 0.00E+00 53353 0 60149

60 7.73 6.13E+04 6.9 60149
90 5.62 53353
120 14.16 6.34E+04 13.44 63142
180 21.14 6.73E+04 11.58 58819 19.788 66606
240 27.25 6.49E+04 16.48 50716 26.088 7.06E+04
300 34.02 7.09E+04 21.86 51287 32.47 7.51E+04
360 40.32 6.17E+04 26.82 59017 39.07 8.04E+04
390 28.63 64038
420 47.11 6.99E+04 46.04 8.64E+04
465 49.25 7.54E+04
480 32.3 68012 53.55 9.35E+04
510 57.32 8.09E+04
540 37.08 73434 61.81 1.02E+05
555 62.15 6.49E+04
600 71.16 9.14E+04 41.8 74867 71 1.12E+05
645 83.02 9.37E+04
660 42.82 97000 81 1.23E+05
705 94.8 1.12E+05
720 56.22 98327 90.39 1.32E+05
780 100 1.26E+05 70.71 120620 96.39 1.38E+05
79.37 109391
840 98.67 1.38E+05
900 99.3 1.37E+05
Homo-propagation rate constants are regressed to fit the conversion data.

Cross-propagation rate constants are calculated using the reactivity ratios.
Homo-termination rate constants are regressed to fit the molecular weights.
Cross-termination rate constants are set to the square root of the product of
the homo-termination rate constants.
In the styrene-ethyl acrylate kinetic scheme, eleven reactions were chosen
and the gel-effect was applied to the termination and initiation reaction.
E VP
Recall that k ko exp . This results in thirty-four kinetic
RT RT
parameters and twenty gel-effect parameters available for fitting. The
available data is not sufficient to regress all these parameters. The following
approach was used to reduce the number of parameters needed for a good
fit.
Since the batch reactor is operated at 1 atm, the effect of activation
volume on the rate constant can be neglected for all the reactions.

Therefore, the activation volume was set to zero for all the reactions. Note
that at high pressures the effect of activation volume cannot be neglected.
The initiator decomposition rate constants were known. Typically these
can be obtained from a good polymer handbook or from the supplier. They
can also be calculated using the half-life data. (See Appendix B of the
Aspen Polymers User Guide, Volume 1).
Chain initiation rate constants are in general faster than the propagation
rate constants. Therefore these constants were set to be the same or
greater than the propagation rate constants.
There are two homo-propagation reactions and two cross-propagation
reactions in the kinetic scheme. The number of regressable parameters is
then eight excluding the activation volume parameters.
The number of regressable propagation parameters can be reduced if the
homo-propagation rate constants and/or the reactivity ratios are known. If
the homo-propagation rate constants are known then reactivity ratios can
be estimated. If the reactivity ratios are known homo-propagation rate
constants can be estimated. In this example, reactivity ratios were given
(Fehervari et al., 1981), and the homo-propagation rate constants were
regressed. The cross-propagation rate constants were calculated using the
following equations:
r1 k 11 12
p / kp
r2 k p22 / k p21
Where:
STY=1
EA=2
Four termination reactions are considered in this scheme. Cross-
termination reactions involving STY and EA segments were set to have the
same rate constant. This reduces specification of the rate constants to
three. If the homo-termination rate constants are known, the cross-
termination rate constants can be estimated using the following
equations:
k12 k11 k 22
k 21 k12
In this example homo-termination rate constants were regressed using
the molecular weight data.
In the kinetic scheme termination by combination was selected. It is
possible that termination by disproportionation can also occur. One needs
to know apriori the termination mechanism. As a general rule if
polydispersity (PDI) is 1.5 termination by combination is controlling and if
PDI is two termination is controlled by the disproportionation reaction.
At high conversion termination is diffusion controlled. This is modeled
using the gel-effect option. Therefore use of low conversion data is
recommended for regression of the kinetic parameters without using gel-
effect. High conversion data is then used to regress the gel-effect
parameters.
Monomer conversion data was used to regress the initiator efficiency,
propagation and the termination rate constants. Molecular weight data

was used to regress the propagation and the termination rate constants.
The gel-effect parameters influence both the conversion and the molecular
weight.
Chain transfer reactions do not affect the conversion but affect the
polymer molecular weight.
The following table summarizes the approach for fitting the kinetic rate
constant parameters:
Required Data
Reaction Parameter Conversion MWn PDI LCB SCB Copolymer

or Composition
DPn
INIT-DEC kd Initiator
PROPAGATIO kp Monomer X X X
N
CHAT-MON ktrm X X
CHAT-SOL ktrs X X
CHAT-AG ktra X X
TERM-DIS ktd Monomer X X
TERM-COM ktc Monomer X X
INHIBITION kx Monomer X X
CHAT-POL ktrp X X
SC-BRANCH kscb X
Process Studies
Input Summary
The input language summary for this example is shown here:DYNAPLUS
DPLUS RESULTS=ON
TITLE 'Data-fit Example Using Free Radical Polymerization'

TEMPERATURE=C TIME=hr VOLUME=l MASS-DENSITY='gm/cc' &
PDROP='N/sqm'
OUT-UNITS SI MASS-FLOW='kg/hr' MOLE-FLOW='kmol/hr' PRESSURE=atm &

TEMPERATURE=C TIME=min VOLUME=l MASS-DENSITY='gm/cc' &
PDROP='N/sqm'
DESCRIPTION "
Batch reactor data for styrene-ethyl acrylate
polymerization is used to regress the propagation

rate constant
"
COMPONENTS
AIBN C8H8 /
STY C8H8 /
EA C5H8O2 /
STY-SEG C8H8-R /
EA-SEG C5H8O2-R-2 /
POLYMER PS-1
FLOWSHEET
BLOCK BATCH IN=FEED OUT=POLYMER
BLOCK MIX IN=MONOMER INIT OUT=FEED
PROPERTIES POLYNRTL
PROP-DATA MW
IN-UNITS ENG
PROP-LIST MW
PVAL AIBN 164.2120
POLYMERS
SEGMENTS STY-SEG REPEAT / EA-SEG REPEAT
POLYMERS POLYMER
ATTRIBUTES POLYMER SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM &
FMOM SMOM
PROP-SET INITCONC
PROPNAME-LIS MOLECONC UNITS='mol/l' SUBSTREAM=MIXED &
COMPS=AIBN
PROP-SET POLY-MF
PROPNAME-LIS MASSFRAC SUBSTREAM=MIXED COMPS=POLYMER PHASE=L
STREAM INIT
PRESSURE=atm TEMPERATURE=C VOLUME=l &
MASS-DENSITY='gm/cc' PDROP='N/sqm'
MOLE-FLOW AIBN .05710370
STREAM MONOMER
PRESSURE=atm TEMPERATURE=C VOLUME=l &
MASS-DENSITY='gm/cc' PDROP='N/sqm'
MOLE-FRAC STY .7620 / EA .2380

BLOCK MIX MIXER
IN-UNITS ENG
BLOCK BATCH RBATCH

PARAM TYPE=T-SPEC PRINT-TIME=1.0 CYCLE-TIME=1.0 &
MAX-TIME=25.0 MAX-NPOINT=27 TEMP=60.0 ERR-METHOD=DYNAMIC
PROP-REACTOR POLY-MF
REACTIONS RXN-IDS=STY-EA
EO-CONV-OPTI
CALCULATOR F-1
DEFINE F PARAMETER 1
F F = 5
EXECUTE FIRST
CALCULATOR K-PROP
DEFINE PROP11 REACT-VAR REACTION=STY-EA VARIABLE=PRPRE-EXP &
SENTENCE=PROPAGATION ID1=STY ID2=STY
SENTENCE=PROPAGATION ID1=STY ID2=EA
SENTENCE=PROPAGATION ID1=EA ID2=STY
SENTENCE=PROPAGATION ID1=EA ID2=EA
F R1 = 0.717
F R2 = 0.128
F PROP12 = PROP11/R1
F PROP21 = PROP22/R2
READ-VARS PROP11 PROP22
WRITE-VARS PROP12 PROP21
CALCULATOR K-TERM
DEFINE TC11 REACT-VAR REACTION=STY-EA VARIABLE=TCPRE-EXP &
SENTENCE=TERM-COMB ID1=STY ID2=STY
SENTENCE=TERM-COMB ID1=STY ID2=EA
SENTENCE=TERM-COMB ID1=EA ID2=STY
SENTENCE=TERM-COMB ID1=EA ID2=EA
DEFINE F PARAMETER 1
F TC12 = F*(TC11*TC22)**0.5
F TC21 = F*(TC11*TC22)**0.5
READ-VARS TC11 TC22
WRITE-VARS TC12 TC21
CONV-OPTIONS
PARAM CHECKSEQ=NO
STREAM-REPOR MOLEFLOW MASSFLOW MOLEFRAC MASSFRAC &

PROPERTIES=INITCONC

REACTIONS STY-EA FREE-RAD
IN-UNITS SI
PARAM QSSA=YES
SPECIES INITIATOR=AIBN MONOMER=STY EA POLYMER=POLYMER
MON-RSEG STY STY-SEG / EA EA-SEG
INIT-DEC AIBN 1.8200E+15 1.2880E+08 EFFIC=.5080
CHAIN-INI STY 4500000.0 2.6000E+07
CHAIN-INI EA 3000000.0 2.2400E+07
PROPAGATION STY STY 2343800.0 2.6000E+07
PROPAGATION STY EA 3265620.0 2.6000E+07
PROPAGATION EA STY 1.4918E+07 2.2400E+07
PROPAGATION EA EA 3000000.0 2.2400E+07
CHAT-MON STY STY 117.190 2.6000E+07
CHAT-MON STY EA 163.30 2.6000E+07
CHAT-MON EA STY 746.0 2.2400E+07
CHAT-MON EA EA 95.50 2.2400E+07
TERM-COMB STY STY 1.4592E+09 7000000.0
TERM-COMB STY EA 6.6300E+10 1.4600E+07
TERM-COMB EA STY 6.6300E+10 1.4600E+07
TERM-COMB EA EA 3.0000E+11 2.2200E+07
GEL-EFFECT INIT-EFF 2 MAX-PARAMS=10 GE-PARAMS=-17.40 &
.055280 17.8240 -.05090 0.0 0.0 0.0 0.0 0.0 2.0
2.570 -.005050 9.560 -.01760 -3.030 .007850 0.0 2.0
REGRESSION K-PROP
DATA WPOLY
VARY REACT-VAR REACTION=STY-EA VARIABLE=PRPRE-EXP &
SENTENCE=PROPAGATION ID1=STY ID2=STY
LIMITS 5E4 1E7
ALGORITHM MXPASS=3000
DATA-SET MWN
IN-UNITS ENG
DEFINE TIME BLOCK-VAR BLOCK=BATCH VARIABLE=VALUE &
SENTENCE=STOP ID1=1
DEFINE MWN COMP-ATTR-VAR STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=POLYMER ATTRIBUTE=MWN ELEMENT=1
INPUT TIME
RESULT MWN
USE STD-DEV .010 5000.0 / DATA 2.0 96148.0 / DATA 4.0 &
96939.0 / DATA 6.0 98547.0 / DATA 8.0 102418.0 / &
DATA 10.0 101941.0 / DATA 12.0 104354.0 / DATA 14.0 &
105066.0 / DATA 15.50 112415.0 / DATA 17.0 112159.0 / &
DATA 18.50 112001.0 / DATA 20.0 114564.0 / DATA &
21.50 135065.0 / DATA 23.50 133690.0 / DATA 27.0 &
120899.0
DATA-SET WPOL-SFR
IN-UNITS ENG
SENTENCE=STOP ID1=1
DEFINE WPOLY MASS-FRAC STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=POLYMER

DEFINE SFRAC COMP-ATTR-VAR STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=POLYMER ATTRIBUTE=SFRAC ELEMENT=1
INPUT TIME
RESULT WPOLY SFRAC
USE STD-DEV .010 .010 .010 / DATA 2.0 .05680 .7590 / &
DATA 4.0 .10790 .7980 / DATA 6.0 .16090 .7660 / &
DATA 8.0 .21060 .7360 / DATA 10.0 .26160 .7710 / &
DATA 12.0 .37550 .7510 / DATA 14.0 .3660 .7630 / &
DATA 20.0 .61440 .780 / DATA 21.50 .68660 .7870 / &
DATA 23.50 .77460 .7970 / DATA 27.0 .97440 .7550
DATA-SET WPOLY
IN-UNITS ENG
SENTENCE=STOP ID1=1
DEFINE WPOLY MASS-FRAC STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=POLYMER
INPUT TIME
RESULT WPOLY
USE STD-DEV .010 .010 / DATA 2.0 .05680 / DATA 4.0 &
.10790 / DATA 6.0 .16090 / DATA 8.0 .21060 / DATA &
10.0 .26160 / DATA 12.0 .37750 / DATA 14.0 .3660 / &
DATA 15.50 .39360 / DATA 17.0 .45970 / DATA 18.50 &
.54680 / DATA 20.0 .61440 / DATA 21.50 .68660 / &
DATA 23.50 .77460
;

The following two figures show estimated molecular weight and monomer
conversion as a function of the experimental data. As shown in these figures,
a good match is obtained between the predictions and experimental data. The
values of the fitted parameters are:
Reaction Parameter Estimate Std. Dev. Confidence Internal
Lower Limit Upper Limit
Styrene homo- Pre-exponential 2.154 x 107 19169.6 2.1168 x 106 2.1919 x 106
propagation factor
EA homo-propagation Pre-exponential 3.0 x 106 6.65 x 106 5 x 105 1 x 107
factor
Styrene homo- Pre-exponential 1.26 x 109 --- --- ---
termination factor
EA homo-termination Pre-exponential 2.6 x 109 --- --- ---
factor
The estimated versus measured MWn is shown here:

The estimated versus measured monomer conversion is shown here:

The following figures show the conversion and molecular weight data
comparison of the simulation results with the experimental data at 50 and
60C respectively.
A comparison of simulation results and experimental data at 50C is shown

here:

A comparison of simulation results and experimental data at 60C is shown
here:

References
Fehervari, A, Foldes-Berezsnich, T., & Tudos, F. (1981). J. Macromol. Sci.
Chem., A16, p. 993.
McManus, N. T., & Penlidis, A. (1996). A Kinetic Investigation of Styrene/Ethyl
Acrylate Copolymerization. J. Polym. Sci. Polym. Chem., 34, p. 237.

B5 Styrene Butadiene
Emulsion Copolymerization
Process
The styrene butadiene emulsion copolymerization process model illustrates

the use of Aspen Polymers to model the free-radical emulsion polymerization
of styrene and butadiene in a semi-batch reactor. The model is used to
examine several process parameters as a function of time: average number
of radicals per particle, monomer concentration in the various phases, and
monomer conversion.
About This Process

In this process, the emulsion copolymerization of styrene and butadiene is
carried out in a batch reactor using ammonium persulfate (APS) as the
initiator, sodium lauryl sulfate (SLS) as the emulsifier and tertiary dodecyl
mercaptane (TDM) as a chain transfer agent. Functionalized styrene-
butadiene emulsions are used in a variety of applications such as paper
coatings, carpet backings, non-wovens, etc. In addition, emulsion
polymerization is the major route for the production of synthetic rubber used
in the tire industries. Most styrene-butadiene rubber (SBR) latexes are
manufactured in semi-batch reactors. SBR production technology is detailed
by Blackley (Blackley, 1983).
In a typical semi-batch process employing in-situ seeding, the initial charge is
used for the production of seed particles, with the desired particle size and
particle size distribution. Usually, anionic emulsifiers and water-soluble
persulfate initiators are used for particle nucleation by the micellar
mechanism.
When the initial mixture is heated, the radicals generated from the initiator
become surface active and enter micelles to form particles. Once the particle
specifications are met, monomers and other ingredients, such as chain
transfer agent, stabilizers, initiators, are continuously added to the reactor,
and the particles are grown to the desired final particle size.
B5 Styrene Butadiene Emulsion Copolymerization Process 143

The latter stage of the reaction is also known as the growth stage of the
reaction, and is responsible for the development of the properties of the
emulsion polymer: molecular weight, composition, micro structure, etc. The
growth stage is the better understood stage of the process. Therefore, this
stage provides more opportunities to control the emulsion process.
The adjustable process parameters include temperature and feeding strategy
of monomer and other ingredients. Control of polymer composition is very
often achieved by feeding the monomers in a manner such that there is no
separate monomer droplet present in the reactor. Very often the productivity
of the reactor is limited by its cooling capacity. Chain transfer agents are
usually added to control molecular weight, and degree of branching.
Process Definition
The process flowsheet consists of the batch reactor with an initial batch
charge and a continuous feed for the addition of monomers and other
ingredients:
This model provides the base case, which can be used to study various
process variables: effect of initiator and emulsifier levels, temperature,
Smith-Ewart kinetics, etc.
Process Conditions

Butadiene BD PURE12 Monomer
Water H2O PURE12 Dispersant
Ammonia APS PURE12 Initiator (Mw=220.0) Select H2O
persulfate
Sodium lauryl SLS PURE12 Emulsifier (Mw=288.0) Select
sulfate H2O
Polymer POLYMER POLYMER Polymer
144 B5 Styrene Butadiene Emulsion Copolymerization Process

Styrene-segment STY-SEG SEGMENT Repeat segment
Butadiene- BD-SEG SEGMENT Repeat segment
segment
Tert dodecyl TDM PURE12 Chain transfer agent (MW= 224,
mercaptane select C8H8)
Polymer Choose emulsion polymer attributes
Characterization Distribution = chain-size
No. of points = 100 (upper = 100000)
Physical POLYNRTL property method with supplied binary interaction
Properties parameters
Feeds
Charge Stream CFEED

Pressure (atm) 10 10
Styrene (kg/hr) 300 700
Butadiene (kg/hr) 300 700
Sodium 30 100
laurylsulfate
(kg/hr)
Ammonium 7 3
persulfate (kg/hr)
TDM (kg/hr) 30 0
Water (kg/hr) 1000 1000
Continuous Feed
Time (hr) Total (kg/hr)

0.0 0.0
1.0 0.0
1.0 1200.0
2.0 1200.0
2.0 0.0
Kinetics EMULSION
Operating
Conditions
B1 Pressure (atm) 10
FLASH Option NO
Temperature
profile
Time (hr) Temperature
(C)
0.0 65.0
0.5 65.0
0.5 70.0
1.0 70.0
1.0 75.0

2.0 75.0

The Polymer Non-Random Two Liquid activity coefficient model (POLYNRTL) is
used as the physical property method. The thermophysical properties
(density, heat capacity, etc.) of the monomers are obtained from the Aspen
Plus pure component databank. The polymer physical properties are
calculated using the van Krevelen method. Initiator concentrations are
calculated for all of the phases.
Note: Prior to release 12, all initiators were required to be in the aqueous
phase for emulsion polymerizations. However, NRTL parameters are now
required to define the initiator APS in the aqueous phase.
The NRTL binary interaction parameters are:
NRTL
H2O STY 3.6260 1513.50 .360 0.0 0.0 0.0 0.0 1000.0
STY H2O -4.4360 2869.70 .360 0.0 0.0 0.0 0.0 1000.0
H2O BD 3.5890 862.820 .30 0.0 0.0 0.0 0.0 1000.0
BD H2O -.8520 702.170 .30 0.0 0.0 0.0 0.0 1000.0
APS STY 0 5000 .01 0.0 0.0 0.0 0.0 1000.0
STY APS 0 5000 .01 0.0 0.0 0.0 0.0 1000.0
APS BD 0 5000 .01 0.0 0.0 0.0 0.0 1000.0
BD APS 0 5000 .01 0.0 0.0 0.0 0.0 1000.0
Reactors / Kinetics
There are considerable data available on the kinetics of emulsion
copolymerization of styrene and butadiene. It is assumed that the primary
chain transfer reaction is similar to that of a monomer.
The rate constants for the kinetic scheme are obtained from Broadhead and
are summarized here (Broadhead, 1984; Ponnuswamy & Hamielec, 1997):
Reaction Phase Comp 1 Comp 2 k0 Ea
(J/kmol)
Initiator Dispersant Ammonium --- 1.0E16 1.402E8

decomposition persulfate
Propagation Polymer Styrene Styrene 2.2E7 3.2E7
Propagation Polymer Styrene Butadiene 4.4E7 3.2E7
Propagation Polymer Butadiene Butadiene 1.2E8 3.88E7
Propagation Polymer Butadiene Styrene 8.5E7 3.88E7
Chain transfer- Polymer Styrene Styrene 2.2E3 3.2E7
monomer
Chain transfer- Polymer Styrene Butadiene 4.4E3 3.2E7
monomer
Chain transfer- Polymer Butadiene Butadiene 1.2E4 2.24E6

Reaction Phase Comp 1 Comp 2 k0 Ea
(J/kmol)
monomer
Chain transfer- Polymer Butadiene Styrene 8.5E3 3.88E7
monomer
Chat-agent Polymer Styrene TDM 2.83E5 2.68E7
Chat-agent Polymer Butadiene TDM 8.5E5 3.88E7
Termination by Polymer Styrene Styrene 1.3E9 9.9E6
combination
Termination by Polymer Styrene Butadiene 1.3E9 9.9E6
combination
Termination by Polymer Butadiene Butadiene 1.3E9 9.9E6
combination
Termination by Polymer Butadiene Styrene 1.3E9 9.9E6
combination
In addition to the free-radical reaction rate constants, the following rate

constants were used for the radical exchange events:
Reaction k0 Ea (J/kmol)
Absorption into particle 1.0E-7 0.0

Absorption into micelles 1.0E-7 0.0
Desorption from particle 0.0 0.0
Other parameters affecting the kinetics are the emulsifier parameters and the
monomer partitioning. These are listed here:
CMC kmol / m3 Area m3 / kmole
Emulsifier parameters 0.009 5.0E6

Monomer partitioning Styrene .70 homosaturation in polymer
(mass)
Butadiene .50 homosaturation in polymer
TDM .8 homosaturation in polymer
Process Studies
The model was used to examine the following process parameters as a
function of time through user profiles:
Glass transition temperature of the polymer (K)
Average number of radicals per particle ---
Percent of soap coverage of particles %
Volume of the monomer phase (m3)
Concentration of monomer 1 in monomer phase (Kmol/ m3)
Concentration of monomer 2 in monomer phase (Kmol/ m3)

Volume of the aqueous phase (m3)
Concentration of the monomer 1 in aqueous phase (Kmol / m3)
Concentration of the monomer 2 in aqueous phase (Kmol / m3)
Volume of the polymer phase (m3)
Concentration of the monomer 1 in polymer phase (Kmol / m3)
Concentration of the monomer 2 in polymer phase (Kmol / m3)
Total mass conversion of monomer to polymer ---
Input Summary
TITLE 'EMULSION COPOLYMERIZATION OF STYRENE AND BUTADIENE'
IN-UNITS SI MASS-FLOW='kg/hr' PRESSURE=bar TEMPERATURE=C TIME=hr &

PDROP='N/sqm'
DESCRIPTION "
THIS EXAMPLE ILLUSTRATES THE USE OF ASPEN POLYMERS TO MODEL
THE COPOLYMERIZATION OF STYRENE AND BUTADIENE IN A BATCH
REACTOR.
"
COMPONENTS
H2O H2O /
STY C8H8 /
BD C4H6-4 /
POLYMER POLYMER /
STY-SEG C8H8-R /
BD-SEG C4H6-R-1 /
APS H2O /
SLS H2O /
TDM C8H8
FLOWSHEET
BLOCK REACTOR IN=CHARGE CONTFEED OUT=PRODUCT
PROPERTIES POLYNRTL

GMREND 1 2 1

PROP-DATA MW
IN-UNITS SI MASS-FLOW='kg/hr' PRESSURE=bar TEMPERATURE=C &
TIME=hr PDROP='N/sqm'
PROP-LIST MW
PVAL APS 228.0
PVAL SLS 288.0
PVAL TDM 202.40
PROP-DATA TGVK
IN-UNITS SI MASS-FLOW='kg/hr' PRESSURE=bar TEMPERATURE=C &
TIME=hr PDROP='N/sqm'
PROP-LIST TGVK
PVAL STY-SEG 100.0
PVAL BD-SEG -54.0
PROP-DATA NRTL-1
IN-UNITS SI
PROP-LIST NRTL
BPVAL H2O STY 3.6260 1513.50 .360 0.0 0.0 0.0 0.0 &
1000.0
BPVAL STY H2O -4.4360 2869.70 .360 0.0 0.0 0.0 0.0 &
1000.0
BPVAL H2O BD 3.5890 862.820 .30 0.0 0.0 0.0 0.0 1000.0
BPVAL BD H2O -.8520 702.170 .30 0.0 0.0 0.0 0.0 1000.0
BPVAL APS STY 0 5000 .01 0.0 0.0 0.0 0.0 1000.000
BPVAL STY APS 0.0 5000 .01 0.0 0.0 0.0 0.0 1000.000
BPVAL APS BD 0 5000 .01 0.0 0.0 0.0 0.0 1000.000
BPVAL BD APS 0.0 5000 .01 0.0 0.0 0.0 0.0 1000.000
POLYMERS
SEGMENTS STY-SEG REPEAT / BD-SEG REPEAT
POLYMERS POLYMER
ATTRIBUTES POLYMER SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM &
FMOM SMOM PSDZMOM PSDFMOM DIAV
DISTRIBUTION POLYMER CHAIN-SIZE CLD NPOINTS=100 FUNCLOG=NO &
UPPER=100000.0
PROP-SET PS-1 MASSFRAC SUBSTREAM=MIXED COMPS=POLYMER PHASE=L
STREAM CHARGE
MASS-FLOW H2O 1000.0 / STY 300.0 / BD 300.0 / POLYMER &
0.0 / APS 7.0 / SLS 30.0 / TDM 30.0
STREAM CONTFEED
MASS-FLOW H2O 1000.0 / STY 700.0 / BD 700.0 / POLYMER &
0.0 / APS 3.0 / SLS 100.0
BLOCK REACTOR RBATCH

USER-VECS NUSER-PROF=13
USERPROF ELEMENT=1 LABEL="TGAVG" UNIT-LABEL="DEG K"
USERPROF ELEMENT=2 LABEL="NBAR" UNIT-LABEL="#/PARTICLE"
USERPROF ELEMENT=3 LABEL="S-COVER" UNIT-LABEL="%"
USERPROF ELEMENT=4 LABEL="M-VOL" UNIT-LABEL="M**3"
USERPROF ELEMENT=5 LABEL="CM-1" UNIT-LABEL="KMOL/M**3"

USERPROF ELEMENT=6 LABEL="CM-2" UNIT-LABEL="KMOL/M**3"
USERPROF ELEMENT=7 LABEL="AQ-VOL" UNIT-LABEL="M**3"
USERPROF ELEMENT=8 LABEL="CAQ-1" UNIT-LABEL="KMOL/M**3"
USERPROF ELEMENT=9 LABEL="CAQ-2" UNIT-LABEL="KMOL/M**3"
USERPROF ELEMENT=10 LABEL="POL-VOL" UNIT-LABEL="M**3"
USERPROF ELEMENT=11 LABEL="CPOL-1" UNIT-LABEL="KMOL/M**3"
USERPROF ELEMENT=12 LABEL="CPOL-2" UNIT-LABEL="KMOL/M**3"
USERPROF ELEMENT=13 LABEL="CONVER" UNIT-LABEL="MASS FRAC"
PARAM TYPE=T-PROFILE PRINT-TIME=.20 CYCLE-TIME=1.0 &
MAX-TIME=10.0 MAX-NPOINT=100 PRES=10.0 NPHASE=1 &
HINIT=.000010 FLASH=NO
INTEG-PARAMS MAXSTEP=.008333333
T-PROF 0.0 65.0 / .50 65.0 / .50 70.0 / 1.0 70.0 / &
1.0 75.0 / 2.0 75.0
PROP-REACTOR PS-1
BLOCK-OPTION STREAM-LEVEL=4 TERM-LEVEL=7
REACTIONS RXN-IDS=EMLRXN
FEED-PROF SID=CONTFEED TIME=0.0 1.0 1.0 2.0 2.0 FLOW=0.0 &
0.0 1200.0 1200.0 0.0
EO-CONV-OPTI
CONV-OPTIONS
PARAM CHECKSEQ=NO
STREAM-REPOR MOLEFLOW MASSFLOW MOLEFRAC MASSFRAC
REACTIONS EMLRXN EMULSION

PARAM KBASIS=MONOMER QSSA=YES
SPECIES INITIATOR=APS MONOMER=STY BD CHAINTAG=TDM &
EMULSIFIER=SLS DISPERSANT=H2O POLYMER=POLYMER
MON-RSEG STY STY-SEG / BD BD-SEG
INIT-DEC DISPERSANT APS 1.0000E+16 1.4020E+08 0.0 &
EFFIC=.80 NRADS=2
PROPAGATION POLYMER STY STY 2.2000E+07 3.2000E+07
PROPAGATION POLYMER STY BD 4.4000E+07 3.2000E+07
PROPAGATION POLYMER BD BD 1.2000E+08 3.8800E+07
PROPAGATION POLYMER BD STY 8.5000E+07 3.8800E+07
CHAT-MON POLYMER STY STY 2200.0 3.2000E+07
CHAT-MON POLYMER STY BD 4400.0 3.2000E+07
CHAT-MON POLYMER BD BD 12000.0 3.8800E+07
CHAT-MON POLYMER BD STY 8500.0 3.8800E+07
CHAT-AGENT POLYMER STY TDM 283000.0 2.6800E+07
CHAT-AGENT POLYMER BD TDM 850000.0 3.8800E+07
TERM-COMB POLYMER STY STY 1.3000E+09 9900000.0
TERM-COMB POLYMER STY BD 1.3000E+09 9900000.0
TERM-COMB POLYMER BD BD 1.3000E+09 9900000.0
TERM-COMB POLYMER BD STY 1.3000E+09 9900000.0
ABS-MIC 1.0000E-07 0.0
ABS-PART 1.0000E-07 0.0
DES-PART 0.0 0.0
EMUL-PARAMS SLS .0090 5000000.0
SPLIT-PM STY .70
SPLIT-PM BD .50
SPLIT-PM TDM .80

The figures that follow show selected results for emulsion polymerization of
styrene and butadiene in a semi-batch reactor.
The nucleation and growth of emulsion polymer particles in the reactor is
shown here:
2e20 4e20 6e20 8e20 1e21 1.2e21 1.4e21
Volume Unswollen Polymer (PSD 1st moment) m3
0.14
1.4
Number of Particles (PSD 0th moment)
0.12
Average Particle Diameter, micron
1.2
0.1
1
0.04 0.06 0.08

0.4 0.6 0.8
0.02
0.2
0
0 1 2 3 4 5 6 7 8 9 10
Time, hr
As shown, the number of particles formed early remains constant throughout

the reaction. In this figure, first moment, which is the total volume of the
unswollen polymer particles, increases throughout the polymerization as
expected. The figure also shows that the average diameter of the unswollen
particle increases as expected.
The mass of monomers and polymer in the reactor is shown here:
1250
Styrene, Kg
1000
Butadiene, Kg
Polymer, Kg
Mass Inventory, Kg
500 750
250
0 1 2 3 4 5 6 7 8 9 10
Time, hr

Although the flow rates of styrene and butadiene are equal, the figure shows
that butadiene reacts faster than styrene due to its higher reactivity.
The volume of the monomer, polymer, and aqueous phases in the reactor is
shown here:
1.6 1.2
Phase Volume, m3
0.8
Monomer
Aqueous
Polymer
0.4
0 1 2 3 4 5 6 7 8 9 10
Time, hr
As shown, the monomer droplets are completely depleted after 2.5 hours. As
expected, the volume of the swollen polymer phase decreases after the
depletion of the monomer droplets.
The number average and weight average degree of polymerization and the
polydispersity is shown here:
6000
DPN
2000 3000 4000 5000
DPW
3.5
Degree of Polymerization
PDI
2.5 3
1000
2
0
0 1 2 3 4 5 6 7 8 9 10
Time, hr
The composition of the polymer is shown here:

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Mole Fraction, SFRAC
Styrene
Butadiene
0 1 2 3 4 5 6 7 8 9 10
Time, hr
As expected, the composition of the reactive butadiene monomer in the

polymer is higher in comparison to styrene.
The chain length distribution is shown here:
0.0002
Distrib Moments
DPN = 1155.97 968.44
DPW = 3926.32 3242.01
0.0001 0.00015
PDI = 3.3965 3.3476

Weight Fraction
Area = 1.0021
5e-5
1 100 10000 1e6

Degree of polymerization
References
Blackley, D. C. (1983). Synthetic Rubbers: Their Chemistry and Technology.
New York: Applied Science Publishers.
Broadhead, T. O. (1984). Dynamic Modeling of the Emulsion Copolymerization
of Styrene/Butadiene. M. E. Thesis, McMaster Univ.
Ponnuswamy, S. R., & Hamielec, A. E. (1997). Emulsion Polymerization
Theory and Practice. Lecture Notes for Intensive Short Course on Polymer
Reaction Engineering, Burlington, Ontario Canada.

B6 Styrene Butadiene Ionic
Polymerization Processes
The styrene butadiene rubber (SBR) ionic solution process model illustrates
the use of Aspen Polymers to model an anionic polymerization of styrene and
butadiene. The model describes the production of tapered block copolymer
using a batch reactor.
About This Process

Block copolymers of styrene and butadiene are formed by living anionic
polymerization initiated by alkyllithiums. These monomers can be polymerized
over a wide range of useful temperatures from room temperature to elevated
temperatures (100C). Adding alkyllithium initiator to styrene and butadiene
in hydrocarbon solution produces a copolymer containing long polybutadiene
and polystyrene blocks (tapered block copolymers).
Although styrene homo-polymerizes more rapidly than butadiene with
alkyllithiums in hydrocarbon solution, it does not polymerize first in the
mixture. Butadiene is incorporated with a small amount of styrene into the
copolymer first, and only then is the residual styrene free to form blocks by
homopolymerization onto the polybutadienyllithium. Because of the stability
of living nature of the allylic lithium end group, butadiene-styrene
copolymers of widely different structures and properties can be prepared. The
SBR copolymer can either be a random, tapered block, or di/tri-block
copolymer.
The solvent influences the reactivity ratios of styrene and butadiene. The
solvents change the overall rates while the general shape of the batch
polymerization curves remains the same. The reactivity ratios (
k ss k
rs = ; rb = bb ) are a strong function of the solvent. For styrene (s) and
k sb k bs
butadiene (b) monomers in cyclohexane solvent, the reactivity ratio, rb, is
about 50 times larger than rs, and these rate constants determine what type
of copolymer will be formed.
If a mixture of styrene and butadiene is polymerized using alkyllithium
initiator and cyclohexane solvent with the above kinetics in a batch reactor,
154 B6 Styrene Butadiene Ionic Polymerization Processes

tapered block copolymer is produced. One segment would be a butadiene-
styrene copolymer and the other would be a polystyrene block with an overall
B/S-S structure. If the same mixture is polymerized in a semi-batch reactor
with sequential addition and polymerization of styrene, butadiene and styrene
again results in a tri-block copolymer. A continuous reactor would produce a
random copolymer (when rs rb 1.0 ).
The kinetics identified using the model may be used to perform studies using
all three (batch, semi-batch, and continuous) operations.
Process Definition
This application demonstrates production of tapered block SBR polymerization
in a continuous reactor. A schematic of a batch reactor using the ionic kinetics
is shown here:
The following components are present in the simulation flowsheet:

BULI-3 Associated BuLi initiator as a trimer
BULI-1 Dissociated BuLi initiator which initiates the
chain
STYRENE Styrene monomer
STY-SEG Styrene segment
BUTDIENE Butadiene monomer
BUT-SEG Bbutadiene segment
HEXANE Cyclohexane as solvent
SBR Polymer
Usually there is greater control over the polymer properties in batch/semi-

batch reactors compared to a CSTR. In this example, the effect of varying
feed conditions is studied on the conversion profile. This simulation is
performed in a batch reactor using Aspen Polymers. Various feed policies can
be studied in the batch reactor to get the desired SBR properties.
B6 Styrene Butadiene Ionic Polymerization Processes 155

Process Conditions
The batch reactor is simulated for an hour with the following components
mass flows in the feed with one-hour reactor cycle time:
Associated Initiator (Butyl Lithium) 0.13 kg/hr
Styrene Monomer 50 kg/hr
Butadiene Monomer 50 kg/hr
Cyclohexane 1000 kg/hr
Even though there is more reactive styrene present in the feed, butadiene is
first consumed during the polymerization. After butadiene is consumed, the
reaction rate jumps as soon as styrene homopolymerization is initiated. This
behavior is governed by cross propagation reactions as discussed earlier. The
key outputs predicted by the model are:
Total amount of polymer formed 100 kg/hr
Mole fraction of styrene in final polymer 0.341
DPn of final polymer 1281
PDI of polymer out of CSTR 1.06
Fraction of growing polymer that is growing 0.146
Fraction of associated polymer 0.853
DPn of associated polymer 1382
Styrene to butadiene molar ratio is approximately 1:2 in the above mixture.

The batch reactor is simulated for an hour.
Kinetics
A comprehensive kinetic scheme for ionic copolymerization of any number of
monomers has been built into Aspen Polymers. The block, tapered-block, and
random SBR can be modeled using this scheme. The built in kinetics can also
handle the presence of multiple propagating species (for example: free-ions,
ion pairs, and dormant esters).
The polymerization kinetic scheme includes a subset of the reactions available
in the Aspen Polymers ionic kinetic model:
Reaction Type Site ID Reacting Description of Reaction
Species
INIT-DISSOC 1 BULI-3 BULI-1 Initiator dissociation (association

number=3) to form active species
BULI-1 (dissociated butyl-
Lithium)
CHAIN-INI-2 1 BULI-1 STYRENE Chain initiation with styrene
monomer
CHAIN-INI-2 1 BULI-1 Chain initiation with butadiene

Reaction Type Site ID Reacting Description of Reaction
Species
BUTDIENE monomer
PROPAGATION 1 BUT-SEG Propagation of butadiene active
BUTDIENE segment with butadiene
monomer
PROPAGATION 1 BUT-SEG Propagation of butadiene active
STYRENE segment with styrene monomer
PROPAGATION 1 STY-SEG Propagation of styrene active
BUTDIENE segment with butadiene
monomer
PROPAGATION 1 STY-SEG Propagation of styrene active
STYRENE segment with styrene monomer
ASSOCIATION 1 STY-SEG Dimeric association of growing
polymer molecules with styrene
active segment
ASSOCIATION 1 BUT-SEG Dimeric association of growing
polymer molecules with butadiene
active segment
Site ID represents the type of active species (a value of 1 assumes only

ion-pair propagates).
This example illustrates styrene copolymerization with butadiene in

cyclohexane solvent. The ionic kinetic scheme consists of the three basic
polymerization reaction steps: formation of active species, chain initiation,
and propagation. The chain transfer and termination reactions can also be
modeled with the ionic kinetic scheme.
Process Studies
Input Summary
TITLE 'SBR (tapered-block) Solution Polymerization'
IN-UNITS MET FLOW='lb/hr' MASS-FLOW='lb/hr' PRESSURE=psig &

TEMPERATURE=F DELTA-T=F PDROP=psi
OUT-UNITS MET
DESCRIPTION "
This example demonstrates tapered block SBR made
by charging the ingredients in a batch reactor
using the Ionic kinetic reaction scheme.
"

COMPONENTS
BULI-6 C24H38O4-D1 /
BULI-1 C4H5N-1 /
STYRENE C8H8 /
STY-SEG C8H8-R /
BUTDIENE C4H6-4 /
BUT-SEG C4H6-R-1 /
HEXANE C6H10-2 /
SBR SBR
FLOWSHEET
BLOCK BATCH IN=FEED OUT=PROD
PROPERTIES POLYNRTL

GMREND 1 2 1
PROP-DATA MW
IN-UNITS MET
PROP-LIST MW
PVAL BULI-6 384
PVAL BULI-1 64
POLYMERS
PARAM NSITES=1 SITCOM=INITIATOR
SEGMENTS STY-SEG REPEAT / BUT-SEG REPEAT
INITIATOR BULI-1
POLYMERS SBR
ATTRIBUTES SBR SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM &
FMOM SMOM LEFLOW LSFLOW LSFRAC LDPN LSMOM LPFRAC &
SSFRAC SSFLOW SDPN SDPW SPDI SMWN SMWW SZMOM SSMOM &
SPFRAC LSSFLOW LSSFRAC LSEFLOW LSEFRAC LSDPN LSSMOM &
LSPFRAC ASEFLOW ASSFLOW ASSMOM ASDPN ADPN ASPDI APDI &
ASFLOW ASPFRAC APFRAC DSEFLOW DSSFLOW DSSMOM
ATTRIBUTES BULI-1 P0FLOW PT0FLOW CIONFLOW
PROP-SET BU-LIC MOLECONC UNITS='mol/l' SUBSTREAM=MIXED &

COMPS=BULI-6 PHASE=L
PROP-SET BUTC MOLECONC UNITS='mol/l' SUBSTREAM=MIXED &

COMPS=BUTDIENE PHASE=L
PROP-SET STYC MOLECONC UNITS='mol/l' SUBSTREAM=MIXED &

COMPS=STYRENE PHASE=L
STREAM FEED
IN-UNITS MET
SUBSTREAM MIXED TEMP=50. <C> PRES=1.
MASS-FLOW BULI-6 0.13 / BULI-1 0. / STYRENE 50. / &
BUTDIENE 50. / HEXANE 1000. / SBR 0.
BLOCK BATCH RBATCH

PARAM TYPE=T-SPEC PRINT-TIME=10. <min> CYCLE-TIME=1. <hr> &
MAX-TIME=7. <hr> MAX-NPOINT=44 PRES=10. <atm> &
TEMP=50. <C> NPHASE=1 PHASE=L FLASH=YES
STOP 1 REACTOR TIME 7.
BLOCK-OPTION SIM-LEVEL=4 TERM-LEVEL=10 FREE-WATER=NO
REACTIONS RXN-IDS=R-ION
EO-CONV-OPTI
STREAM-REPOR MOLEFLOW MASSFLOW MOLEFRAC PROPERTIES=BU-LIC BUTC &

STYC
REACTIONS R-ION IONIC

IN-UNITS MET
SPECIES INIT=BULI-1 ASSO-INI=BULI-6 POLYMER=SBR
MON-RSEG STYRENE STY-SEG / BUTDIENE BUT-SEG
INIT-DISSOC BULI-6 BULI-1 0.001 0. 2E+026 0. ASSO-NO=6 REF-TEMP=50. <C>
CHAIN-INI-2 1 BULI-1 STYRENE 0.45 0. REF-TEMP=50. <C>
CHAIN-INI-2 1 BULI-1 BUTDIENE 0.8 0. REF-TEMP=50. <C>
PROPAGATION 1 STY-SEG STYRENE 5. 0. REF-TEMP=50. <C>
PROPAGATION 1 STY-SEG BUTDIENE 200. 0. REF-TEMP=50. <C>
PROPAGATION 1 BUT-SEG STYRENE 0.16556 0. REF-TEMP=50. <C>
PROPAGATION 1 BUT-SEG BUTDIENE 2.5 0. REF-TEMP=50. <C>
ASSOCIATION 1 STY-SEG 1000. 0. 0.01 0. REF-TEMP=50. <C>
ASSOCIATION 1 BUT-SEG 1000. 0. 0.01 0. REF-TEMP=50. <C>

The rate of consumption of monomers and formation of SBR polymer is shown
here:
Block BATCH (RBATCH) Profiles Composition
50
100
45
40
80
Accumulated mass MIXED STYRENE

35
Accumulated mass MIXED BUTDIENE

Accumulated mass MIXED SBR
30
60
MASS kg
MASS kg
25
20
40
15
10
20
5
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7

Time hr

The figure shows the mass of monomers and polymer in the batch reactor.
The consumption of styrene increases only after most of the butadiene
monomer is incorporated into the polymer. The kick in polymerization takes
place after most of the butadiene is depleted and styrene homopolymerization
begins.
The copolymer composition during polymerization is shown here:
Block BATCH (RBATCH) Profiles Component Attr.
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
Component attribute MIXED #0 SBR SFRAC STY-SEG

Component attribute MIXED #1 SBR SFRAC BUT-SEG
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7

Time MIXED hr
The figure shows the cumulative segment fraction of monomer in the polymer
as a function of time. As shown, during the first phase of the polymerization,
only about 10% of styrene is incorporate in the polymer. The final molar
composition of styrene in the polymer is 34%.
The degree of polymerization for live (LDPN), composite (DPN), and
associated (ADPN) is shown here:

Block BATCH (RBATCH) Profiles Component Attr.
900 1000 1100 1200 1300 1400

Component attribute MIXED #50 SBR ADPN ADPN
Component attribute MIXED #4 SBR DPN DPN
Component attribute MIXED #18 SBR LDPN LDPN
800
700
600
500
400
300
200
100
1 6 11 16 21 26 31 36 41 46
NPOINT
The degree of polymerization of associated polymer (ADPN) is twice the DPN

of live polymer (LDPN) for a dimeric polymer association reaction.
The SBR produced by ionic polymerization has control over the amount of cis,
trans, and vinyl configuration in the polymer. This configuration is usually a
function of temperature. The amount of cis, trans, and vinyl polymer formed
is also possible to track in Aspen Polymers using user kinetics subroutines.
Other user subroutines (for example, viscosity correlating to fraction of
aggregate polymer and weight averages) may also be used to calculate and
track product specific non-molecular properties.

B7 High-Density
Polyethylene High
Temperature Solution
Process
The HDPE high temperature solution process model illustrates the use of
Aspen Polymers to model a Ziegler-Natta solution polymerization of ethylene.
The model is used to study the effect of feed flow rate on conversion and
polymer properties, and to study the effect of hydrogen concentration on melt
index and polydispersity index.
About This Process

Polyethylene is the largest synthetic commodity polymer. It is widely used
throughout the world due to its versatile physical and chemical properties.
The current worldwide capacity for polyethylene is over 30 million tons and
the average annual rate of capacity increase is 5-8%. The commercial
production of polyethylene is done in continuous processes, gas-phase
processes, slurry processes, or solution processes using highly active Ziegler-
Natta catalysts such as titanium supported catalysts.
Aspen Polymers has been used to model the high temperature solution
process for polyethylene using a Ziegler-Natta catalyst. Ziegler-Natta
catalysts are multi-site catalysts containing different site types, with each
type having different reactivities. For this reason, each site type produces a
polymer with distinct molecular weight. As a result, the composite polymer
has a broad molecular weight distribution.
The Ziegler-Natta model in Aspen Polymers takes into account the important
reactions found in this chemistry, including site activation, chain initiation,
chain propagation, chain transfer, site deactivation, site inhibition, branching
reactions, etc. The model is quite flexible and can be configured for
homopolymerization or copolymerization with any number of monomers.
Users can also specify any number of site types for the catalyst. The model
predicts the various polymer properties, such as molecular weight,
162 B7 High-Density Polyethylene High Temperature Solution Process

polydispersity index, melt index, and copolymer composition, and returns this
information for the polymer produced at each catalyst site.
Process Definition
In this example, the solution polymerization of ethylene is carried out at
160C using n-hexane as solvent. Hydrogen is used as a chain transfer agent
to control molecular weight. The flowsheet consists of two reactors and a
flash unit as shown:
The first reactor produces a high molecular weight polymer while the second
produces a low molecular weight polymer. Solvent, unreacted monomer, and
hydrogen are removed from the product in a flash tank.
An intermediate feed stream going to the second reactor is used to set the
concentration of hydrogen in that reactor to be several times higher than in
the first reactor. A total of four site types are used for the catalyst. Two sites
are considered to be active in the first reactor and all four sites are active in
the second reactor.
Process Conditions
Ethylene C2H4 PURE12 Monomer

Hydrogen H2 PURE12 Chain transfer agent
n-Hexane HEXANE PURE12 Solvent
Catalyst TICl4 PURE12 Catalyst
Cocatalyst TEA PURE12 Cocatalyst
HDPE HDPE POLYMER Polymer
C2H4-R SEGMENT Ethylene segment
Physical POLYPCSF property method with supplied parameters for catalyst
Properties and cocatalyst (PCSFTM=20)
Feeds Feed R1FEED FEED2
Composition Ethylene (E2) 10.0 20.0

(% by Hydrogen (H2) 5.0E-4 0.02
weight)
Hexane 89.975 79.95
B7 High-Density Polyethylene High Temperature Solution Process 163

Catalyst (TICl4)* 0.01 0.01
Cocatalyst (TEA) 0.015 0.015
Condition Temperature 70C 70C
Pressure 200 atm 200 atm
Phase Liquid Liquid
Mass Flow 60,000 kg/hr 10,000 kg/hr
Kinetics ZIEGLER-NAT model
Operating Block Temp (C) Pres Size

Conditions (atm)
CSTR-1 160 200 60 m3

CSTR-2 160 200 60 m3
FLASH 160 10 ---
* Mole fraction of potential site fraction is one.
Reactors / Kinetics
The set of reactions included from the built-in kinetics for this model are:
Site activation by cocatalyst C ps + Am P0

k
Spontaneous site activation C ps P 0k

Chain initiation P 0 + M i P i i
k
Propagation P n,j + M i P n + i i
k
Chain transfer to hydrogen P n,j + H 2 D n + P 0

k k k
Chain transfer to monomer P n,j + M i D n- + P i ,i

k k k
Spontaneous chain transfer P n,j

k
D nk- + P 0k
Spontaneous site P0
k
C ds
deactivation
Pn,j
k
C ds + Dkn
Process Studies
In order to determine the effect of feed flowrate on conversion and polymer
properties, and the effect of hydrogen concentration on melt index and
polydispersity index, a sensitivity study is carried out. Melt index is calculated
in a user supplied subroutine (Xie et al., 1994) and is chosen as one of the
sampled parameters in a SENSITIVITY block. Other sampled parameters
include the polymer properties, the component fractions used to determine
conversion, and the flowrates.

Input Summary
;This application example requires a user FORTRAN subroutine USRPRP.F
;Please copy USRPRP.F from the Application example directory and
;compile it in your local working directory. The subroutine provides
;the correlations for melt viscosity, IV and zero shear viscosity. If
;you change the component names, property name or the subroutine name
;you must update the names in the subroutine.
;
;If you don't have a compiler you can copy USERFORT.DLL and
;USERFORT.DLOPT from the Application folder to your working directory,
;enter USERFORT.DLOPT in the Run/Settings/Engine Files/Linker Options
;box and run the simulation.
DYNAPLUS
DPLUS RESULTS=ON
TITLE 'Ziegler-Natta Solution Polymerization of Ethylene'

DIAGNOSTICS
TERMINAL SIM-LEVEL=4 CONV-LEVEL=4 COST-LEVEL=4 PROP-LEVEL=4 &
ECON-LEVEL=4 STREAM-LEVEL=4 SYS-LEVEL=4
DESCRIPTION "Solution polymerization of ethylene. This file requires

user FORTRAN USRPRP to calculate polymer properties."
COMPONENTS
TICL4 TICL4 /
TEA C6H15AL /
C2H4 C2H4 /
H2 H2 /
HEXANE C6H14-1 /
HDPE HDPE /
C2H4-R C2H4-R
FLOWSHEET
BLOCK CSTR-1 IN=R1FEED OUT=R1PROD
BLOCK CSTR-2 IN=R1PROD FEED2 OUT=R2PROD
BLOCK FLASH IN=R2PROD OUT=RECYCLE POLYMER
;
; THE PROPERTY CALCULATION METHOD (OPTION SET) SPECIFICATION FOLLOWS
;

PROPERTIES POLYPCSF
PROP-DATA PCSAFT
PROP-LIST PCSFTM
PVAL TICL4 20
PVAL TEA 20
POLYMERS
PARAM NSITES=4
CATALYST TICL4 .00010
POLYMERS HDPE
ATTRIBUTES HDPE SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM &
LEFRAC LPFRAC SSFRAC SSFLOW SDPN SDPW SPDI SMWN SMWW &
SZMOM SFMOM SSMOM SPFRAC LSDPN LSZMOM LSFMOM LSSFLOW &
LSSFRAC LSEFLOW LSEFRAC LSPFRAC
ATTRIBUTES TICL4 CPSFLOW CPSFRAC CVSFLOW CVSFRAC CDSFLOW &
CDSFRAC
DISTRIBUTION HDPE CHAIN-SIZE CLD NPOINTS=100 FUNCLOG=YES &
UPPER=100000.
USER-PROPERT DENS SUBROUTINE=USRPRP UNIT-TYPE=DENSITY
USER-PROPERT IV SUBROUTINE=USRPRP
USER-PROPERT MI-K SUBROUTINE=USRPRP
USER-PROPERT MI-S SUBROUTINE=USRPRP
USER-PROPERT ZVIS SUBROUTINE=USRPRP UNIT-TYPE=VISCOSITY
PROP-SET DENS DENS SUBSTREAM=MIXED
PROP-SET IV IV SUBSTREAM=MIXED
PROP-SET MI-KAR MI-K SUBSTREAM=MIXED
PROP-SET MI-SIN MI-S SUBSTREAM=MIXED
PROP-SET ZVIS ZVIS SUBSTREAM=MIXED
STREAM FEED2
SUBSTREAM MIXED TEMP=70.0 PRES=200.0 MASS-FLOW=10000.0 &
NPHASE=1 PHASE=L
MASS-FRAC TICL4 .00010 / TEA .000150 / C2H4 .20 / H2 &
.00020 / HEXANE 0.79955
COMP-ATTR TICL4 CPSFLOW ( 0.0 )
COMP-ATTR TICL4 CPSFRAC ( 1.0 )
COMP-ATTR TICL4 CVSFLOW ( 0.0 0. 0. 0. )
COMP-ATTR TICL4 CVSFRAC ( 0.0 0.0 0.0 0.0 )
COMP-ATTR TICL4 CDSFLOW ( 0.0 )
COMP-ATTR TICL4 CDSFRAC ( 0.0 )
STREAM R1FEED

NPHASE=1 PHASE=L
MASS-FRAC TICL4 .00010 / TEA .000150 / C2H4 .10 / H2 &
5.0000E-06 / HEXANE 0.899745
COMP-ATTR TICL4 CVSFLOW ( 0.0 0. 0. 0. )
BLOCK FLASH FLASH2

BLOCK CSTR-1 RCSTR

MB-MAXIT=50 MB-TOL=.00010
MASS-FLOW MIXED C2H4 2500.
MASS-FLOW MIXED HDPE 3500.
COMP-ATTR MIXED TICL4 CPSFLOW ( .000010 )
COMP-ATTR MIXED TICL4 CDSFLOW ( 3.9581E-06 )
BLOCK-OPTION TERM-LEVEL=7 RESTART=NO
REACTIONS RXN-IDS=ZN-R1
BLOCK CSTR-2 RCSTR

MB-MAXIT=50 MB-TOL=.00010
MASS-FLOW MIXED C2H4 2100.
MASS-FLOW MIXED HDPE 5800.
COMP-ATTR MIXED TICL4 CPSFLOW ( .000010 )
COMP-ATTR MIXED TICL4 CDSFLOW ( 3.9581E-06 )
BLOCK-OPTION TERM-LEVEL=7 RESTART=NO
EO-CONV-OPTI
SENSITIVITY RTIME
PARAM BASE-CASE=LAST
DEFINE RHDPE2 MASS-FLOW STREAM=R2PROD SUBSTREAM=MIXED &
COMPONENT=HDPE
DEFINE RMW2 COMP-ATTR-VAR STREAM=R2PROD SUBSTREAM=MIXED &
COMPONENT=HDPE ATTRIBUTE=MWW ELEMENT=1
DEFINE RMN2 COMP-ATTR-VAR STREAM=R2PROD SUBSTREAM=MIXED &
COMPONENT=HDPE ATTRIBUTE=MWN ELEMENT=1
DEFINE RPDI2 COMP-ATTR-VAR STREAM=R2PROD SUBSTREAM=MIXED &
COMPONENT=HDPE ATTRIBUTE=PDI ELEMENT=1
DEFINE RE22 MASS-FLOW STREAM=R2PROD SUBSTREAM=MIXED &
COMPONENT=C2H4
COMPONENT=HDPE

COMPONENT=C2H4
DEFINE RMI2 STREAM-PROP STREAM=R2PROD PROPERTY=MI-KAR
DEFINE R2H2 MASS-FRAC STREAM=R2PROD SUBSTREAM=MIXED &
COMPONENT=H2
COMPONENT=H2
F CONV2 = RHDPE2/(RHDPE2+RE22) * 100
TABULATE 1 "CONV1" COL-LABEL="CONV1"
TABULATE 3 "RMW1" COL-LABEL="MW1"
TABULATE 5 "RMN1" COL-LABEL="MN1"
TABULATE 7 "RPDI1" COL-LABEL="PDI1"
TABULATE 9 "R1H2*1.0E6" COL-LABEL="R1H2" "PPM"
TABULATE 11 "RMI1" COL-LABEL="MI1"
VARY STREAM-VAR STREAM=R1FEED SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
RANGE LOWER="2E4" UPPER="1.5E6" NPOINT="20"
SENSITIVITY RTIME2
COMPONENT=HDPE
COMPONENT=C2H4
COMPONENT=HDPE
COMPONENT=C2H4
COMPONENT=H2
COMPONENT=H2

VARY MASS-FLOW STREAM=FEED2 SUBSTREAM=MIXED COMPONENT=H2
RANGE LOWER="0.0" UPPER="20" INCR="2.0"
CONV-OPTIONS
PARAM CHECKSEQ=NO
SEQUENCE S-1 CSTR-1 CSTR-2 RTIME CSTR-1 CSTR-2 (RETURN RTIME) &
RTIME2 CSTR-2 FLASH (RETURN RTIME2)
STREAM-REPOR NARROW MOLEFLOW MASSFLOW MASSFRAC PROPERTIES=DENS &

IV MI-KAR MI-SIN ZVIS
REACTIONS ZN-R1 ZIEGLER-NAT

DESCRIPTION "Ziegler-Natta Kinetic Scheme"
PARAM
SPECIES CATALYST=TICL4 COCATALYST=TEA MONOMER=C2H4 &
SOLVENT=HEXANE HYDROGEN=H2 POLYMER=HDPE
MON-RSEG C2H4 C2H4-R
ACT-SPON 1 TICL4 .080 0.0 ORDER=1.0
ACT-SPON 3 TICL4 0.0 0.0 ORDER=1.0
ACT-SPON 4 TICL4 0.0 0.0 ORDER=1.0
ACT-COCAT 1 TICL4 TEA .150 0.0 ORDER=1.0
ACT-COCAT 3 TICL4 TEA 0.0 0.0 ORDER=1.0
ACT-COCAT 4 TICL4 TEA 0.0 0.0 ORDER=1.0
CHAIN-INI 1 C2H4 255.0 0.0 ORDER=1.0
PROPAGATION 1 C2H4 C2H4 255.0 0.0 ORDER=1.0
CHAT-MON 1 C2H4 C2H4 .090 0.0 ORDER=1.0
CHAT-MON 3 C2H4 C2H4 0.0 0.0 ORDER=1.0
CHAT-MON 4 C2H4 C2H4 0.0 0.0 ORDER=1.0
CHAT-H2 1 C2H4 H2 5.550 0.0 ORDER=1.0
CHAT-H2 2 C2H4 H2 18.50 0.0 ORDER=1.0
CHAT-H2 3 C2H4 H2 0.0 0.0 ORDER=1.0
CHAT-H2 4 C2H4 H2 0.0 0.0 ORDER=1.0
CHAT-SPON 1 C2H4 .0040 0.0 ORDER=1.0
CHAT-SPON 3 C2H4 0.0 0.0 ORDER=1.0

CHAT-SPON 4 C2H4 0.0 0.0 ORDER=1.0
DEACT-SPON 1 .00010 0.0 ORDER=1.0
DEACT-SPON 3 0.0 0.0 ORDER=1.0
DEACT-SPON 4 0.0 0.0 ORDER=1.0

PARAM
SOLVENT=HEXANE HYDROGEN=H2 POLYMER=HDPE
CHAT-H2 1 C2H4 H2 5.550 0.0 ORDER=1.0
CHAT-H2 2 C2H4 H2 18.50 0.0 ORDER=1.0
CHAT-H2 3 C2H4 H2 5.550 0.0 ORDER=1.0
CHAT-H2 4 C2H4 H2 18.50 0.0 ORDER=1.0
;

The results for the sensitivity study to determine the effect of feed flowrate to
CSTR-1 on ethylene conversion, Mn, Mw, PDI, and melt index are shown in the
figures that follow.
The effect of feed flow rate on ethylene conversion is shown here:

90
80
70
CSTR1
Ethylene Conversion
60 CSTR2
50
40
30
20
10
0
0 500000 1000000 1500000
Feed Flow Rate to CSTR-1, kg/hr
Properties of the product exiting from CSTR-2 are influenced by the flowrates
of both feeds. Increasing the feed to CSTR-1 decreases the residence time in
CSTR-1 and CSTR-2, as shown, this leads to a decrease in conversion in both
reactors.
Although conversion decreases with increases in CSTR-1 feed, the next two
figures show an increase in the CSTR-2 polymer Mn and Mw. This is due to the
concentration of hydrogen in CSTR-2. As CSTR-1 feed flow increases,
hydrogen concentration in CSTR-2 decreases. As a result, chain transfer rate
decreases, allowing longer polymer chain length.
The effect of feed flow rate on Mn is shown here:

40000
35000 CSTR1
CSTR2
Mn
30000
25000
20000
0 500000 1000000 1500000
The effect of feed flow rate on Mw is shown here:
120000
115000
110000
105000
Mw
100000
95000 CSTR1
CSTR2
90000
85000
80000
0 500000 1000000 1500000
The effect of feed flow rate on the hydrogen concentration (PPM) is shown
here:

70
65
60
55
CSTR1
H2 Concentration (ppm)
50
45 CSTR2
40
35
30
25
20
15
10
5
0
0 500000 1000000 1500000
The effect of feed flow rate on the polydispersity index is shown here:
4.2
CSTR1
3.8 CSTR2
3.6
3.4
3.2
3
0 500000 1000000 1500000
The effect of feed flow rate on the melt index is shown here:

2.75
2.5
2.25
CSTR1
2
CSTR2
Melt Index 1.75
1.5
1.25
0.75
0.5
0.25
0 500000 1000000 1500000
The results for the sensitivity studies to determine the effects of hydrogen
flowrate on polymer properties are shown in the three figures that follow. In
this case, hydrogen flowrate in the intermediate feed to CSTR-2 is varied. As
hydrogen flowrate increases, average molecular weight of HDPE in CSTR-2
decreases as shown in the first figure.
The effect of hydrogen concentration on Mn and Mw is shown here:
140000
120000
100000
Molecular Weight
80000
60000
Mn
40000 Mw
20000
0
0 50 100 150 200 250 300
Hydrogen Conc. in CSTR-2, ppm
The effect of hydrogen concentration on melt index and PDI is shown here:

10
9
8
7
6
5
4
3
PDI
2 Melt Index
1
0
0 50 100 150 200 250 300
Hydrogen Conc. in CSTR-2, ppm
The molecular weight distribution for polymer produced at the different sites
is shown here:
0.5
0.4 Composite
Site_1
Weight Fraction
0.3 Site_2
Site_3
0.2 Site_4
0.1
0.0
1 10 100 1000 10000 100000
Polymer Chain Length
As shown, although the polymer at each site follows the Flory distribution, the
composite polymer MWD is quite broad. In conclusion, the studies show the
importance of choosing the right operating conditions in order to optimize
reactor performance and product properties.

A stream summary for the base case simulation is shown here:
FEED2 POLYMER R1FEED R1PROD R2PROD

----------------------------------
STREAM ID FEED2 POLYMER R1FEED R1PROD R2PROD

FROM : ---- FLASH ---- CSTR-1 CSTR-2
TO : CSTR-2 ---- CSTR-1 CSTR-2 FLASH
SUBSTREAM: MIXED
COMPONENTS: KG/HR
TICL4 1.0000 7.0000 6.0000 6.0000 7.0000

TEA 1.5000 10.4999 9.0000 8.9999 10.4999
C2H4 2000.0000 7.0265 6000.0000 2448.3134 2153.7923
H2 2.0000 9.6960-04 0.3000 0.2793 2.1816
HEXANE 7995.5000 2055.1866 5.3985+04 5.3985+04 6.1980+04
HDPE 0.0 5846.3263 0.0 3551.7074 5846.3263
TICL4 1.0000-04 8.8316-04 1.0000-04 1.0000-04 1.0000-04
TEA 1.5000-04 1.3247-03 1.5000-04 1.5000-04 1.5000-04
C2H4 0.2000 8.8651-04 0.1000 4.0805-02 3.0768-02
H2 2.0000-04 1.2233-07 5.0000-06 4.6543-06 3.1165-05
HEXANE 0.7996 0.2593 0.8997 0.8997 0.8854
HDPE 0.0 0.7376 0.0 5.9195-02 8.3519-02
TOTAL FLOW:
KMOL/HR 165.0820 232.6255 840.5730 840.5634 1005.6005
KG/HR 1.0000+04 7926.0403 6.0000+04 6.0000+04 7.0000+04
CUM/SEC 4.8344-03 3.1006-03 2.7440-02 2.9458-02 3.3779-02
STATE VARIABLES:
TEMP C 70.0000 160.0000 70.0000 160.0000 160.0000
PRES ATM 200.0000 10.0000 200.0000 200.0000 200.0000
VFRAC 0.0 0.0 0.0 0.0 0.0
LFRAC 1.0000 1.0000 1.0000 1.0000 1.0000
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL -8.5807+07 -6.2134+07 -1.2849+08 -1.2707+08 -1.2625+08
J/KG -1.4165+06 -1.8236+06 -1.8001+06 -1.7801+06 -1.8137+06
WATT -3.9348+06 -4.0150+06 -3.0002+07 -2.9669+07 -3.5266+07
ENTROPY:
J/KMOL-K -3.9499+05 -2.3531+05 -4.9143+05 -4.6289+05 -4.5417+05
J/KG-K -6520.6535 -6906.2266 -6884.7737 -6484.7471 -6524.4803
DENSITY:
KMOL/CUM 9.4853 20.8405 8.5092 7.9263 8.2696
KG/CUM 574.5816 710.0783 607.3833 565.7847 575.6452
AVG MW 60.5759 34.0721 71.3799 71.3807 69.6102
TICL4 CPSFLOW
CPSFLOW 1.0000-04 1.7859-07 6.0000-04 1.8329-06 1.7859-07
CPSFRAC
CPSFRAC 1.0000 2.5512-04 1.0000 3.0549-03 2.5512-04
CVSFLOW
SITE_1 0.0 7.7194-08 0.0 1.4019-08 7.7194-08
SITE_2 0.0 2.4029-07 0.0 6.7671-08 2.4029-07
SITE_3 0.0 7.2433-09 0.0 0.0 7.2433-09
SITE_4 0.0 3.8375-08 0.0 0.0 3.8375-08
CVSFRAC
SITE_1 0.0 1.1028-04 0.0 2.3365-05 1.1028-04
SITE_2 0.0 3.4327-04 0.0 1.1279-04 3.4327-04
SITE_3 0.0 1.0348-05 0.0 0.0 1.0348-05
SITE_4 0.0 5.4822-05 0.0 0.0 5.4822-05
CDSFLOW
CDSFLOW 0.0 3.5591-04 0.0 2.1510-04 3.5591-04
CDSFRAC
CDSFRAC 0.0 0.5084 0.0 0.3585 0.5084
HDPE SFRAC
C2H4-R MISSING 1.0000 MISSING 1.0000 1.0000
SFLOW
DPN

DPN MISSING 993.2823 MISSING 1174.3925 993.2823
DPW
DPW MISSING 3590.2126 MISSING 4202.4206 3590.2126
PDI
PDI MISSING 3.6145 MISSING 3.5784 3.6145
MWN
MWN MISSING 2.7865+04 MISSING 3.2946+04 2.7865+04
MWW
MWW MISSING 1.0072+05 MISSING 1.1789+05 1.0072+05
ZMOM
ZMOM MISSING 0.2098 MISSING 0.1078 0.2098
FMOM
FMOM MISSING 208.3930 MISSING 126.6029 208.3930
SMOM
SMOM MISSING 7.4818+05 MISSING 5.3204+05 7.4818+05
LDPN
LDPN MISSING 1128.9483 MISSING 1696.5667 1128.9483
LZMOM
LZMOM MISSING 3.4355-04 MISSING 3.8299-04 3.4355-04
LFMOM
LFMOM MISSING 0.3879 MISSING 0.6498 0.3879
LSFLOW
LSFRAC
LEFLOW
C2H4-R MISSING 3.4355-04 MISSING 3.8299-04 3.4355-04
LEFRAC
LPFRAC
LPFRAC MISSING 1.6375-03 MISSING 3.5527-03 1.6375-03
SSFRAC
C2H4-R_1 MISSING 1.0000 MISSING 1.0000 1.0000
C2H4-R_3 MISSING 1.0000 MISSING MISSING 1.0000
C2H4-R_4 MISSING 1.0000 MISSING MISSING 1.0000
SSFLOW
SDPN
SITE_1 MISSING 1940.9634 MISSING 2443.8053 1940.9634
SDPW
SPDI
SMWN

SITE_1 MISSING 5.4451+04 MISSING 6.8558+04 5.4451+04
SITE_3 MISSING 4.0763+04 MISSING 0.0 4.0763+04
SMWW
SZMOM
SITE_1 MISSING 8.9016-02 MISSING 4.3475-02 8.9016-02
SITE_2 MISSING 0.1094 MISSING 6.4328-02 0.1094
SITE_3 MISSING 4.2487-03 MISSING 0.0 4.2487-03
SFMOM
SSMOM
SPFRAC
LSDPN
LSZMOM
LSFMOM
LSSFLOW
C2H4-R_2 MISSING 1.3473-02 MISSING 4.2576-02 1.3473-02
C2H4-R_3 MISSING 3.1346-02 MISSING 0.0 3.1346-02
LSSFRAC
LSEFLOW

LSEFRAC
LSPFRAC
MIXED SUBSTREAM PROPERTIES:
*** ALL PHASES ***

DENS KG/CUM 0.0 925.7174 0.0 925.7174 925.7174
IV UNITLESS 0.0 1.0014 0.0 1.0335 1.0014
MI-K UNITLESS 0.0 0.8950 0.0 0.4745 0.8950
MI-S UNITLESS 0.0 1.4246 0.0 0.8246 1.4246
ZVIS N-SEC/SQM 0.0 83.1969 0.0 83.7338 83.1969
RECYCLE
-------
STREAM ID RECYCLE
FROM : FLASH
TO : ----
SUBSTREAM: MIXED
PHASE: VAPOR
COMPONENTS: KG/HR
TICL4 3.0502-09
TEA 4.5753-09
C2H4 2146.7657
H2 2.1806
HEXANE 5.9925+04
HDPE 0.0
TICL4 4.9139-14
TEA 7.3707-14
C2H4 3.4584-02
H2 3.5129-05
HEXANE 0.9654
HDPE 0.0
TOTAL FLOW:
KMOL/HR 772.9750
KG/HR 6.2074+04
CUM/SEC 0.6172
STATE VARIABLES:
TEMP C 160.0000
PRES ATM 10.0000
VFRAC 1.0000
LFRAC 0.0
SFRAC 0.0
ENTHALPY:

J/KMOL -1.2586+08
J/KG -1.5673+06
WATT -2.7025+07
ENTROPY:
J/KMOL-K -4.7043+05
J/KG-K -5858.0069
DENSITY:
KMOL/CUM 0.3479
KG/CUM 27.9349
AVG MW 80.3053
References
MacAuley, K. B., MacGregor, J. F., & Hamielec, A. E. (1990). AIChE J., 36, p.
837.
Xie, T., McAuley, K. B., Hsu, J. C. C., & Bacon, D. W. (1994). Gas phase
ethylene polymerization: Production processes, polymer properties and
reactor modeling. Ind. Eng. Chem. Res., 33, pp. 449-479.

B8 Low-Density
Polyethylene High Pressure
Process
The LDPE high-pressure process model illustrates the use of Aspen Polymers
to model a high pressure free-radical process for low-density polyethylene.
The model considers the tubular jacketed reactor along with the post-
polymerization devolatization. Among the parameters studied in the model
are reactor temperature profile, monomer conversion, polymer molecular
weight and degree of branching.
About This Process

Low density polyethylene (LDPE), is part of the polyolefin family of polymers.
This polymer exhibits a number of desirable properties, including strength,
flexibility, impact resistance, resistance to solvents, to chemicals, and to
oxidating agents. For this reason, it is one of the highest volume polymers in
terms of production.
LDPE is produced by free-radical polymerization. It has been produced in
batch processes. However, continuous processes are more commonly found,
because they allow better control of the polymerization. Polymerization is
carried out in tubular and autoclave reactors under high pressure (1300-3400
atm), and high temperatures (150-340C). At such high compression states,
the gaseous ethylene monomer behaves like a liquid. The reactor of choice for
the production of LDPE is a tubular reactor. Some processes involve multizone
tubular reactors with multiple initiator injection points along the length of the
reactor.
Process Definition
In this example, polymerization of ethylene is carried out in a jacketed
tubular reactor divided into four sections, with two initiator injection points.
High and low pressure separators are also used. The flowsheet for the process
is shown here:
B8 Low-Density Polyethylene High Pressure Process 181

182 B8 Low-Density Polyethylene High Pressure Process
Process Conditions
Initiator INI1 PURE12 Initiator

2nd initiator INI2 PURE12 Initiator
Ethylene E2 PURE12 Monomer
Polyethylene LDPE POLYMER Polymer
E2-SEG SEGMENT Ethylene segment
Water WATER PURE12 Coolant
Physical Properties POLYSL property method with supplied parameters
Feeds E2FD1B E2FD2B INIFD1 INIFD2 Coolant Streams
Temperature (C) 140 50 0 0 160

Pressure (bar) 2010 2000 2010 2010 100
Component flows:
(kg/hr) 40000 25000 --- --- ---
E2 --- --- 6 12 ---
INI1 --- --- 1.5 3 ---
INI2 --- --- --- --- 160000
WATER
Kinetics FREE-RAD model (see Reactors / Kinetics on page 184 for rate
constant parameters)
Operating Conditions Block Temp (C) Pres Pres Size
(atm) Drop
(bar)
PFR1 170 --- 100 250 m length by 0.059

(coolant) m diam*
PFR2 170 --- 100 220 m length by 0.059
(coolant) m diam*
PFR3 170 --- 100 250 m length by 0.059
(coolant) m diam*
PFR4 170 --- 100 220 m length by 0.059
(coolant) m diam*
FDMIX1 --- 2000 --- ---
FDMIX2 --- 1900 --- ---
HPS Duty=0 250 --- ---
LPS Duty=0 1 --- ---
* A user heat transfer subroutine (Carr et al., 1955; Eirmann, 1965) is

provided to these plug flow reactors.

The POLYSL equation-of-state property method is used for the physical
property calculations and phase equilibria. The unary input parameters for
POLYSL are SLTSTR, SLPSTR, and SLRSTR, and correspond to the Sanchez-
Lacombe equation of state T*, P*, and * parameters, respectively. The
parameters were obtained by Sanchez-Lacombe by fitting experimental data
(Sanchez & Lacombe, 1976). An input summary containing these parameter
values is given in the Process Studies section on page 185.
To improve predictions for phase equilibria in the high- and low-pressure
separators, two binary interaction parameters between polyethylene and
ethylene were introduced, namely SLKIJ and SLETIJ. These parameters were
obtained by fitting VLE experimental data of polyethylene-ethylene binary
systems at various temperatures. An input summary containing these
parameter values is given in the Process Studies section on page 185.
Ideal gas heat capacity coefficients (CPIG) are entered for ethylene segment
and pure ethylene. The coefficients are obtained from fitting heat capacity
data. CPIG is used for the calculation of ideal-gas enthalpy and entropy,
which are added to the departure values calculated by the Sanchez-Lacombe
equation of state. An input summary containing these parameter values is
given in the Process Studies section on page 185.
Reactors / Kinetics
The built-in free-radical reactions used in this example are:
Description k0 Ea V
(m3/kmol) (J/kmol) (m3/kmol)
Initiator 1 decomposition 2.5E14 126E6 0

Initiator 2 decomposition 5.93E18 195E6 0
Chain initiation 2.5E8 35.3E6 0

Propagation 2.5E8 35.3E6 -21.3E-3
Chain transfer to monomer 1.25E6 45.4E6 0
Chain transfer to polymer 1.24E6 30.4E6 1.6E-3
Termination by combination 2.5E9 4.19E6 1E-3
Termination by disproportionation 2.5E9 4.19E6 1E-3
Beta scission 6.07E7 45.3E6 0
Short chain branching 1.3E9 41.6E6 0
k0 is frequency factor, Ea is activation energy, and V is activation volume

k0 is two times higher than in Mavridis and Kiparissides (1985).

Process Studies
The model is used to examine the reactor temperature profile, monomer
conversion, number and weight average molecular weights, and frequency of
short and long chain branches.
Input Summary
DYNAPLUS
DPLUS RESULTS=ON
TITLE &
'High-Pressure LDPE tubular reactor flowsheet with four
sections'
IN-UNITS SI MASS-FLOW='kg/hr' MOLE-FLOW='kmol/hr' PRESSURE=bar &

DESCRIPTION "
This flowsheet models a high-pressure LDPE tubular
reactor flowsheet with four sections, two initiator
and monomer injection points, and high and low
pressure separators.
This application requires a FORTRAN subroutine

to calculate the heat transfer coefficient
along the reactor length. Please copy USRHPE.F
located in the application directory to your
working directory and compile it by typing.
ASPCOMP USRHPE
This subroutine locates the monomer and polymer

components by looking for the names E2 and LDPE
respectively. If you change component names you
must update the subroutine.
If you don't have compiler you can copy USERFORT.DLL

and USERFORT.DLOPT from APPlication folder to the working
directory, enter USERPORT.DLOPT in the Run/Settings
/Engine Files/Linker Options box and run the simulation.
"

COMPONENTS
INI1 C14H10O4 /
E2 C2H4 /
LDPE PE /
E2-SEG C2H4-R /
INI2 C8H18O2 /
WATER H2O
FLOWSHEET
BLOCK PFR1 IN=FEED1 CIN1 OUT=OUT1 COUT1
BLOCK PFR2 IN=OUT1 CIN2 OUT=OUT2 COUT2
BLOCK FDMIX2 IN=OUT2 INIFD2 E2FD2B OUT=FEED2
BLOCK PFR3 IN=FEED2 CIN3 OUT=OUT3 COUT3
BLOCK PFR4 IN=OUT3 CIN4 OUT=OUT4 COUT4
BLOCK HPS IN=OUT4 OUT=HP-RECY HPSB
BLOCK LPS IN=HPSB OUT=LP-RECY LPSB
BLOCK FDMIX1 IN=E2FD1B INIFD1 OUT=FEED1
BLOCK FSPLIT1 IN=E2FD OUT=E2FD2A E2FD1A
BLOCK EFD1 IN=E2FD1A OUT=E2FD1B
BLOCK EFD2 IN=E2FD2A OUT=E2FD2B
PROPERTIES POLYSL
PROPERTIES STEAM-TA
PROP-DATA POLYSL
PRESSURE=bar PDROP='N/sqm'
PROP-LIST SLTSTR / SLPSTR / SLRSTR
PVAL E2 333.0 / 2400.0 / 631.0
PVAL LDPE 667.70 / 3500.0 / 894.0
PVAL INI1 530 / 3040 / 1120
PVAL INI2 530 / 3040 / 1120
PVAL WATER 623.0 / 2.6871390E+04 / 1105.0
PROP-DATA TGTM
PRESSURE=bar TEMPERATURE=C PDROP='N/sqm'
PROP-LIST TGVK / TMVK / CRITMW
PVAL LDPE -36.0 / 141.60 / 3500.0
PROP-DATA VLSTD
PROP-LIST VLSTD
PVAL E2-SEG 0.0
PROP-DATA CPIG-1
PROP-LIST CPIG
PVAL E2-SEG 35342.0 70.20
PVAL E2 42291.0 47.3550
PROP-DATA MULMH-1

PROP-LIST MULMH
PVAL LDPE .0005740 5000.0 7.54220 1.0 1.0
PROP-DATA SLETIJ-1
IN-UNITS SI
PROP-LIST SLETIJ
BPVAL LDPE E2 -.15
BPVAL E2 LDPE -.15
PROP-DATA SLKIJ-1
IN-UNITS SI
PROP-LIST SLKIJ
BPVAL LDPE E2 .04
BPVAL E2 LDPE .04
POLYMERS
SEGMENTS E2-SEG REPEAT
POLYMERS LDPE
ATTRIBUTES LDPE DPN DPW PDI MWN MWW ZMOM FMOM SMOM &
SFLOW SFRAC FLCB FSCB LCB SCB LSFLOW LSFRAC LEFLOW &
LEFRAC
STREAM CIN1
SUBSTREAM MIXED TEMP=160.0 PRES=100.0 NPHASE=1 PHASE=L
MASS-FLOW WATER 160000.0
STREAM CIN2
STREAM CIN3
STREAM CIN4
STREAM E2FD
SUBSTREAM MIXED TEMP=100. PRES=2020.
MASS-FLOW E2 65000.
STREAM E2FD1B
MASS-FLOW E2 40000.
STREAM E2FD2B
MASS-FLOW E2 25000.
STREAM FEED1
SUBSTREAM MIXED TEMP=140. PRES=2000.0 MASS-FLOW=63000.0 &
NPHASE=1 PHASE=L
MASS-FRAC INI1 2.2E-005 / E2 0.999976 / INI2 1.1E-005
STREAM INIFD1

MASS-FLOW INI1 6. / INI2 1.5
STREAM INIFD2
SUBSTREAM MIXED TEMP=0. PRES=2010. NPHASE=1 PHASE=L
MASS-FLOW INI1 12. / INI2 3.
BLOCK FDMIX1 MIXER

PARAM PRES=2000. NPHASE=1 PHASE=L
BLOCK FDMIX2 MIXER

PARAM PRES=1900. NPHASE=1 PHASE=L
BLOCK FSPLIT1 FSPLIT

MASS-FLOW E2FD1A 40000.
BLOCK EFD1 HEATER

PARAM TEMP=140. PRES=-10. NPHASE=1 PHASE=L
BLOCK EFD2 HEATER

PARAM TEMP=50. PRES=-20. NPHASE=1 PHASE=L
BLOCK HPS FLASH2

PARAM PRES=250.0 DUTY=0.0
BLOCK LPS FLASH2

PARAM PRES=1.0 DUTY=0.0
BLOCK PFR1 RPLUG

SUBROUTINE QTRANS=USRHPE
USER-VECS NREALQ=2
REALQ VALUE-LIST=40. 100.
PARAM TYPE=COUNTER-COOL LENGTH=250.0 DIAM=.0590 NPHASE=1 &
PHASE=L PDROP=100. <bar> NPOINT=40 INT-TOL=1E-005 &
CORR-METHOD=DIRECT ERR-METHOD=STATIC
COOLANT PDROP=4. <bar> NPHASE=1 PHASE=L TEMP=170.0
PROPERTIES POLYSL / STEAM-TA
BLOCK PFR2 RPLUG

USER-VECS NREALQ=2
BLOCK PFR3 RPLUG

USER-VECS NREALQ=2

BLOCK PFR4 RPLUG

USER-VECS NREALQ=2
EO-CONV-OPTI
CONV-OPTIONS
PARAM CHECKSEQ=NO
PROPERTY-REP NOPCES
DESCRIPTION "Free-Radical Kinetic Scheme"
PARAM QSSA=YES
SPECIES INITIATOR=INI1 INI2 MONOMER=E2 POLYMER=LDPE
MON-RSEG E2 E2-SEG
INIT-DEC INI1 2.5000E+14 1.2600E+08 0.0 EFFIC=0.4 NRADS=2
INIT-DEC INI2 5.93E+018 1.9500E+08 0.0 EFFIC=0.4 NRADS=2
CHAIN-INI E2 2.5000E+08 3.5300E+07 0.0
PROPAGATION E2 E2 2.5000E+08 3.5300E+07 -.02130
CHAT-MON E2 E2 1250000.0 4.5400E+07 0.0
CHAT-POL E2 E2 1240000.0 3.0400E+07 .00160
B-SCISSION E2 6.0700E+07 4.5300E+07 0.0
TERM-DIS E2 E2 2.5000E+09 4190000.0 .0010
TERM-COMB E2 E2 2.5000E+09 4190000.0 .0010
SC-BRANCH E2 E2 1.3000E+09 4.1600E+07 0.0

This model was used to study several process parameters for the production
of LDPE. The parameters evaluated for the first reactor section (PFR1) are
plotted in the figures that follow.
DPn and DPw versus reactor length for PFR1 is shown here:

5000
4500
4000
Degree of Polymerization
3500
DPN
3000
DPW
2500
2000
1500
1000
500
0
0 50 100 150 200 250
Length, m
Initiator decomposition rate versus reactor length for PFR1 is shown here:
2.00E-05
INI1
Initiator Mole Fraction
1.50E-05 INI2
1.00E-05
5.00E-06
0.00E+00
0 50 100 150 200 250
Length, m
Coolant and reactant temperature profiles for PFR1 are shown here:

350
300
Temperature (C)
250
Process
200 Coolant
150
100
0 50 100 150 200 250
Length, m
The remaining ethylene mole fraction profile in PFR1 and PFR3 is shown here:
PFR1
0.95
Ethylene Mole Fraction
PFR3
0.9
0.85
0.8
0.75
0 50 100 150 200 250
Length, m
The reactor temperature profiles are shown here:

350
300
PFR1
Temperature (C)
PFR2
250
PFR3
PFR4
200
150
100
0 50 100 150 200 250
Length, m

The stream summary for this example is shown here:
CIN1 CIN2 CIN3 CIN4 COUT1

-------------------------
STREAM ID CIN1 CIN2 CIN3 CIN4 COUT1

FROM : ---- ---- ---- ---- PFR1
TO : PFR1 PFR2 PFR3 PFR4 ----
SUBSTREAM: MIXED
COMPONENTS: KMOL/HR
INI1 0.0 0.0 0.0 0.0 0.0
E2 0.0 0.0 0.0 0.0 0.0
LDPE 0.0 0.0 0.0 0.0 0.0
INI2 0.0 0.0 0.0 0.0 0.0
WATER 8881.3496 8881.3496 8881.3496 8881.3496 8881.3496
COMPONENTS: KG/HR
INI1 0.0 0.0 0.0 0.0 0.0
E2 0.0 0.0 0.0 0.0 0.0
LDPE 0.0 0.0 0.0 0.0 0.0
INI2 0.0 0.0 0.0 0.0 0.0
WATER 1.6000+05 1.6000+05 1.6000+05 1.6000+05 1.6000+05
INI1 0.0 0.0 0.0 0.0 0.0
E2 0.0 0.0 0.0 0.0 0.0
LDPE 0.0 0.0 0.0 0.0 0.0
INI2 0.0 0.0 0.0 0.0 0.0
WATER 1.0000 1.0000 1.0000 1.0000 1.0000

TOTAL FLOW:
KMOL/HR 8881.3496 8881.3496 8881.3496 8881.3496 8881.3496
KG/HR 1.6000+05 1.6000+05 1.6000+05 1.6000+05 1.6000+05
CUM/SEC 4.8564-02 4.8899-02 4.8556-02 4.8704-02 4.9225-02
STATE VARIABLES:
TEMP C 157.6171 164.1454 157.4568 160.3683 170.0000
PRES BAR 100.0000 100.0000 100.0000 100.0000 96.0000
VFRAC 0.0 0.0 0.0 0.0 0.0
LFRAC 1.0000 1.0000 1.0000 1.0000 1.0000
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL -2.7564+08 -2.7514+08 -2.7565+08 -2.7543+08 -2.7468+08
J/KG -1.5300+07 -1.5272+07 -1.5301+07 -1.5289+07 -1.5247+07
WATT -6.8002+08 -6.7877+08 -6.8005+08 -6.7950+08 -6.7766+08
ENTROPY:
J/KMOL-K -1.3543+05 -1.3427+05 -1.3546+05 -1.3494+05 -1.3322+05
J/KG-K -7517.7040 -7452.9519 -7519.3030 -7490.3316 -7394.9629
DENSITY:
KMOL/CUM 50.7995 50.4520 50.8079 50.6543 50.1180
KG/CUM 915.1666 908.9073 915.3180 912.5509 902.8902
AVG MW 18.0153 18.0153 18.0153 18.0153 18.0153
COUT2 COUT3 COUT4 E2FD E2FD1A

-----------------------------
STREAM ID COUT2 COUT3 COUT4 E2FD E2FD1A

FROM : PFR2 PFR3 PFR4 ---- FSPLIT1
TO : ---- ---- ---- FSPLIT1 EFD1
SUBSTREAM: MIXED
PHASE: LIQUID LIQUID LIQUID VAPOR VAPOR
COMPONENTS: KMOL/HR
INI1 0.0 0.0 0.0 0.0 0.0
E2 0.0 0.0 0.0 2316.9800 1425.8338
LDPE 0.0 0.0 0.0 0.0 0.0
INI2 0.0 0.0 0.0 0.0 0.0
WATER 8881.3496 8881.3496 8881.3496 0.0 0.0
COMPONENTS: KG/HR
INI1 0.0 0.0 0.0 0.0 0.0
E2 0.0 0.0 0.0 6.5000+04 4.0000+04
LDPE 0.0 0.0 0.0 0.0 0.0
INI2 0.0 0.0 0.0 0.0 0.0
WATER 1.6000+05 1.6000+05 1.6000+05 0.0 0.0
INI1 0.0 0.0 0.0 0.0 0.0
E2 0.0 0.0 0.0 1.0000 1.0000
LDPE 0.0 0.0 0.0 0.0 0.0
INI2 0.0 0.0 0.0 0.0 0.0
WATER 1.0000 1.0000 1.0000 0.0 0.0
TOTAL FLOW:
KMOL/HR 8881.3496 8881.3496 8881.3496 2316.9800 1425.8338
KG/HR 1.6000+05 1.6000+05 1.6000+05 6.5000+04 4.0000+04
CUM/SEC 4.9225-02 4.9225-02 4.9225-02 3.2683-02 2.0113-02
STATE VARIABLES:
TEMP C 170.0000 170.0000 170.0000 100.0000 100.0000
PRES BAR 96.0000 96.0000 96.0000 2020.0000 2020.0000
VFRAC 0.0 0.0 0.0 1.0000 1.0000

LFRAC 1.0000 1.0000 1.0000 0.0 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL -2.7468+08 -2.7468+08 -2.7468+08 5.3717+07 5.3717+07
J/KG -1.5247+07 -1.5247+07 -1.5247+07 1.9148+06 1.9148+06
WATT -6.7766+08 -6.7766+08 -6.7766+08 3.4573+07 2.1276+07
ENTROPY:
J/KMOL-K -1.3322+05 -1.3322+05 -1.3322+05 -1.1907+05 -1.1907+05
J/KG-K -7394.9629 -7394.9629 -7394.9629 -4244.2535 -4244.2535
DENSITY:
KMOL/CUM 50.1180 50.1180 50.1180 19.6923 19.6923
KG/CUM 902.8902 902.8902 902.8902 552.4417 552.4417
AVG MW 18.0153 18.0153 18.0153 28.0538 28.0538
E2FD1B E2FD2A E2FD2B FEED1 FEED2

--------------------------------
STREAM ID E2FD1B E2FD2A E2FD2B FEED1 FEED2

FROM : EFD1 FSPLIT1 EFD2 FDMIX1 FDMIX2
TO : FDMIX1 EFD2 FDMIX2 PFR1 PFR3
SUBSTREAM: MIXED
PHASE: LIQUID VAPOR LIQUID LIQUID LIQUID
COMPONENTS: KMOL/HR
INI1 0.0 0.0 0.0 2.4770-02 4.9539-02
E2 1425.8338 891.1461 891.1461 1425.8338 2147.5521
LDPE 0.0 0.0 0.0 0.0 169.6952
INI2 0.0 0.0 0.0 1.0258-02 2.0516-02
WATER 0.0 0.0 0.0 0.0 0.0
COMPONENTS: KG/HR
INI1 0.0 0.0 0.0 6.0000 12.0000
E2 4.0000+04 2.5000+04 2.5000+04 4.0000+04 6.0247+04
LDPE 0.0 0.0 0.0 0.0 4760.5891
INI2 0.0 0.0 0.0 1.5000 3.0000
WATER 0.0 0.0 0.0 0.0 0.0
INI1 0.0 0.0 0.0 1.4997-04 1.8455-04
E2 1.0000 1.0000 1.0000 0.9998 0.9266
LDPE 0.0 0.0 0.0 0.0 7.3214-02
INI2 0.0 0.0 0.0 3.7493-05 4.6138-05
WATER 0.0 0.0 0.0 0.0 0.0
TOTAL FLOW:
KMOL/HR 1425.8338 891.1461 891.1461 1425.8689 2317.3174
KG/HR 4.0000+04 2.5000+04 2.5000+04 4.0007+04 6.5023+04
CUM/SEC 2.0772-02 1.2570-02 1.2129-02 2.0803-02 3.3515-02
STATE VARIABLES:
TEMP C 140.0000 100.0000 50.0000 140.6072 145.4816
PRES BAR 2010.0000 2020.0000 2000.0000 2000.0000 1900.0000
VFRAC 0.0 1.0000 0.0 0.0 0.0
LFRAC 1.0000 0.0 1.0000 1.0000 1.0000
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL 5.5884+07 5.3717+07 5.1043+07 5.5875+07 4.8595+07
J/KG 1.9920+06 1.9148+06 1.8195+06 1.9914+06 1.7319+06
WATT 2.2134+07 1.3297+07 1.2635+07 2.2131+07 3.1281+07
ENTROPY:
J/KMOL-K -1.1342+05 -1.1907+05 -1.2647+05 -1.1331+05 -1.1659+05

J/KG-K -4043.0332 -4244.2535 -4508.1238 -4038.3549 -4155.2568
DENSITY:
KMOL/CUM 19.0672 19.6923 20.4089 19.0396 19.2061
KG/CUM 534.9065 552.4417 572.5456 534.2197 538.9116
AVG MW 28.0538 28.0538 28.0538 28.0583 28.0594
LDPE DPN
DPN MISSING MISSING MISSING MISSING 1204.7748
DPW
DPW MISSING MISSING MISSING MISSING 4334.8385
PDI
PDI MISSING MISSING MISSING MISSING 3.5980
MWN
MWN MISSING MISSING MISSING MISSING 3.3798+04
MWW
MWW MISSING MISSING MISSING MISSING 1.2161+05
ZMOM
ZMOM MISSING MISSING MISSING MISSING 0.1406
FMOM
FMOM MISSING MISSING MISSING MISSING 169.4279
SMOM
SMOM MISSING MISSING MISSING MISSING 7.3444+05
SFLOW
E2-SEG MISSING MISSING MISSING MISSING 169.4279
SFRAC
FLCB
FLCBN MISSING MISSING MISSING MISSING 0.3476
FSCB
FSCBN MISSING MISSING MISSING MISSING 26.5545
LCB
LCBN MISSING MISSING MISSING MISSING 5.8890-02
SCB
SCBN MISSING MISSING MISSING MISSING 4.4991
LSFLOW
LSFRAC
LEFLOW
LEFRAC
HP-RECY HPSB INIFD1 INIFD2 LP-RECY

----------------------------------
STREAM ID HP-RECY HPSB INIFD1 INIFD2 LP-RECY

FROM : HPS HPS ---- ---- LPS
TO : ---- LPS FDMIX1 FDMIX2 ----
SUBSTREAM: MIXED
PHASE: VAPOR LIQUID LIQUID LIQUID VAPOR
COMPONENTS: KMOL/HR
INI1 0.0 0.0 2.4770-02 4.9539-02 0.0
E2 1829.6532 51.0738 0.0 0.0 50.9159
LDPE 0.0 437.0550 0.0 0.0 0.0
INI2 0.0 0.0 1.0258-02 2.0516-02 0.0

WATER 0.0 0.0 0.0 0.0 0.0
COMPONENTS: KG/HR
INI1 0.0 0.0 6.0000 12.0000 0.0
E2 5.1329+04 1432.8126 0.0 0.0 1428.3826
LDPE 0.0 1.2261+04 0.0 0.0 0.0
INI2 0.0 0.0 1.5000 3.0000 0.0
WATER 0.0 0.0 0.0 0.0 0.0
INI1 0.0 0.0 0.8000 0.8000 0.0
E2 1.0000 0.1046 0.0 0.0 1.0000
LDPE 0.0 0.8954 0.0 0.0 0.0
INI2 0.0 0.0 0.2000 0.2000 0.0
WATER 0.0 0.0 0.0 0.0 0.0
TOTAL FLOW:
KMOL/HR 1829.6532 488.1288 3.5028-02 7.0055-02 50.9159
KG/HR 5.1329+04 1.3694+04 7.5000 15.0000 1428.3826
CUM/SEC 8.9115-02 5.9683-03 1.8926-06 3.7852-06 0.6322
STATE VARIABLES:
TEMP C 262.7789 262.7789 0.0 0.0 264.7096
PRES BAR 250.0000 250.0000 2010.0000 2010.0000 1.0000
VFRAC 1.0000 0.0 0.0 0.0 1.0000
LFRAC 0.0 1.0000 1.0000 1.0000 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL 6.1408+07 -3.0694+07 -3.1707+08 -3.1707+08 6.4279+07
J/KG 2.1889+06 -1.0941+06 -1.4808+06 -1.4808+06 2.2913+06
WATT 3.1210+07 -4.1619+06 -3085.0561 -6170.1122 9.0912+05
ENTROPY:
J/KMOL-K -7.5346+04 -1.7337+05 -8.1205+05 -8.1205+05 -2.4668+04
J/KG-K -2685.7755 -6179.9927 -3792.5618 -3792.5618 -879.3212
DENSITY:
KMOL/CUM 5.7032 22.7187 5.1411 5.1411 2.2372-02
KG/CUM 159.9951 637.3438 1100.7884 1100.7884 0.6276
AVG MW 28.0538 28.0538 214.1170 214.1170 28.0538
LDPE DPN
DPN MISSING 1109.1855 MISSING MISSING MISSING
DPW
DPW MISSING 5901.7459 MISSING MISSING MISSING
PDI
PDI MISSING 5.3208 MISSING MISSING MISSING
MWN
MWN MISSING 3.1117+04 MISSING MISSING MISSING
MWW
MWW MISSING 1.6557+05 MISSING MISSING MISSING
ZMOM
ZMOM MISSING 0.3933 MISSING MISSING MISSING
FMOM
FMOM MISSING 436.2529 MISSING MISSING MISSING
SMOM
SMOM MISSING 2.5747+06 MISSING MISSING MISSING
SFLOW
E2-SEG MISSING 436.2529 MISSING MISSING MISSING
SFRAC
FLCB
FLCBN MISSING 0.6653 MISSING MISSING MISSING

FSCB
FSCBN MISSING 28.7473 MISSING MISSING MISSING
LCB
LCBN MISSING 0.2902 MISSING MISSING MISSING
SCB
SCBN MISSING 12.5411 MISSING MISSING MISSING
LSFLOW
LSFRAC
LEFLOW
LEFRAC
LPSB OUT1 OUT2 OUT3 OUT4

------------------------
STREAM ID LPSB OUT1 OUT2 OUT3 OUT4

FROM : LPS PFR1 PFR2 PFR3 PFR4
TO : ---- PFR2 FDMIX2 PFR4 HPS
SUBSTREAM: MIXED
COMPONENTS: KMOL/HR
INI1 0.0 0.0 0.0 0.0 0.0
E2 0.1579 1256.4059 1256.4059 1880.7270 1880.7270
LDPE 437.0550 169.6952 169.6952 437.0550 437.0550
INI2 0.0 0.0 0.0 0.0 0.0
WATER 0.0 0.0 0.0 0.0 0.0
COMPONENTS: KG/HR
INI1 0.0 0.0 0.0 0.0 0.0
E2 4.4300 3.5247+04 3.5247+04 5.2761+04 5.2761+04
LDPE 1.2261+04 4760.5891 4760.5891 1.2261+04 1.2261+04
INI2 0.0 0.0 0.0 0.0 0.0
WATER 0.0 0.0 0.0 0.0 0.0
INI1 0.0 0.0 0.0 0.0 0.0
E2 3.6118-04 0.8810 0.8810 0.8114 0.8114
LDPE 0.9996 0.1190 0.1190 0.1886 0.1886
INI2 0.0 0.0 0.0 0.0 0.0
WATER 0.0 0.0 0.0 0.0 0.0
TOTAL FLOW:
KMOL/HR 437.2129 1426.1012 1426.1012 2317.7820 2317.7820
KG/HR 1.2265+04 4.0008+04 4.0008+04 6.5023+04 6.5023+04
CUM/SEC 4.8136-03 2.1985-02 2.1512-02 3.6219-02 3.5501-02
STATE VARIABLES:
TEMP C 264.7096 243.8088 202.7850 278.5977 237.8896
PRES BAR 1.0000 1900.0000 1800.0000 1800.0000 1700.0000
VFRAC 0.0 0.0 0.0 0.0 0.0
LFRAC 1.0000 1.0000 1.0000 1.0000 1.0000
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL -4.1755+07 4.9898+07 4.7084+07 4.4866+07 4.2011+07
J/KG -1.4884+06 1.7787+06 1.6783+06 1.5993+06 1.4975+06
WATT -5.0710+06 1.9767+07 1.8652+07 2.8886+07 2.7048+07
ENTROPY:

J/KMOL-K -1.8722+05 -1.0741+05 -1.1198+05 -1.0825+05 -1.1258+05
J/KG-K -6673.7654 -3828.7824 -3991.4944 -3858.7028 -4012.9062
DENSITY:
KMOL/CUM 25.2300 18.0187 18.4148 17.7760 18.1354
KG/CUM 707.7974 505.4927 516.6047 498.6843 508.7674
AVG MW 28.0538 28.0538 28.0538 28.0538 28.0538
LDPE DPN
DPN 1109.1855 1204.7748 1204.7748 1109.1855 1109.1855
DPW
DPW 5901.7459 4334.8385 4334.8385 5901.7459 5901.7459
PDI
PDI 5.3208 3.5980 3.5980 5.3208 5.3208
MWN
MWN 3.1117+04 3.3798+04 3.3798+04 3.1117+04 3.1117+04
MWW
MWW 1.6557+05 1.2161+05 1.2161+05 1.6557+05 1.6557+05
ZMOM
ZMOM 0.3933 0.1406 0.1406 0.3933 0.3933
FMOM
FMOM 436.2529 169.4279 169.4279 436.2529 436.2529
SMOM
SMOM 2.5747+06 7.3444+05 7.3444+05 2.5747+06 2.5747+06
SFLOW
E2-SEG 436.2529 169.4279 169.4279 436.2529 436.2529
SFRAC
E2-SEG 1.0000 1.0000 1.0000 1.0000 1.0000
FLCB
FLCBN 0.6653 0.3476 0.3476 0.6653 0.6653
FSCB
FSCBN 28.7473 26.5545 26.5545 28.7473 28.7473
LCB
LCBN 0.2902 5.8890-02 5.8890-02 0.2902 0.2902
SCB
SCBN 12.5411 4.4991 4.4991 12.5411 12.5411
LSFLOW
E2-SEG 0.0 0.0 0.0 0.0 0.0
LSFRAC
E2-SEG 0.0 0.0 0.0 0.0 0.0
LEFLOW
E2-SEG 0.0 0.0 0.0 0.0 0.0
LEFRAC
E2-SEG 0.0 0.0 0.0 0.0 0.0
References
Brandup, J., & Immergut, E. H. (1989). Polymer Handbook, 3rd Ed. NewYork:
John Wiley.
Carr, N. L., Parent, J. D., & Peck, R. E. (1955). Viscosity of Gases and Gas
Mixtures at High Pressures. Chem. Eng. Progr. Symposium Ser. No. 16, 51,
91.
Danner, R. P., & High, M. S. (1982). Handbook of Polymer Solution
Thermodynamics. DIPPR.

Eirmann, K. (1965). Modellmssige Deutung de Wrmeleitfahigkeit von
Hochpolymeren. Koll. Z., 201, p. 3.
Hellwege, K. H., Knoppf, W., & Wetzel, W. (1962). Spezifische Warme von
Polyolefinen und einigen anderen Hochpolymeren im Temperaturbereich von
300C - 180C. Koll. Z., 180, p. 126.
Mavridis, I., & Kiparissides, C. (1985). Optimization of a High-Pressure
Polyethylene Tubular Reactor. Polymer Process Engineering, 3(3), pp. 263-
290.
Michels, A., & Geldermans, M. (1942). Isotherms of Ethylene Up to 3,000
Atmospheres Between 0C and 150C. Physica, 9, p. 967.
Odian, G. (1991). Principles of Polymerization, 3rd Ed. New York: John Wiley
and Sons.
Sanchez, I. C., & Lacombe, R. H. (1976). An Elementary Molecular Theory of
Chemical Fluids. Pure Fluids. J. Phys. Chem., 80(21), pp. 2352-2362.
Sanchez, I. C., & Lacombe, R. H. (1978). Statistical Thermodynamics of
Polymer Solutions. Macromolecules, 11(6), pp. 1145-1156.

B9 Nylon 6 Caprolactam
Polymerization Process
The nylon 6 caprolactam polymerization process model illustrates the use of

Aspen Polymers to simulate the polymerization of caprolactam to Nylon 6.
This multistage reactor model accounts for the step-growth polymerization
kinetics. This model is used to study the effect of feed flow rate on
caprolactam conversion, degree of polymerization, and extraction value.
About This Process

Nylon 6 is produced industrially on a large scale for synthetic fibers, films,
plastics, etc. In one process, it is obtained by polymerizing caprolactam in the
presence of water in a continuous flowsheet. Process modeling plays an
important role in quality control, modification of existing plants, development
of new processes, etc.
Nylon is commonly produced in a conventional VK column reactor. The reactor
is essentially a vertical tube operating at atmospheric pressure. A mixture of
caprolactam, water and stabilizer is continuously fed to the top of the column.
The ring opening reaction initiates polymerization in zone 1 and the excess
water is evaporated in this zone. The vapor coming out of zone 1 is sent to a
distillation column. Caprolactam from the distillation column is recycled to the
reactor and condensate water is removed. In zone 2, polymerization proceeds
under near adiabatic conditions. No water is evaporated in this zone.
A representation of a conventional VK column is shown here:
200 B9 Nylon 6 Caprolactam Polymerization Process

The feed to the process is a mixture of caprolactam (99% by weight) and
water (1% by weight) at 260C, 1 atm. When this mixture is heated to
temperatures above 220-260C, five main equilibrium reactions occur:
Ring opening of caprolactam
Polycondensation of the end groups
Polyaddition of caprolactam
Ring opening of cyclic dimmer
Polyaddition of cyclic dimer.
The model must account for all of these reactions.
Process Definition
In this example, the top portion of the VK column (zone 1) will be modeled as
two stirred tank reactors. The bottom portion of the column (zone 2 and
below) will be modeled as a plug flow reactor. The distillation column will be
included in the simulations as a multistage separator. A flash tank will be
inserted after each stirred tank in zone 1 to account for VLE calculations. The
plug flow reactor will be considered liquid filled.
B9 Nylon 6 Caprolactam Polymerization Process 201

The flowsheet consists of two RCSTR in series, with a Flash2 in the middle, a
second Flash2 followed by an RPlug, and finally a RadFrac block for the water-
caprolactam separation:
Process Conditions
Caprolactam CL PURE12 Monomer

Aminocaproic ACA PURE12 Monomer
Acid
Cyclic Dimer CD PURE12 Monomer
Water H2O PURE12 Catalyst
Nylon NYLON POLYMER Polymer
T-NH2 SEGMENT NH2 segment

T-COOH SEGMENT COOH segment
B-ACA SEGMENT ACA segment
Physical POLYNRTL property method with supplied parameters
Properties
Feeds
Temperature 260
(C)
Pressure (atm) 1
Flowrate 40
(kg/hr)
Caprolactam 99.0% by weight
Water 1.0% by weight
Kinetics STEP-GROWTH model
Operating Block Temp Pres Size

Conditions (C) (atm)
CSTR-1 260 1 10 m3 (7.5 m3 liquid)

CSTR-2 260 1 10 m3 (all liquid)
PLUG 260 1 20 m length by 1.85 m diam
DISTIL --- 1 19 total condenser, reflux ratio of
3

The Polymer Non-Random Two Liquid activity coefficient model property
method (POLYNRTL) is used. Antoine constants for vapor pressure are
entered for the components.
Reaction Kinetics
The main reactions used in the step-growth kinetics are:
1 Ring-opening of
caprolactam NH(CH2)5 CO + H2O H2N (CH2)5 COOH
2 Polycondensation
NH2 + HOOC NHCO + H2O
3 Polyaddition of
NH2 + CO (CH2)5 - NH NHCO - (CH2)5 - NH2
caprolactam
4 Ring-opeining of cyclic
dimer NH(CH2)5CONH(CH2)5CO + H2O H2N(CH2)5 CONH(CH2)5 COOH
5 Polyaddition of cyclic
dimer NH2 + NH(CH 2)5CONH(CH2)5CO NHCO(CH2)5NHCO(CH2 )5 NH2

A set of rate parameters reported in the literature was used in this example
and is given here:
Ao Eo Ac Ec
Ring opening of (f) 5.9874x105 19.88 4.3075x107 18.806

caprolactam (r) 3.1663x10 7
17.962 2.2779x109 16.88
10 10
Polycondensation (f) 1.8942x10 23.271 1.2114x10 20.670
10 9
(r) 1.17802x10 29.216 7.5338x10 26.616
Polayaddition of (f) 2.8558x109 22.845 1.6377x1010 20.107
caprolactam (r) 9.4153x1010 26.888 5.3993x1011 24.151
11
Ring opening of cyclic (f) 8.5778x10 42.000 2.3307x1012 37.400
dimer (r) 1.2793x10 15
51.600 3.4761x10 15
47.000
Polyaddition of cyclic (f) 2.5701x108 21.300 3.011x109 20.400
dimer (r) 1.9169x10 8
24.469 2.2458x10 9
23.569
o= uncatalyzed c = catalyzed f = forward reaction r = reverse reaction

Ao in kg/mol/h, Ac in kg2/mol2/h, Eo and Ec in kcal/mol
The polycondensation reaction is modeled using the step-growth kinetics. The
functionality of the amine and acid end groups are defined in the step-growth
Species sheet, as shown here:
The model generates the reaction network based on these functional groups.
To keep the model consistent with Tai and Tagawa, we have cleared the
reaction generation option for re-arrangement reactions on the Options
sheet, as shown here:

Note the Concentration basis has been set to mol/kgthis forces the
model to use the same mass concentration basis reported in Tai and Tagawa.
The generated reactions are shown on the Reactions sheet:
The Tai/Tagawa model presumes that all condensation reactions (model

generated reactions 1-4 above) have the same rate constants. The model also
assumes that the hydrolysis reactions (reactions 5-8 above) have the same
rate constants.
These data are entered on the Rate Constants sheet as shown here:

The catalyst terms refer to the acid catalysis (aminocaproic acid, ACA, and
acid end groups, T-COOH, both contain an acid end).
The Assign Rate Constants sheet is used to link each set of rate constants
to an appropriate set of reactions:
Rate constants 1, 2, and 3 are assigned to condensation reactions (e.g., the

reactions between acid and amine end groups). Rate constants 4, 5, and 6
are assigned to the hydrolysis reactions (e.g., the reactions in which water
attacks a polymer chain).
The step-growth model does not automatically generate ring opening or ring
addition reactions. These must be defined as user-specified reactions on the
User Reactions sheet. The forward and reverse components of these
reactions are entered separately, as shown here:

The model includes reactions for cyclic monomer (CL) and cyclic dimer (CD).
The formation of cyclic trimer and higher cyclics is considered negligible and
is not considered in the present model.
On the User Reactions sheet, reactions 1 and 2 refer to ring opening of
caprolactam and its reverse reaction (ring closure). The forward reaction is
set first order with respect to caprolactam and water. The reverse reaction is
set first order with respect to aminocaproic acid (the model assumes that the
concentration of linear dimer is equal to the concentration of aminocaproic
acidthis assumption is used to keep the model consistent with the
Tai/Tagawa model, which also assumes [P1] = [P2] = [P3].)
Reaction 3 refers to ring addition of caprolacatam to polymer amine end
groups. Reaction 4 is the corresponding cyclodepolymerization reaction. The
forward reaction is presumed to be first order with respect to caprolactam and
amine end groups. The reverse reaction is assumed to be first order with
respect to amine end groups.
Reaction 5 refers to ring addition of caprolacatam to monomeric aminocaproic
acid. Reaction 6 is the corresponding cyclodepolymerization reaction. The
forward reaction is presumed to be first order with respect to caprolactam and
aminocaproic acid. The reverse reaction is assumed to be first order with
respect to aminocaproic acid (once again, the model assumes that the
concentration of linear dimer is equal to the concentration of aminocaproic
acid).
Reactions 7-12 (which apply to cyclic dimer) are analogous to reactions 1-6
(which apply to cyclic monomer).
The rate constants for the user specified reactions are specified on the User
Rate Constants sheet:

In total, twenty-four sets of rate constants are specified. These rate constants
are linked to the reactions on the Assign User Rate Constants sheet,
shown here:

Process Studies
In order to determine the effect of feed flow rate on caprolactam conversion,
degree of polymerization, and extraction value, a sensitivity study is carried
out with the feed mass flow as the varied parameter. The sampled
parameters are the polymer properties, the component fractions used to
determine conversion, and the flowrates.
Input Summary
TITLE 'CAPROLACTAM POLYMERIZATION'

VOLUME-FLOW='l/hr' PRESSURE=atm TEMPERATURE=C TIME=hr &
VOLUME=l MOLE-ENTHALP='kcal/mol' MOLE-ENTROPY='kcal/mol-K' &
INVERSE-TIME='1/hr' LN-INV-TIME='ln(1/hr)' PDROP='N/sqm'
DIAGNOSTICS
HISTORY SIM-LEVEL=3 PROP-LEVEL=3
DESCRIPTION "THIS IS A MODEL OF A NYLON-6 PROCESS. "
DATABANKS POLYMER / PURE12 / SEGMENT / AQUEOUS / SOLIDS &

/ INORGANIC / NOASPENPCD
PROP-SOURCES POLYMER / PURE12 / SEGMENT / AQUEOUS / &

SOLIDS / INORGANIC
COMPONENTS
H2O H2O /
CL C6H11NO /
ACA C6H11NO /
CD C6H11NO /
NYLON NYLON6 /
T-NH2 C6H12NO-E-1 /
T-COOH C6H12NO2-E-1 /
B-ACA C6H11NO-R-1
FLOWSHEET
BLOCK STAGE1 IN=FEED RECYCLE R2-VAP OUT=R1-OLIGO R1VAP
BLOCK DISTIL IN=R1VAP OUT=COND RECYCLE
BLOCK STAGE2 IN=R1-OLIGO OUT=R2-VAP R2-OLIGO
BLOCK PLUG IN=R2-OLIGO OUT=POLYMER
PROPERTIES POLYNRTL
PROP-DATA MW
IN-UNITS SI
PROP-LIST MW
PVAL ACA 131.174760

PVAL CD 226.318960
PROP-DATA PLXANT-1
IN-UNITS SI PRESSURE=atm PDROP='N/sqm'
PROP-LIST PLXANT
PVAL ACA -40.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PVAL CD -40.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1000.0
PROP-DATA NRTL-1
IN-UNITS ENG
PROP-LIST NRTL
BPVAL H2O CL -4.01840 1634.2356470 .30 0.0 0.0 0.0 &
105.80000320 508.99999990
BPVAL CL H2O -.79760 3537.9406520 .30 0.0 0.0 0.0 &
105.80000320 508.99999990
BPVAL H2O ACA -4.01840 1634.2356470 .30 0.0 0.0 0.0 &
105.80000320 508.99999990
BPVAL ACA H2O -.79760 3537.9406520 .30 0.0 0.0 0.0 &
105.80000320 508.99999990
BPVAL H2O CD -4.01840 1634.2356470 .30 0.0 0.0 0.0 &
105.80000320 508.99999990
BPVAL CD H2O -.79760 3537.9406520 .30 0.0 0.0 0.0 &
105.80000320 508.99999990
POLYMERS
SEGMENTS T-NH2 END / T-COOH END / B-ACA REPEAT
POLYMERS NYLON
ATTRIBUTES NYLON SFLOW ZMOM FMOM DPN MWN EFRAC SFRAC
STREAM FEED
SUBSTREAM MIXED TEMP=260.0 PRES=1.0 MASS-FLOW=3600. &
NPHASE=1 PHASE=L
MASS-FRAC H2O .010 / CL .990
STREAM RECYCLE
SUBSTREAM MIXED TEMP=116.523631 PRES=1 MASS-FLOW=145.425133
MASS-FRAC H2O 0.217256374 / CL 0.782743626
BLOCK DISTIL RADFRAC

PARAM NSTAGE=20
FEEDS R1VAP 21
PRODUCTS COND 1 L / RECYCLE 20 L
P-SPEC 1 1.0
BLOCK STAGE1 RCSTR

DESCRIPTION "CAPROLACTAM POLYMERIZATION"
PARAM VOL=10. <cum> TEMP=260.0 PRES=1.0 NPHASE=2 PHASE=L &
PHASE-VOL=6.75 <cum> MB-MAXIT=350 MB-TOL=.000010 &
DAMP-FAC=.10
PRODUCTS R1-OLIGO L / R1VAP V
MOLE-FLOW MIXED CL 6.5
MOLE-FLOW MIXED H2O 1.6
MOLE-FLOW MIXED NYLON 10.5
MOLE-FLOW MIXED ACA 0.01

REACTIONS RXN-IDS=NYLON
BLOCK STAGE2 RCSTR

MB-MAXIT=350 MB-TOL=.000010 DAMP-FAC=.10
PRODUCTS R2-VAP V / R2-OLIGO L
MOLE-FLOW MIXED H2O .00280
MOLE-FLOW MIXED CL .03850
MOLE-FLOW MIXED ACA .00001610
MOLE-FLOW MIXED NYLON .137780
BLOCK PLUG RPLUG

PARAM TYPE=T-SPEC LENGTH=20. DIAM=1.85 PHASE=L PRES=1.40 &
NPOINT=20 INT-TOL=.000010 FLASH=YES
COOLANT TOL=.000010
T-SPEC 0.0 260.0 / 1.0 260.0
EO-CONV-OPTI
SENSITIVITY FLOW
DEFINE R1CL MASS-FLOW STREAM=R1-OLIGO SUBSTREAM=MIXED &
COMPONENT=CL
DEFINE R1NYL MASS-FLOW STREAM=R1-OLIGO SUBSTREAM=MIXED &
COMPONENT=NYLON
DEFINE R1MN COMP-ATTR-VAR STREAM=R1-OLIGO SUBSTREAM=MIXED &
COMPONENT=NYLON ATTRIBUTE=MWN ELEMENT=1
DEFINE R2CL MASS-FLOW STREAM=R2-OLIGO SUBSTREAM=MIXED &
COMPONENT=CL
DEFINE R2NYL MASS-FLOW STREAM=R2-OLIGO SUBSTREAM=MIXED &
COMPONENT=NYLON
DEFINE R2MN COMP-ATTR-VAR STREAM=R2-OLIGO SUBSTREAM=MIXED &
DEFINE R3MN COMP-ATTR-VAR STREAM=POLYMER SUBSTREAM=MIXED &
DEFINE R3CL MASS-FLOW STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=CL
DEFINE R3NYL MASS-FLOW STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=NYLON
DEFINE R3ACA MASS-FLOW STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=ACA
DEFINE R3CD MASS-FLOW STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=CD
DEFINE R3F STREAM-VAR STREAM=FEED SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE R1COND MASS-FLOW STREAM=COND SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE R3FW MASS-FRAC STREAM=R2-OLIGO SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE R2COND MASS-FLOW STREAM=R2-VAP SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE R2FW MASS-FRAC STREAM=R1-OLIGO SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE FWF MASS-FRAC STREAM=FEED SUBSTREAM=MIXED &

COMPONENT=H2O
DEFINE R3H2O MASS-FLOW STREAM=POLYMER SUBSTREAM=MIXED &
COMPONENT=H2O
F EV = (R3CL+R3H2O+R3ACA+R3CD)/R3F*100
TABULATE 1 "R1NYL/(R1NYL+R1CL)" COL-LABEL="R1-CONV"
TABULATE 4 "R1MN" COL-LABEL="R1-MN"
TABULATE 7 "EV" COL-LABEL="EXTRACTE"
TABULATE 8 "FWF*100." COL-LABEL="FEED WF" "WATER" "PERCENT."
TABULATE 9 "R2FW*100." COL-LABEL="R2OUT" "WATER" "PERCENT."
TABULATE 10 "R3FW*100." COL-LABEL="R3WF" "WATER" "PERCENT."
TABULATE 11 "R1COND" COL-LABEL="R1-COND"
TABULATE 12 "R2COND" COL-LABEL="R2-COND"
TABULATE 13 "R3CD"
TABULATE 14 "R3CL"
VARY STREAM-VAR STREAM=FEED SUBSTREAM=MIXED VARIABLE=MASS-FLOW
RANGE LOWER="1200" UPPER="9000" INCR="600"
CONV-OPTIONS
PARAM TRACE=.00010 CHECKSEQ=YES
WEGSTEIN MAXIT=50
STREAM-REPOR NOZEROFLOW MOLEFLOW MASSFLOW MASSFRAC
REACTIONS NYLON STEP-GROWTH

REAC-TYPES REARRANGE=NO EXCHANGE=NO
OPTIONS CONC-BASIS="MOL/KG"
SPECIES POLYMER=NYLON
REAC-GROUP TNH2 E-GRP / TCOOH N-GRP / BCAP EN-GRP
SG-RATE-CON 1 PRE-EXP=1.8940E+10 ACT-ENERGY=23.2710
SG-RATE-CON 2 CAT-SPEC=ACA PRE-EXP=1.2110E+10 &
ACT-ENERGY=20.670
SG-RATE-CON 3 CAT-SPEC=T-COOH PRE-EXP=1.2110E+10 &
ACT-ENERGY=20.670
SG-RATE-CON 4 PRE-EXP=1.1780E+10 ACT-ENERGY=29.21680
SG-RATE-CON 5 CAT-SPEC=ACA PRE-EXP=7.5340E+09 &
ACT-ENERGY=26.61580
SG-RATE-CON 6 CAT-SPEC=T-COOH PRE-EXP=7.5340E+09 &
ACT-ENERGY=26.61580
RXN-SET 1 ELECTRO-GRP=TNH2 NUCLEO-GRP=TCOOH RC-SETS=1 2 3
RXN-SET 2 NUCLEOPHILE=H2O RC-SETS=4 5 6
SPECIES-GRP T-NH2 TNH2 1 / T-NH2 BCAP 1 / T-COOH TCOOH &
1 / T-COOH BCAP 1 / ACA TNH2 1 / ACA TCOOH 1 / &
ACA BCAP 1 / B-ACA BCAP 1 / H2O TNH2 1 / H2O TCOOH 1
STOIC 1 CL -1.0 / H2O -1.0 / ACA 1.0
STOIC 2 ACA -1.0 / CL 1.0 / H2O 1.0
STOIC 3 CL -1.0 / B-ACA 1.0
STOIC 4 B-ACA -1.0 / CL 1.0
STOIC 5 CL -1.0 / ACA -1.0 / T-NH2 1.0 / T-COOH 1.0
STOIC 6 T-NH2 -1.0 / T-COOH -1.0 / ACA 1.0 / CL 1.0
STOIC 7 CD -1.0 / H2O -1.0 / T-NH2 1.0 / T-COOH 1.0
STOIC 8 T-NH2 -1.0 / T-COOH -1.0 / CD 1.0 / H2O 1.0
STOIC 9 CD -1.0 / B-ACA 2.0
STOIC 10 B-ACA -2.0 / CD 1.0

STOIC 11 CD -1.0 / ACA -1.0 / T-NH2 1.0 / T-COOH 1.0 / B-ACA 1.0
STOIC 12 T-NH2 -1.0 / T-COOH -1.0 / B-ACA -1.0 / ACA &
1.0 / CD 1.0
RATE-CON 1 598740.0 19.880 0.0
RATE-CON 2 4.3080E+07 18.8060 0.0 CATALYST=ACA
RATE-CON 3 4.3080E+07 18.8060 0.0 CATALYST=T-COOH
RATE-CON 4 3.1660E+07 17.9620 0.0
RATE-CON 7 2.8560E+09 22.8450 0.0
RATE-CON 10 9.4200E+10 26.8880 0.0
RATE-CON 13 8.5800E+11 42.0 0.0
RATE-CON 16 1.2800E+15 51.60 0.0
RATE-CON 19 2.5700E+08 21.30 0.0
RATE-CON 22 1.9200E+08 24.50 0.0
POWLAW-EXP 1 CL 1.0 / H2O 1.0
POWLAW-EXP 2 ACA 1.0
POWLAW-EXP 3 CL 1.0 / T-NH2 1.0
POWLAW-EXP 4 T-NH2 1.0
POWLAW-EXP 5 CL 1.0 / ACA 1.0
POWLAW-EXP 7 CD 1.0 / H2O 1.0
POWLAW-EXP 9 CD 1.0 / T-NH2 1.0
POWLAW-EXP 10 T-NH2 1.0
POWLAW-EXP 11 CD 1.0 / ACA 1.0
ASSIGN-URC 1 RC-SETS=1 2 3

The following three figures show the effect of feed flow rate on caprolactam
conversion, number-average molecular weight (Mn), and extraction value.
Increasing the feed to CSTR-1 decreases the total residence time. Therefore,
caprolactam conversion decreases in all of the reactors as shown here:
0.84 0.86 0.88 0.92
0.9
CL Conversion
Stage 1
0.82
Stage 2
Product
1000 2000 3000 4000 5000 6000 7000 8000 9000

As flow rate increases, the reactor residence time decreases. The average
molecular weight of the polymer at each point in the reactor decreases with
the residence time.
22000
Number Average Molecular Weight (Mn)
Stage 1
Stage 2
20000
Product
16000 18000
1000 2000 3000 4000 5000 6000 7000 8000 9000

Extraction value (EV) is the sum of the extractables from the polymer. These
include unreacted caprolactam, aminocaproic acid, cyclic dimer and water.
Extraction value is an indicator of the cost of recycling unreacted monomers.
Since conversion decreases with an increase in feed flow rate, EV increases.
Therefore, one has to find the optimum feed flow rate that increases the
production rate while minimizing the percentage of extractables.
The effect of feed flow rate on extraction value is shown here:

9.25
Percent Extractables
9.15 9.2
1000 2000 3000 4000 5000 6000 7000 8000 9000


The summary report for the flowsheet streams in the base case simulation is
shown here:
STREAM ID COND FEED POLYMER R1-OLIGO R1VAP

FROM : DISTIL ---- PLUG STAGE1 STAGE1
TO : ---- STAGE1 ---- STAGE2 DISTIL
SUBSTREAM: MIXED
PHASE: LIQUID LIQUID LIQUID LIQUID VAPOR
COMPONENTS: KMOL/HR
H2O 1.4138 1.9983 0.4199 0.4074 3.1676
CL 0.0 31.4954 2.5820 4.3448 1.0059
ACA 0.0 0.0 9.3725-04 1.3062-03 0.0
CD 0.0 0.0 0.1336 9.1208-02 0.0
NYLON 0.0 0.0 28.6715 26.9949 0.0
COMPONENTS: KG/HR
H2O 25.4704 36.0000 7.5647 7.3389 57.0643
CL 0.0 3564.0000 292.1742 491.6540 113.8274
ACA 0.0 0.0 0.1229 0.1713 0.0
CD 0.0 0.0 30.2269 20.6420 0.0
NYLON 0.0 0.0 3244.4503 3054.7330 0.0
H2O 1.0000 1.0000-02 2.1163-03 2.0531-03 0.3339
CL 0.0 0.9900 8.1738-02 0.1375 0.6661
ACA 0.0 0.0 3.4394-05 4.7932-05 0.0
CD 0.0 0.0 8.4562-03 5.7747-03 0.0
NYLON 0.0 0.0 0.9077 0.8546 0.0
TOTAL FLOW:
KMOL/HR 1.4138 33.4937 31.8078 31.8396 4.1735
KG/HR 25.4704 3600.0000 3574.5391 3574.5392 170.8917
L/HR 26.4708 4128.3629 4076.1662 4082.4945 1.8156+05

STATE VARIABLES:
TEMP C 100.0178 260.0000 260.0000 260.0000 260.0000
PRES ATM 1.0000 1.0000 1.4000 1.0000 1.0000
VFRAC 0.0 0.0 0.0 0.0 1.0000
LFRAC 1.0000 1.0000 1.0000 1.0000 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
KCAL/MOL -66.9095 -60.9440 -33.5836 -35.2702 -54.0250
J/KG -1.5550+07 -2.3740+06 -1.2512+06 -1.3153+06 -5.5240+06
WATT -1.1002+05 -2.3740+06 -1.2423+06 -1.3060+06 -2.6222+05
ENTROPY:
KCAL/MOL-K -3.4934-02 -0.1333 -0.1249 -0.1257 -3.1706-02
J/KG-K -8118.6922 -5190.5311 -4652.7256 -4689.3221 -3241.8948
DENSITY:
KMOL/CUM 53.4106 8.1131 7.8034 7.7991 2.2987-02
KG/CUM 962.2076 872.0164 876.9365 875.5772 0.9413
AVG MW 18.0153 107.4830 112.3792 112.2671 40.9473
NYLON SFLOW
T-NH2 MISSING MISSING 0.1637 0.1758 MISSING
T-COOH MISSING MISSING 0.1637 0.1758 MISSING
B-ACA MISSING MISSING 28.3181 26.6153 MISSING
ZMOM
ZMOM MISSING MISSING 0.1637 0.1758 MISSING
FMOM
FMOM MISSING MISSING 28.6454 26.9669 MISSING
DPN
DPN MISSING MISSING 175.0405 153.3812 MISSING
MWN
MWN MISSING MISSING 1.9826+04 1.7375+04 MISSING
EFRAC
T-NH2 MISSING MISSING 0.5000 0.5000 MISSING
T-COOH MISSING MISSING 0.5000 0.5000 MISSING
SFRAC
T-NH2 MISSING MISSING 5.7130-03 6.5197-03 MISSING
T-COOH MISSING MISSING 5.7130-03 6.5197-03 MISSING
B-ACA MISSING MISSING 0.9886 0.9870 MISSING
R2-OLIGO R2-VAP RECYCLE

-----------------------
STREAM ID R2-OLIGO R2-VAP RECYCLE

FROM : STAGE2 STAGE2 DISTIL
TO : PLUG STAGE1 STAGE1
MAX CONV. ERROR: 0.0 0.0 -8.2523-05

SUBSTREAM: MIXED
PHASE: LIQUID MISSING LIQUID
COMPONENTS: KMOL/HR
H2O 0.4130 0.0 1.7537
CL 2.6584 0.0 1.0060
ACA 9.4242-04 0.0 0.0
CD 0.1232 0.0 0.0
NYLON 28.6169 0.0 0.0
COMPONENTS: KG/HR
H2O 7.4394 0.0 31.5941

CL 300.8186 0.0 113.8368
ACA 0.1236 0.0 0.0
CD 27.8857 0.0 0.0
NYLON 3238.2718 0.0 0.0
H2O 2.0812-03 MISSING 0.2172
CL 8.4156-02 MISSING 0.7828
ACA 3.4584-05 MISSING 0.0
CD 7.8012-03 MISSING 0.0
NYLON 0.9059 MISSING 0.0
TOTAL FLOW:
KMOL/HR 31.8123 0.0 2.7597
KG/HR 3574.5391 0.0 145.4309
L/HR 4077.5613 0.0 142.7860
STATE VARIABLES:
TEMP C 260.0000 MISSING 116.5236
PRES ATM 1.2000 MISSING 1.0000
VFRAC 0.0 MISSING 0.0
LFRAC 1.0000 MISSING 1.0000
SFRAC 0.0 MISSING 0.0
ENTHALPY:
KCAL/MOL -33.6554 MISSING -67.3955
J/KG -1.2540+06 MISSING -5.3545+06
WATT -1.2452+06 MISSING -2.1631+05
ENTROPY:
KCAL/MOL-K -0.1250 MISSING -7.7525-02
J/KG-K -4656.2050 MISSING -6159.2868
DENSITY:
KMOL/CUM 7.8018 MISSING 19.3277
KG/CUM 876.6365 MISSING 1018.5232
AVG MW 112.3633 MISSING 52.6976
NYLON SFLOW
T-NH2 0.1706 0.0 0.0
T-COOH 0.1706 0.0 0.0
B-ACA 28.2485 0.0 0.0
ZMOM
ZMOM 0.1706 0.0 0.0
FMOM
FMOM 28.5897 MISSING MISSING
DPN
DPN 167.5852 MISSING MISSING
MWN
MWN 1.8982+04 MISSING MISSING
EFRAC
T-NH2 0.5000 MISSING MISSING
T-COOH 0.5000 MISSING MISSING
SFRAC
T-NH2 5.9671-03 MISSING MISSING
T-COOH 5.9671-03 MISSING MISSING
B-ACA 0.9881 MISSING MISSING

References
Gupta, A. K., & Gandhi, K. S. (1985). Modeling of Backmixing in Continuous
Polymerization of Caprolactam in VK Column Reactors. Ind. Eng. Chem.
Product Research and Development, 24, p. 327.
Hotyzer P. J., Hoogschagen, J., & Van Krevelen, D. W. (1965). Optimization of
Caprolactam Polymerization. Chem. Eng. Sci., 20, p. 247.
Reimschuessel H. K. (1977). Nylon 6: Chemistry and Mechanisms. J.
Polymerization Sci.: Macromolecular Reviews, 12, p. 65.
Tai K., Arai, Y., & Tagawa, T. (1982). The Simulation of Hydrolytic
Polymerization of Caprolactam in Various Reactors. J. Appl. Polymer Sci., 22,
p. 731.
Tai K., & Tagawa, T. (1983). Simulation of Hydrolytic Polymerization of
Caprolactam in Various Reactors. A review on recent advances in reaction
engineering of polymerization. Industrial & Engineering Chemistry Research,
22, p. 192.

B10 Methyl Methacrylate
Polymerization in Ethyl
Acetate
The methyl methacrylate polymerization in ethyl acetate model illustrates the

use of Aspen Polymers to model a solution polymerization process for methyl
methacrylate in ethyl acetate. Among the studies carried out using this model
are the effect of initiator concentration and reactor temperature on molecular
weight and conversion.
About This Process

Polymethyl methacrylate is part of the polyacrylic group of polymers. It is
used in the manufacture of lenses or other clear coverings and is also known
under the trade names plexiglass, lucite, acrylate, etc.
This methyl methacrylate polymerization is carried out in a free-radical
solution process. Solution polymerization is used when both the monomer and
the initiator are soluble in the solvent. Typically, solution processes result in
low viscosity, provide good mixing, and improve heat transfer limitations,
while improving temperature control and reducing gel effect. On the other
hand, these processes result in lower reaction rate and in lower polymer
molecular weight due to chain transfer to solvents. Furthermore, solvent
removal can be costly.
The flowsheet for this process consists of a batch reactor followed by a
devolatizer for solvent removal. The reactor feed contains methyl
methacrylate dissolved in ethyl acetate, with AIBN as the initiator. The
reactor operates under constant temperature and pressure.
Process Definition
The batch reactor is modeled using RBatch, and the devolitizer using Flash2:
B10 Methyl Methacrylate Polymerization in Ethyl Acetate 219

Process Conditions
Methyl-methacrylate MMA PURE12 Monomer

Ethyl-acetate EA PURE12 Solvent
Polymethylmethacrylate PMMA POLYMER Polymer
MMA-R SEGMENT Methyl methacrylate
segment
AIBN AIBN PURE12 Initiator (Mw=164.210)
Physical Properties POLYNRTL property method with supplied parameters
Feed Streams
Temperature (C) 0
Pressure (atm) 1
Methylmethacrylate 100 (25 wt%)
(kg/h)
Ethyl Acetate (kg/hr) 300 (75 wt%)
Initiator (kg/hr) 3.757
The feed is sent to RBATCH as a batch feed
Operating Conditions RBATCH FLASH
Pressure 1 atm 100 mmHg
220 B10 Methyl Methacrylate Polymerization in Ethyl Acetate

Reactors / Kinetics
The kinetic parameters of solution polymerization of methyl methacrylate are
available in literature (Ellis et al., 1988). The reactions used in this model and
their rate constant parameters are:
Description k0 Ea (J/Kmol) Efficiency
Initiator decomposition 1.2525E14 1.228E8 0.5

Chain initiation 4.92E5 1.824E7 ---
Propagation 4.92E5 1.82E7 ---
Chain transfer to monomer 7.177E9 7.513E7 ---
Chain transfer to solvent 4.673E8 6.57E7 ---
Termination by disproportionation 9.8E7 2.937E6 ---
Because of the presence of a large amount of solvents (75% by weight), gel-

effect is not significant and is therefore not considered. At high monomer
conversion, gel-effect can be used to improve the agreement between the
model predictions and experimental data.
In the batch reactor two reactor stop conditions are provided: stop after 5
hours of reaction time, or stop at 99% monomer conversion (corresponds to
PMMA mass fraction of 0.2452). The first option is used to obtain conversion
and polymer molecular weight information as a function of time. The second
option is used to examine the effect of temperature and initiator
concentration of PMMA properties at a given conversion.
Process Studies
The PMMA process model is used to examine process variables such as
conversion number and weight average molecular weight as a function of
time, at three different reactor temperatures. The model predictions are
compared against literature data (Ellis, 1990).
The model is also used to study the effects of initiator concentration and
polymerization temperature on the following: reaction time to reach 99%
monomer conversion, peak heat load, number and weight average molecular
weight.
A sensitivity study is also performed to show the percent solids as a function
of outlet temperature.
Input Summary
DYNAPLUS
DPLUS RESULTS=ON
TITLE 'Polymerization of MMA'
IN-UNITS MET

DESCRIPTION "
Polymerization of methyl methacrylate(MMA) in a batch.
reactor "
COMPONENTS
MMA C5H8O2-D3 /
EA C4H8O2-3 /
AIBN C5H8O2-D3 /
PMMA PMMA /
MMA-R C5H8O2-R-1
FLOWSHEET
BLOCK FLASH IN=PROD OUT=FV FL
BLOCK RBATCH IN=FEED OUT=PROD
PROPERTIES POLYNRTL
PROP-DATA MW
IN-UNITS MET
PROP-LIST MW
PVAL AIBN 164.210
POLYMERS
SEGMENTS MMA-R REPEAT
POLYMERS PMMA
ATTRIBUTES PMMA SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM &
LEFRAC LPFRAC
DISTRIBUTION PMMA CHAIN-SIZE CLD NPOINTS=100 UPPER=10000.
PROP-SET PS-1 MASSFRAC SUBSTREAM=MIXED COMPS=PMMA MMA EA &

PHASE=L
PROP-SET PS-2 MOLECONC UNITS='kmol/cum' SUBSTREAM=MIXED &

COMPS=AIBN PHASE=L
PROP-SET PS-3 MOLECONC UNITS='kmol/cum' SUBSTREAM=MIXED &

COMPS=AIBN MMA PHASE=L
STREAM FEED
MASS-FLOW MMA 100.0 / EA 300.0 / AIBN 3.7570
BLOCK FLASH FLASH2

PARAM TEMP=333.150 PRES=.131578947
BLOCK RBATCH RBATCH

PARAM TYPE=T-SPEC PRINT-TIME=.50 CYCLE-TIME=1.0 &
MAX-TIME=100.0 MAX-NPOINT=202 PRES=1.0 TEMP=323.0
STOP 1 REACTOR MASS-FRAC .24520 FROM-BELOW COMP=PMMA &

SSID=MIXED
PROP-REACTOR PS-1
REACTIONS RXN-IDS=REAC-1
EO-CONV-OPTI
CALCULATOR F-1
DEFINE FTEMP STREAM-VAR STREAM=FEED SUBSTREAM=MIXED &
VARIABLE=TEMP
DEFINE RTEMP BLOCK-VAR BLOCK=RBATCH VARIABLE=TEMP &
SENTENCE=PARAM
F FTEMP = RTEMP
EXECUTE BEFORE BLOCK RBATCH
CONV-OPTIONS
PARAM CHECKSEQ=NO
STREAM-REPOR MOLEFLOW MASSFLOW PROPERTIES=PS-2 PS-3
REACTIONS REAC-1 FREE-RAD

IN-UNITS SI
PARAM
SPECIES INITIATOR=AIBN MONOMER=MMA SOLVENT=EA POLYMER=PMMA
MON-RSEG MMA MMA-R
INIT-DEC AIBN 1.2525E+14 1.2280E+08 EFFIC=.50
CHAIN-INI MMA 492000.0 1.8240E+07
PROPAGATION MMA MMA 492000.0 1.8240E+07
CHAT-MON MMA MMA 7.1770E+09 7.5130E+07
CHAT-SOL MMA EA 4.6730E+08 6.5700E+07
TERM-DIS MMA MMA 9.8000E+07 2937000.0

The mass flow of PMMA versus the time is shown here:
100
T = 323K
80 T = 333K
PMMA Mass (Kg)
T = 338K
60 T = 343K
40
20
0
0 1 2 3 4 5
Time (Hr)

The mass flow of PMMA is equivalent to monomer conversion versus time
since the feed rate is 100 kg/hr. As shown, at high temperature, over 90% of
monomers are converted within 5 hours, while at low temperature (50C),
only 40% of monomers are converted. These results are within 1% deviation
from literature simulation results (Ellis, 1988).
The PMMA number-average molecular weight versus time at different reacting
temperatures is shown here:
70000
60000
T = 323K
50000
T = 333K
PMMA MWN
T = 338K
40000
T = 343K
30000
20000
10000
0
0 1 2 3 4 5
Time (Hr)
As temperature increases, the number-average molecular weight of PMMA

decreases. The Aspen Polymers predictions agree closely with literature
simulation. At high monomer conversion, the addition of gel-effect is needed
to improve agreement between the predictions and experimental data.
The reaction time, in hours, needed to reach 99% monomer conversion at
various temperatures and initiator charges is shown here:
50
45 AIBN Charge = 3
Time for 99% Conversion
40
AIBN Charge = 3.757
35
AIBN Charge = 6
30
AIBN Charge = 10
25
20
15
10
5
0
320 325 330 335 340 345 350 355
Temperature (K)

The different curves correspond to different initiator charges. At a particular
initiator charge, the reaction time decreases with temperature. At constant
temperature, the reaction time decreases as the initiator charge (and hence
concentration) increases. Therefore, higher reaction temperature and initiator
concentration allow faster monomer conversion.
The following two figures show the molecular weight dependency of
temperature and initiator charge. In general, both the number and weight-
average molecular weight increase as temperature increases and initiator
charge decreases. The ratio of Mw and Mn gives the polydispersity index
(PDI).
MWn at 99% conversion versus temperature and initiator charge is shown
here:
25000
AIBN Charge = 3
20000 AIBN Charge = 3.757
MWN at 99% Conversion
AIBN Charge = 6
15000 AIBN Charge = 10
10000
5000
0
320 325 330 335 340 345 350 355
Temperature (K)
MWw at 99% conversion versus temperature and initiator charge is shown

here:

90000
80000 AIBN Charge = 3
AIBN Charge = 3.757
MWW at 99% Conversion

70000
AIBN Charge = 6
60000
AIBN Charge = 10
50000
40000
30000
20000
10000
0
320 325 330 335 340 345 350 355
Temperature (K)
The PMMA polydispersity index is shown here:
4.4
4.2 AIBN Charge = 3

AIBN Charge = 3.757
PDI at 99% Conversion
4
AIBN Charge = 6
3.8 AIBN Charge = 10
3.6
3.4
3.2
2.8
320 325 330 335 340 345 350 355
Temperature (K)
As shown, at a given conversion, PDI decreases as temperature increases,

and increases as initiator charge increases.
The maximum in the reactor instantaneous heat duty as a function of reactor
temperature and initiator concentration is shown here:

Te mpe rature (K)
320 325 330 335 340 345 350 355
0
-500
Max. Duty (cal/s)
-1000
-1500 AIBN Charge = 3

AIBN Charge = 3.757
-2000 AIBN Charge = 6
AIBN Charge = 10
-2500
For the case of a reactor with specified temperature, the maximum heat duty
occurs immediately after reactions start. In the simulation results presented
above, the heat duty reported at 0.5 hr is taken to be the maximum. This is
the second profile point computed when the time interval is set to 0.5 hour.
Technically it is not the true peak heat duty. Smaller time intervals between
profile points may be used to obtain more accurate peak heat duty.
The results of the sensitivity study on the flash block are shown here:
0.96
0.94
PMMA Mass Fraction
0.92
0.9
0.88
0.86
0.84
320 325 330 335 340 345 350 355
Flash Temperature (K)
As the flash temperature varies, the polymer content in the liquid output
stream changes accordingly. No binary parameters are used in the polymer
NRTL model. If liquid-vapor equilibria data is available, the binary parameters
may be fitted to allow more accurate predictions.

References
Ellis, M. F., Taylor, T. W. X., Gonzalez, V., & Jensen, K. F. (1988). Estimation
of the Molecular Weight Distribution in Batch Polymerization. AIChE J., 34, p.
1341.
Ellis, M. F. (1990). Online Control and Estimation of the Molecular Weight
Distribution in a Batch Polymerization Reactor. PhD Thesis, Dept. of Chem.
Engr., Univ. of Minn.
Grulke, E. A. (1994). Polymer Process Engineering. New Jersey: Prentice Hall.
Tulig, T. J., & Tirrell, M. (1981). Toward a Molecular Theory of the
Trommsdorff Effect. Macromolecules, 14, p. 1501.

B11 Polypropylene Gas
Phase Polymerization
Processes
The polypropylene gas-phase polymerization process model illustrates the use

of Aspen Polymers to model a gas-phase UNIPOL process for propylene
homopolymerization using a four site Ziegler-Natta kinetic model. The atactic
content, melt flow ratio and molecular weight averages are some of the
polymer product properties and attributes predicted by the simulation.
About This Process

There are three types of processes commonly employed for the manufacture
of isotactic polypropylene (PP) homo- and co-polymers. These include liquid
slurry processes, bulk or liquid pool processes, and gas-phase processes. The
following table provides basic information on these processes and lists some
of the companies that have commercialized the process technology:
Process Reactor Diluent / Catalyst Tacticity Temp. Press. Residence Company
Solvent (%) (C) (atm) Time (hr)
Bulk Loop reactor Liquid Supported Ti up tp 60-80 30-40 1-2 Himont

(Liquid monomer Catalyst 99% Mitsui
Pool)
CSTR Liquid Unsupported up to 60-75 30-40 2.0 Dart
monomer or supported 98% El Paso
Ti catalyst Montedison
Sumitomo
Diluent CSTR n-hexane, Unsupported up to 60-80 15-20 3-4 Amoco
Slurry n-heptane or supported 98% Montedison
Ti catalyst
Gas Fluidized bed N2 Supported Ti up to 60-80 20 3-5 Sumitomo
catalyst 98% Union Carbide
Vertical stirred --- Unsupported up to 70-90 20 4 BASF
bed or supported 98% ICI
Ti catalyst USI
Horizontal --- Unsupported up to 70-90 20 4 Amoco
B11 Polypropylene Gas Phase Polymerization Processes 229

Process Reactor Diluent / Catalyst Tacticity Temp. Press. Residence Company
Solvent (%) (C) (atm) Time (hr)
compartmented or supported 98%
stirred bed Ti catalyst
All of these processes use a Ziegler-Natta catalyst (usually TiCl4) in either a

supported or non-supported form together with an alkylaluminum or
aluminum chlorides (for example, triethyl-aluminum) cocatalyst.
Liquid slurry processes use an inert hydrocarbon diluent as the slurry medium
or polymer suspending agent. This process is still the most widely used
process for PP manufacture. Continuous stirred tank reactors are usually used
and several reactors may be used in series or parallel arrangements. Typical
reactor operating conditions and residence times were listed in the previous
table.
Bulk or liquid pool processes are a special case of the slurry processes. They
use liquid propylene instead of an inert diluent as the slurry medium to
suspend the polymer. The increased monomer concentration leads to higher
polymerization rates in liquid pool processes relative to slurry processes.
Hence, shorter reactor residence times may be employed. Several reactor
types, including stirred autoclaves with evaporative cooling and loop reactors,
are used to attain good heat transfer rates.
In gas-phase processes, gaseous propylene is contacted with solid
catalyst/polymer powder in fluidized bed or mechanically stirred bed reactors.
The reactor temperature is usually controlled by evaporative cooling of liquid
propylene. The unreacted monomer is removed from the reactor headspace,
condensed or cooled and recirculated to the reactor.
Aspen Polymers can be used with Aspen Plus for the simulation of steady-
state operation of any of the PP processes described above. Aspen Polymers
can be used with Aspen Custom Modeler when dynamic simulation or detailed
modeling of the flow patterns or heat transfer within the reactor is desired.
This example describes a steady-state simulation of a gas-phase UNIPOL
flowsheet.
Process Definition
An Aspen Polymers model is developed to simulate a PP gas-phase UNIPOL
flowsheet. The flowsheet includes the fluidized bed reactor, the gas
recycle/cooling loop, discharge, and purge units:
230 B11 Polypropylene Gas Phase Polymerization Processes

The fluidized bed reactor is modeled using the CSTR reactor in Aspen Plus
with two phases: a gas phase and a polymer phase. The POLYPCSF (PCSAFT)
thermodynamic model is used to relate the gas phase monomer, hydrogen,
etc. composition to their concentrations in the polymer phase. The multisite
Ziegler-Natta kinetic model is used to describe the polymerization reactions in
the polymer phase. The kinetic model calculates the reaction rates for the
components and polymer attributes at each site type. User-Property models
are used to calculate polymer properties such as melt flow index (MFI),
isotactic index (or atactic fraction) from the polymer attributes.
Process Conditions
Components
Titanium Tetrachloride (CAT) Catalyst

Triethyl-Aluminium (COCAT) Co-catalyst
Propylene (C3=) Monomer
Propane (C3) Inert
Polypropylene (PP) Polymer
H2 Chain transfer agent
N2 Inert
Water (H2O) Cooling water
Propylene Segment (C3-SEG) Polymer segment
Component Flow rate (Kg/Hr)

Catalyst 3.0
Co-catalyst 10.0
Propylene 17462.0
Propane 162.29
H2 1.38
N2 1.45
Operating Conditions
Temperature 69 C
Pressure drop 200 KPa
Total volume 90 m3
Polymer Phase volume 60 m3
The reactor feed also includes a large recycle stream with partially condensed
propylene and other volatile components.
An Aspen Plus CSTR reactor model is used to represent the fluid-bed reactor.
The reactor is considered to have two phases; a vapor phase and a polymer
phase.

The polymer PCSAFT equation of state model (POLYPCSF) is used as the
physical property method.
Reactors / Kinetics
The Ziegler-Natta kinetic scheme used in the model includes spontaneous site
activation, chain initiation, propagation, chain transfer to hydrogen, monomer
and co-catalyst, and spontaneous site deactivation. Four site types are used
in this example to represent the broad molecular weight distributions that are
typically observed for Ziegler-Natta polymers. The actual number of site types
necessary to model a given catalyst-polymerization system is determined by
deconvolution of the polymer molecular weight distribution curve obtained
from a GPC analysis.
The rate parameters used in the model are:
Reaction Site ID Comp. ID Comp. ID Pre- Activation Order Ref.
1 2 exp Energy Temp.
(kcal/mol) (C)
ACT-SPON 1 TICL4 0.0013 7.64 1 69

ACT-SPON 2 TICL4 0.0013 7.64 1 69
ACT-SPON 3 TICL4 0.0013 7.64 1 69
ACT-SPON 4 TICL4 0.0013 7.64 1 69
CHAIN-INI 1 C3H6 108.85 7.2 1 69
CHAIN-INI 2 C3H6 24.5 7.2 1 69
CHAIN-INI 3 C3H6 170.8 7.2 1 69
CHAIN-INI 4 C3H6 60.55 7.2 1 69
PROPAGATION 1 C3H6 C3H6 108.85 7.2 1 69
CHAT-MON 1 C3H6 C3H6 0.012 12.42 1 69
CHAT-MON 2 C3H6 C3H6 0.012 12.42 1 69
CHAT-MON 3 C3H6 C3H6 0.012 12.42 1 69
CHAT-MON 4 C3H6 C3H6 0.012 12.42 1 69
CHAT-COCAT 1 C3H6 TEA 0.12 12 1 69
CHAT-H2 1 C3H6 H2 4.8 10.7 0.5 69
CHAT-H2 2 C3H6 H2 8.88 10.7 0.5 69
CHAT-H2 3 C3H6 H2 2.64 10.7 0.5 69
CHAT-H2 4 C3H6 H2 6.6 10.7 0.5 69
DEACT-SPON 1 0.001 1 1 69
DEACT-SPON 2 0.001 1 1 69

Reaction Site ID Comp. ID Comp. ID Pre- Activation Order Ref.
1 2 exp Energy Temp.
(kcal/mol) (C)
DEACT-SPON 3 0.001 1 1 69
DEACT-SPON 4 0.001 1 1 69
ATACT-PROP 1 C3H6 C3H6 13.2 7.2 1 69
ATACT-PROP 2 C3H6 C3H6 31.8 7.2 1 69
ATACT-PROP 3 C3H6 C3H6 8 7.2 1 69
ATACT-PROP 4 C3H6 C3H6 18.5 7.2 1 69
The units for the frequency factor and activation energy are in SI units.
Process Studies
Input Summary
TITLE 'Ziegler-Natta Gas-Phase Polymerization of Propylene'
IN-UNITS SI MASS-FLOW='kg/hr' MOLE-FLOW='kmol/hr' TEMPERATURE=C &

TIME=hr DELTA-T=C
SIM-OPTIONS
VOLUME-FLOW='cum/hr' PRESSURE=kPa TEMPERATURE=C TIME=hr &
PDROP=kPa
SIM-OPTIONS FLASH-TOL=1E-006
DESCRIPTION "
Ziegler-Natta gas-Phase polymerization of propylene
"
COMPONENTS
TICL4 TICL4 /
TEA C6H15AL /
C3H6 C3H6-2 /
C3H8 C3H8 /
PP PP /
H2 H2 /
N2 N2 /

H2O H2O /
C3H6-R C3H6-R
FLOWSHEET
BLOCK REACTOR IN=RFEED1 OUT=VAP-A POWDER1
BLOCK FMIX1 IN=CAT COCAT H2FEED C3FEED N2FEED CYCGAGB &
OUT=RFEED1
BLOCK EXC1 IN=H2O-IN VAP-B OUT=H2O-OUT CYCGAGB
BLOCK COMP1 IN=VAP-A OUT=VAP-B
BLOCK STRIP1 IN=POWDER1 OUT=GAS1 POWDER2
BLOCK STRIP2 IN=POWDER2 STRIP-N2 OUT=GAS2 PP-PROD
PROPERTIES POLYPCSF
PROP-DATA PCSAFT
TEMPERATURE=C TIME=hr DELTA-T=C
PROP-LIST PCSFTM
PVAL TICL4 20
PVAL TEA 20
PROP-LIST PCSFTV
PVAL C3H6-R 4.1473
POLYMERS
PARAM NSITES=4
CATALYST TICL4 0.00045
POLYMERS PP
ATTRIBUTES PP SFRAC SFLOW DPN DPW PDI MWN MWW ZMOM FMOM &
LPFRAC SSFRAC SSFLOW SDPN SDPW SPDI SMWN SMWW SZMOM &
SFMOM SSMOM SPFRAC LSDPN LSZMOM LSFMOM LSSFLOW LSSFRAC &
LSEFLOW LSEFRAC LSPFRAC ATFLOW ATFRAC SATFLOW SATFRAC
ATTRIBUTES TICL4 CPSFLOW CPSFRAC CVSFLOW CVSFRAC CDSFLOW &
CDSFRAC
DISTRIBUTION PP
STREAM C3FEED
PDROP=kPa
MASS-FRAC C3H6 .9980 / C3H8 .0020
STREAM CAT
PDROP=kPa
NPHASE=1 PHASE=L
MASS-FRAC TICL4 .010 / C3H6 .9880 / C3H8 .0020
COMP-ATTR TICL4 CVSFLOW ( 0.0 0.0 0.0 0.0 )

STREAM COCAT
PDROP=kPa
NPHASE=1 PHASE=L
MASS-FRAC TEA 1.0
STREAM CYCGAGB
PDROP=kPa
MASS-FLOW C3H6 800300.0 / C3H8 15930.0 / H2 3998.70 / &
N2 5098.0
STREAM H2FEED
PDROP=kPa
MASS-FRAC H2 1.0
STREAM H2O-IN
PRESSURE=kPa TEMPERATURE=C TIME=hr DELTA-T=C PDROP=kPa
MASS-FLOW H2O 847500.0
STREAM N2FEED
PDROP=kPa
MASS-FRAC N2 1.0
STREAM RFEED1
MASS-FLOW TICL4 3.0 / TEA 10.0 / C3H6 817500.0 / C3H8 &
16100.0 / H2 4000.0 / N2 5100.0
COMP-ATTR TICL4 CVSFLOW ( 0.0 0.0 0.0 0.0 )
STREAM STRIP-N2
MASS-FLOW N2 500.0
BLOCK FMIX1 MIXER

PDROP=kPa
BLOCK STRIP1 FLASH2

BLOCK STRIP2 FLASH2

BLOCK EXC1 MHEATX

PDROP=kPa
COLD-SIDE IN=H2O-IN OUT=H2O-OUT TEMP=44. FREE-WATER=NO
HOT-SIDE IN=VAP-B OUT=CYCGAGB FREE-WATER=NO
BLOCK REACTOR RCSTR

USER-VECS NREAL=1
PARAM VOL=90.0 TEMP=69.0 PRES=-200.0 NPHASE=2 PHASE=L &
PHASE-VOL=60.0 MB-MAXIT=20 SCALING=COMPONENTS &
ALGORITHM=SOLVER
PRODUCTS VAP-A V / POWDER1 L
MASS-FLOW MIXED PP 15000.
BLOCK-OPTION SIM-LEVEL=8 TERM-LEVEL=7
BLOCK COMP1 COMPR

PDROP=kPa
PARAM TYPE=ISENTROPIC DELP=250.0
EO-CONV-OPTI
CALCULATOR SETFEED
DEFINE RC3E MASS-FLOW STREAM=CYCGAGB SUBSTREAM=MIXED &
COMPONENT=C3H6
DEFINE RC3 MASS-FLOW STREAM=CYCGAGB SUBSTREAM=MIXED &
COMPONENT=C3H8
DEFINE RH2 MASS-FLOW STREAM=CYCGAGB SUBSTREAM=MIXED &
COMPONENT=H2
DEFINE RN2 MASS-FLOW STREAM=CYCGAGB SUBSTREAM=MIXED &
COMPONENT=N2
DEFINE FC3E MASS-FLOW STREAM=C3FEED SUBSTREAM=MIXED &
COMPONENT=C3H6
DEFINE FC3 MASS-FLOW STREAM=C3FEED SUBSTREAM=MIXED &
COMPONENT=C3H8

DEFINE FN2 MASS-FLOW STREAM=N2FEED SUBSTREAM=MIXED &
COMPONENT=N2
DEFINE FH2 MASS-FLOW STREAM=H2FEED SUBSTREAM=MIXED &
COMPONENT=H2
DEFINE FTC3 STREAM-VAR STREAM=C3FEED SUBSTREAM=MIXED &
VARIABLE=TEMP
DEFINE FPC3 STREAM-VAR STREAM=C3FEED SUBSTREAM=MIXED &
VARIABLE=PRES
DEFINE FTH2 STREAM-VAR STREAM=H2FEED SUBSTREAM=MIXED &
VARIABLE=TEMP
DEFINE FPH2 STREAM-VAR STREAM=H2FEED SUBSTREAM=MIXED &
VARIABLE=PRES
DEFINE FTN2 STREAM-VAR STREAM=N2FEED SUBSTREAM=MIXED &
VARIABLE=TEMP
DEFINE FPN2 STREAM-VAR STREAM=N2FEED SUBSTREAM=MIXED &
VARIABLE=PRES
F DC3E = 8.172E5
F DC3 = 1.61E4
F DH2 = 4.0E3
F DN2 = 5.1E3
F FC3E = DC3E - RC3E
F FC3 = DC3 - RC3
F FH2 = DH2 - RH2
F FN2 = DN2 - RN2
F FTC3 = 30
F FPC3 = 3000
F FTH2 = 30
F FPH2 = 3000
F FTN2 = 30
F FPN2 = 3000
READ-VARS RC3E RC3 RH2 RN2
WRITE-VARS FC3E FC3 FN2 FH2 FTC3 FPC3 FTH2 FPH2 FTN2 &
FPN2
CONV-OPTIONS
PARAM CHECKSEQ=NO

IN-UNITS MET
PARAM
HYDROGEN=H2 POLYMER=PP
ACT-SPON 1 TICL4 0.0013 7.64 <kcal/mol> ORDER=1.0 REF-TEMP=69. <C>
CHAIN-INI 1 C3H6 108.85 7.2 <kcal/mol> ORDER=1.0 REF-TEMP=69. <C>
PROPAGATION 1 C3H6 C3H6 108.85 7.2 <kcal/mol> ORDER=1.0 REF-TEMP=69. <C>

CHAT-MON 1 C3H6 C3H6 0.012 12.42 <kcal/mol> ORDER=1.0 REF-TEMP=69. <C>
CHAT-COCAT 1 C3H6 TEA 0.12 12. <kcal/mol> ORDER=1.0 REF-TEMP=69. <C>
CHAT-H2 1 C3H6 H2 4.8 10.7 <kcal/mol> ORDER=.50 REF-TEMP=69. <C>
DEACT-SPON 1 0.001 1. <kcal/mol> ORDER=1.0 REF-TEMP=69. <C>
ATACT-PROP 1 C3H6 C3H6 13.2 7.2 <kcal/mol> REF-TEMP=69. <C>
ATACT-PROP 3 C3H6 C3H6 8. 7.2 <kcal/mol> REF-TEMP=69. <C>

The results include component mass flowrates, thermophysical information
(temperature, pressure, enthalpy, etc.) and catalyst and polymer attributes.
The polymer attributes are reported for the composite polymer and the
polymer made at each site type. The polymer atactic fraction and melt flow
ratio are reported at the end of the stream report.

The stream summary results for selected streams are shown here:
C3FEED CAT COCAT CYCGAGB GAS1

-----------------------------
STREAM ID C3FEED CAT COCAT CYCGAGB GAS1

FROM : ---- ---- ---- EXC1 STRIP1
TO : FMIX1 FMIX1 FMIX1 FMIX1 ----
SUBSTREAM: MIXED
PHASE: LIQUID LIQUID LIQUID MIXED VAPOR
COMPONENTS: KMOL/HR
TICL4 0.0 1.5815-02 0.0 0.0 0.0
TEA 0.0 0.0 8.7591-02 0.0 0.0
C3H6 481.8696 7.0436 0.0 1.8938+04 93.4567
C3H8 2.0007 1.3607-02 0.0 363.1075 1.8182
PP 0.0 0.0 0.0 0.0 0.0
H2 0.0 0.0 0.0 1983.2900 0.2875
N2 0.0 0.0 0.0 181.9875 6.7409-02
H2O 0.0 0.0 0.0 0.0 0.0
COMPONENTS: KG/HR

TICL4 0.0 3.0000 0.0 0.0 0.0
TEA 0.0 0.0 10.0000 0.0 0.0
C3H6 2.0277+04 296.4000 0.0 7.9692+05 3932.7172
C3H8 88.2250 0.6000 0.0 1.6012+04 80.1756
PP 0.0 0.0 0.0 0.0 0.0
H2 0.0 0.0 0.0 3998.0747 0.5796
N2 0.0 0.0 0.0 5098.1034 1.8883
H2O 0.0 0.0 0.0 0.0 0.0
TICL4 0.0 1.0000-02 0.0 0.0 0.0
TEA 0.0 0.0 1.0000 0.0 0.0
C3H6 0.9957 0.9880 0.0 0.9695 0.9794
C3H8 4.3321-03 2.0000-03 0.0 1.9478-02 1.9967-02
PP 0.0 0.0 0.0 0.0 0.0
H2 0.0 0.0 0.0 4.8637-03 1.4433-04
N2 0.0 0.0 0.0 6.2018-03 4.7028-04
H2O 0.0 0.0 0.0 0.0 0.0
TOTAL FLOW:
KMOL/HR 483.8703 7.0730 8.7591-02 2.1466+04 95.6298
KG/HR 2.0366+04 300.0000 10.0000 8.2203+05 4015.3608
CUM/SEC 1.1203-02 1.6602-04 1.5554-05 3.6892 0.1422
STATE VARIABLES:
TEMP C 30.0000 30.0000 30.0000 60.4597 65.0000
PRES N/SQM 3.0000+06 3.0000+06 3.0000+06 3.0500+06 5.0000+05
VFRAC 0.0 0.0 0.0 0.9501 1.0000
LFRAC 1.0000 1.0000 1.0000 4.9906-02 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL 4.0704+06 1.9775+06 2.3114+08 1.4874+07 1.9601+07
J/KG 9.6710+04 4.6624+04 2.0246+06 3.8841+05 4.6682+05
WATT 5.4710+05 3885.3294 5623.7639 8.8690+07 5.2069+05
ENTROPY:
J/KMOL-K -2.1278+05 -2.1338+05 -1.6270+06 -1.5446+05 -1.4871+05
J/KG-K -5055.4997 -5030.7049 -1.4252+04 -4033.4369 -3541.6804
DENSITY:
KMOL/CUM 11.9974 11.8340 1.5643 1.6163 0.1868
KG/CUM 504.9576 501.9360 178.5894 61.8946 7.8448
AVG MW 42.0890 42.4146 114.1666 38.2939 41.9886
TICL4 CPSFLOW
CPSFLOW MISSING 1.3500-03 MISSING MISSING MISSING
CPSFRAC
CPSFRAC MISSING 1.0000 MISSING MISSING MISSING
CVSFLOW
SITE_1 MISSING 0.0 MISSING MISSING MISSING
CVSFRAC
CDSFLOW
CDSFLOW MISSING 0.0 MISSING MISSING MISSING
CDSFRAC
CDSFRAC MISSING 0.0 MISSING MISSING MISSING

GAS2 H2FEED H2O-IN H2O-OUT N2FEED
---------------------------------
STREAM ID GAS2 H2FEED H2O-IN H2O-OUT N2FEED

FROM : STRIP2 ---- ---- EXC1 ----
TO : ---- FMIX1 EXC1 ---- FMIX1
SUBSTREAM: MIXED
PHASE: VAPOR VAPOR LIQUID LIQUID VAPOR
COMPONENTS: KMOL/HR
TICL4 0.0 0.0 0.0 0.0 0.0
TEA 0.0 0.0 0.0 0.0 0.0
C3H6 9.3084 0.0 0.0 0.0 0.0
C3H8 0.1833 0.0 0.0 0.0 0.0
PP 0.0 0.0 0.0 0.0 0.0
H2 4.1346-04 0.9551 0.0 0.0 0.0
N2 17.8059 0.0 0.0 0.0 6.7702-02
H2O 0.0 0.0 4.7043+04 4.7043+04 0.0
COMPONENTS: KG/HR
TICL4 0.0 0.0 0.0 0.0 0.0
TEA 0.0 0.0 0.0 0.0 0.0
C3H6 391.7052 0.0 0.0 0.0 0.0
C3H8 8.0813 0.0 0.0 0.0 0.0
PP 0.0 0.0 0.0 0.0 0.0
H2 8.3348-04 1.9253 0.0 0.0 0.0
N2 498.8065 0.0 0.0 0.0 1.8966
H2O 0.0 0.0 8.4750+05 8.4750+05 0.0
TICL4 0.0 0.0 0.0 0.0 0.0
TEA 0.0 0.0 0.0 0.0 0.0
C3H6 0.4359 0.0 0.0 0.0 0.0
C3H8 8.9932-03 0.0 0.0 0.0 0.0
PP 0.0 0.0 0.0 0.0 0.0
H2 9.2754-07 1.0000 0.0 0.0 0.0
N2 0.5551 0.0 0.0 0.0 1.0000
H2O 0.0 0.0 1.0000 1.0000 0.0
TOTAL FLOW:
KMOL/HR 27.2981 0.9551 4.7043+04 4.7043+04 6.7702-02
KG/HR 898.5939 1.9253 8.4750+05 8.4750+05 1.8966
CUM/SEC 0.2096 2.2702-04 0.2391 0.2412 1.5692-05
STATE VARIABLES:
TEMP C 60.0000 30.0000 35.0000 44.0000 30.0000
PRES N/SQM 1.0000+05 3.0000+06 3.0000+06 3.0000+06 3.0000+06
VFRAC 1.0000 1.0000 0.0 0.0 1.0000
LFRAC 0.0 0.0 1.0000 1.0000 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL 7.4863+06 1.8496+05 -2.8683+08 -2.8602+08 -4.6019+04
J/KG 2.2742+05 9.1750+04 -1.5921+07 -1.5877+07 -1642.7572
WATT 5.6767+04 49.0676 -3.7481+09 -3.7376+09 -0.8654
ENTROPY:
J/KMOL-K -3.9913+04 -2.7710+04 -1.6580+05 -1.6323+05 -2.8251+04
J/KG-K -1212.4972 -1.3746+04 -9203.5570 -9060.3732 -1008.4905
DENSITY:
KMOL/CUM 3.6182-02 1.1686 54.6449 54.1828 1.1985
KG/CUM 1.1910 2.3557 984.4427 976.1187 33.5736

AVG MW 32.9179 2.0159 18.0153 18.0153 28.0135
POWDER1 POWDER2 PP-PROD RFEED1 STRIP-N2

---------------------------------------
STREAM ID POWDER1 POWDER2 PP-PROD RFEED1 STRIP-N2

FROM : REACTOR STRIP1 STRIP2 FMIX1 ----
TO : STRIP1 STRIP2 ---- REACTOR STRIP2
MAX CONV. ERROR: 0.0 0.0 0.0 -3.4466-06 0.0

SUBSTREAM: MIXED
PHASE: LIQUID LIQUID LIQUID MIXED VAPOR
COMPONENTS: KMOL/HR
TICL4 1.5815-02 1.5815-02 1.5815-02 1.5815-02 0.0
TEA 8.7165-02 8.7165-02 8.7165-02 8.7591-02 0.0
C3H6 103.4097 9.9530 0.6446 1.9427+04 0.0
C3H8 2.0143 0.1961 1.2883-02 365.1218 0.0
PP 385.5366 385.5366 385.5366 0.0 0.0
H2 0.2879 4.1377-04 3.1201-07 1984.2451 0.0
N2 6.7702-02 2.9362-04 4.2896-02 182.0552 17.8486
H2O 0.0 0.0 0.0 0.0 0.0
COMPONENTS: KG/HR
TICL4 3.0000 3.0000 3.0000 3.0000 0.0
TEA 9.9514 9.9514 9.9514 10.0000 0.0
C3H6 4351.5476 418.8304 27.1252 8.1750+05 0.0
C3H8 88.8250 8.6494 0.5681 1.6101+04 0.0
PP 1.6224+04 1.6224+04 1.6224+04 0.0 0.0
H2 0.5804 8.3411-04 6.2897-07 4000.0000 0.0
N2 1.8966 8.2254-03 1.2017 5100.0000 500.0000
H2O 0.0 0.0 0.0 0.0 0.0
TICL4 1.4507-04 1.8003-04 1.8444-04 3.5599-06 0.0
TEA 4.8122-04 5.9717-04 6.1181-04 1.1866-05 0.0
C3H6 0.2104 2.5134-02 1.6677-03 0.9701 0.0
C3H8 4.2953-03 5.1904-04 3.4926-05 1.9106-02 0.0
PP 0.7845 0.9736 0.9974 0.0 0.0
H2 2.8066-05 5.0054-08 3.8669-11 4.7466-03 0.0
N2 9.1713-05 4.9360-07 7.3879-05 6.0519-03 1.0000
H2O 0.0 0.0 0.0 0.0 0.0
TOTAL FLOW:
KMOL/HR 491.4193 395.7895 386.3400 2.1958+04 17.8486
KG/HR 2.0679+04 1.6664+04 1.6265+04 8.4271+05 500.0000
CUM/SEC 7.9047-03 5.7517-03 5.5169-03 3.7533 4.1618-02
STATE VARIABLES:
TEMP C 69.0000 65.0000 60.0000 59.6604 30.0000
PRES N/SQM 2.8000+06 5.0000+05 1.0000+05 3.0000+06 3.0000+05
VFRAC 0.0 0.0 0.0 0.9225 1.0000
LFRAC 1.0000 1.0000 1.0000 7.7502-02 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
J/KMOL -6.3962+07 -8.1459+07 -8.4134+07 1.4632+07 1.2595+05
J/KG -1.5200+06 -1.9347+06 -1.9984+06 3.8126+05 4495.9140
WATT -8.7311+06 -8.9557+06 -9.0289+06 8.9247+07 624.4325
ENTROPY:
J/KMOL-K -2.9520+05 -3.2452+05 -3.3033+05 -1.5564+05 -8597.9812
J/KG-K -7015.1378 -7707.6093 -7846.1345 -4055.5540 -306.9230

DENSITY:
KMOL/CUM 17.2690 19.1147 19.4524 1.6251 0.1191
KG/CUM 726.6967 804.7944 818.9732 62.3680 3.3372
AVG MW 42.0810 42.1034 42.1015 38.3775 28.0135
TICL4 CPSFLOW
CPSFLOW 3.3358-05 3.3358-05 3.3358-05 1.3500-03 MISSING
CPSFRAC
CPSFRAC 2.4709-02 2.4709-02 2.4709-02 1.0000 MISSING
CVSFLOW
SITE_1 4.6857-08 4.6857-08 4.6857-08 0.0 MISSING
SITE_2 3.8123-07 3.8123-07 3.8123-07 0.0 MISSING
SITE_3 1.6479-08 1.6479-08 1.6479-08 0.0 MISSING
SITE_4 1.1552-07 1.1552-07 1.1552-07 0.0 MISSING
CVSFRAC
SITE_1 3.4709-05 3.4709-05 3.4709-05 0.0 MISSING
SITE_2 2.8239-04 2.8239-04 2.8239-04 0.0 MISSING
SITE_3 1.2206-05 1.2206-05 1.2206-05 0.0 MISSING
SITE_4 8.5569-05 8.5569-05 8.5569-05 0.0 MISSING
CDSFLOW
CDSFLOW 1.1634-03 1.1634-03 1.1634-03 0.0 MISSING
CDSFRAC
CDSFRAC 0.8618 0.8618 0.8618 0.0 MISSING
PP SFRAC
C3H6-R 1.0000 1.0000 1.0000 0.0 MISSING
SFLOW
C3H6-R 385.5035 385.5035 385.5035 MISSING MISSING
DPN
DPN 535.8466 535.8466 535.8466 0.0 MISSING
DPW
DPW 2435.3752 2435.3752 2435.3752 0.0 MISSING
PDI
PDI 4.5449 4.5449 4.5449 0.0 MISSING
MWN
MWN 2.2549+04 2.2549+04 2.2549+04 0.0 MISSING
MWW
MWW 1.0248+05 1.0248+05 1.0248+05 MISSING MISSING
ZMOM
ZMOM 0.7194 0.7194 0.7194 MISSING MISSING
FMOM
FMOM 385.5035 385.5035 385.5035 MISSING MISSING
SMOM
SMOM 9.3885+05 9.3885+05 9.3885+05 MISSING MISSING
LDPN
LDPN 791.0950 791.0950 791.0950 0.0 MISSING
LZMOM
LZMOM 1.5271-04 1.5271-04 1.5271-04 MISSING MISSING
LFMOM
LFMOM 0.1208 0.1208 0.1208 MISSING MISSING
LSFLOW
C3H6-R 0.1208 0.1208 0.1208 0.0 MISSING
LSFRAC
LEFLOW
C3H6-R 1.5271-04 1.5271-04 1.5271-04 MISSING MISSING
LEFRAC

LPFRAC
LPFRAC 2.1226-04 2.1226-04 2.1226-04 MISSING MISSING
SSFRAC
C3H6-R_1 1.0000 1.0000 1.0000 MISSING MISSING
C3H6-R_2 1.0000 1.0000 1.0000 0.0 MISSING
C3H6-R_4 1.0000 1.0000 1.0000 0.0 MISSING
SSFLOW
C3H6-R_4 64.0082 64.0082 64.0082 0.0 MISSING
SDPN
SITE_1 750.2711 750.2711 750.2711 MISSING MISSING
SITE_2 95.8851 95.8851 95.8851 0.0 MISSING
SDPW
SPDI
SITE_1 1.9987 1.9987 1.9987 0.0 MISSING
SITE_2 1.9896 1.9896 1.9896 0.0 MISSING
SITE_3 1.9995 1.9995 1.9995 0.0 MISSING
SITE_4 1.9968 1.9968 1.9968 0.0 MISSING
SMWN
SITE_1 3.1572+04 3.1572+04 3.1572+04 MISSING MISSING
SMWW
SZMOM
SITE_3 9.0312-02 9.0312-02 9.0312-02 MISSING MISSING
SFMOM
SSMOM
SPFRAC
SITE_1 0.2985 0.2985 0.2985 0.0 MISSING
SITE_2 6.7202-02 6.7202-02 6.7202-02 0.0 MISSING
SITE_3 0.4683 0.4683 0.4683 0.0 MISSING
SITE_4 0.1660 0.1660 0.1660 0.0 MISSING

LSDPN
LSZMOM
SITE_1 3.8270-05 3.8270-05 3.8270-05 0.0 MISSING
SITE_2 3.7936-05 3.7936-05 3.7936-05 0.0 MISSING
SITE_3 3.8300-05 3.8300-05 3.8300-05 0.0 MISSING
SITE_4 3.8201-05 3.8201-05 3.8201-05 0.0 MISSING
LSFMOM
LSSFLOW
C3H6-R_1 2.8713-02 2.8713-02 2.8713-02 MISSING MISSING
LSSFRAC
LSEFLOW
LSEFRAC
C3H6-R_1 1.0000 1.0000 1.0000 0.0 MISSING
C3H6-R_2 1.0000 1.0000 1.0000 0.0 MISSING
C3H6-R_3 1.0000 1.0000 1.0000 0.0 MISSING
C3H6-R_4 1.0000 1.0000 1.0000 0.0 MISSING
LSPFRAC
ATFLOW
ATFLOW 75.1546 75.1546 75.1546 0.0 MISSING
ATFRAC
ATFRAC 0.1950 0.1950 0.1950 0.0 MISSING
SATFLOW
SITE_1 13.9341 13.9341 13.9341 0.0 MISSING
SITE_2 33.2752 33.2752 33.2752 0.0 MISSING
SATFRAC
VAP-A VAP-B

-----------
STREAM ID VAP-A VAP-B

FROM : REACTOR COMP1
TO : COMP1 EXC1
SUBSTREAM: MIXED
PHASE: VAPOR VAPOR
COMPONENTS: KMOL/HR
TICL4 0.0 0.0
TEA 0.0 0.0
C3H6 1.8938+04 1.8938+04
C3H8 363.1075 363.1075
PP 0.0 0.0
H2 1983.2900 1983.2900
N2 181.9875 181.9875
H2O 0.0 0.0
COMPONENTS: KG/HR
TICL4 0.0 0.0
TEA 0.0 0.0
C3H6 7.9692+05 7.9692+05
C3H8 1.6012+04 1.6012+04
PP 0.0 0.0
H2 3998.0747 3998.0747
N2 5098.1034 5098.1034
H2O 0.0 0.0
TICL4 0.0 0.0
TEA 0.0 0.0
C3H6 0.9695 0.9695
C3H8 1.9478-02 1.9478-02
PP 0.0 0.0
H2 4.8637-03 4.8637-03
N2 6.2018-03 6.2018-03
H2O 0.0 0.0
TOTAL FLOW:
KMOL/HR 2.1466+04 2.1466+04
KG/HR 8.2203+05 8.2203+05
CUM/SEC 4.6162 4.2580
STATE VARIABLES:
TEMP C 69.0000 74.8156
PRES N/SQM 2.8000+06 3.0500+06
VFRAC 1.0000 1.0000
LFRAC 0.0 0.0
SFRAC 0.0 0.0
ENTHALPY:
J/KMOL 1.6384+07 1.6641+07
J/KG 4.2784+05 4.3456+05
WATT 9.7693+07 9.9228+07
ENTROPY:
J/KMOL-K -1.4945+05 -1.4924+05
J/KG-K -3902.5890 -3897.1742
DENSITY:
KMOL/CUM 1.2917 1.4004
KG/CUM 49.4656 53.6268
AVG MW 38.2939 38.2939

References
Choi, K.-Y., & Ray, W. H. (1985). Recent Developments in Transition Metal
Catalyzed Olefin Polymerization - A Survey. II. Propylene Polymerization.
JMS-Rev. Macromol. Chem. Phys., C25(1).
Debling, J. A., Han, G. C., Kuijpers, F., VerBurg, J., Zacca, J., & Ray, W.H.
(1994). Dynamic Modeling of Product Grade Transitions for Olefin
Polymerization Processes. AIChE J., 40 (3).
Hutchinson, R. A. (1990). Modeling of Particle Growth in Heterogeneous
Catalysed Olefin Polymerization. Ph.D. thesis, University of Wisconsin -
Madison.
Kissin, Y. V. (1985). Isospecific Polymerization of Olefins with Heterogeneous
Ziegler-Natta Catalysts. New York: Springer-Verlag.
Soares, J. B. P., & Hamielec, A. E. (1995). Deconvolution of Chain-length
Distributions of Linear Polymers Made by Multiple-site-type Catalysts.
Polymer, 36 (11).

styrene butadiene ionic
polymerization 15764
styrene ethyl acrylate
copolymerization 13044
azo-bis-isobutyronitrile 131
Index B
benzene 70, 106
binary interaction parameters 40
blocks
distribution data 22
entering conditions 61
entering convergence 61
2 entering convergence sequence
65
2,6 dimethyl phenol
entering mixer specifications 18
polymerization 30
improving convergence 17
property results 37
in flowsheets 6
overriding global values 17
A renaming 7
ammonium persulfate 145 specifying 16
antisolvents 70 bulk polymerization 93105
aromatic polyether 30 butadiene
Aspen Polymers styrene emulsion
calculating end-use properties copolymerization 14456
8392 styrene ionic polymerization
creating simulation models 528 15764
expanded polystyrene
suspension polymerization C
12029
caprolactam
fitting kinetic parameters 5269
conversion 217
fractionation 7082
example flowsheet 204
HDPE modeling 16583
example input summary 212
LDPE modeling 184202
example kinetics 206
linking with Excel 27
example process conditions 205
methyl methacrylate
example process studies 212
example results 217
nylon 6 caprolactam
example stream summary 218
extraction value results 218
polyproplylene gas phase
Mn results 217
nylon 6 polymerization 20221
polystyrene modeling 93105
step-growth polymerization 203
polystyrene with styrene
catalysts for Ziegler-Natta 165
monomer distillation 10619
chain length distribution
predicting physical properties
results (SBR) 155
2939
chain transfer agents
regressing property parameters
dodecyl mercaptan 95
4051
ethyl benzene 95, 106
simulation examples 592
hydrogen 166
styrene butadiene emulsion
tertiary dodecyl mercaptane 145
components
248 Index
entering pure component input summary 90
parameters 57 EPS See expanded polystyrene
predicting properties for 2939 equations of state
specifying 9, 31 fitting parameters 4051
convergence Sanchez-Lacombe 40
for blocks 61, 65 ethanol 70
improving 17 ethyl acetate polymerization 221
crystallinity 34 31
custom property parameters 11 ethyl acrylate copolymerization
13044
D ethyl benzene 95, 106
ethylene
data conversion 174
experimental 44 HDPE polymerization 16583
fitting 5269 LDPE polymerization 184202
regression 4051 ethylene-polyethylene 40
sets 62 examples
data fit calculating end-use properties
folder 62 8392
specifying regression cases 64 expanded polystyrene
data regression suspension polymerization
entering experimental data 44 12029
example for property parameters fitting kinetic parameters 5269
4051 fractionating oligomers 7082
input summary 49 HDPE polymerization 16583
results 66 LDPE polymerization 184202
specifying 62 methyl methacrylate
specifying regression cases 46 polymerization 22131
density nylon 6 caprolactam
predicting 29 polymerization 20221
descriptions for simulations 9 polypropylene gas phase
distillation of polystyrene 10619 polymerization 23250
distributions polystyrene bulk polymerization
for flowsheets 22 93105
for reactors 22 polystyrene with styrene
for streams 22 monomer distillation 10619
linking with Excel 27 predicting physical properties
live plots 23 2939
plots for multiple simulations 25 regressing property parameters
plotting 22 4051
tables 22 styrene butadiene emulsion
tracking 11 copolymerization 14456
di-tert-butyl peroxide 95 styrene butadiene ionic
dodecyl mercaptan 95 polymerization 15764
DRS See data regression styrene ethyl acrylate
copolymerization 13044
E Excel
linking 27
emulsifiers 145
expanded polystyrene
emulsion polymerization of styrene
conversion effects 128
butadiene 14456
end-use properties
calculating 8392
Index 249
example process conditions 122 G
gas-phase polymerization 23250
example results 128
gel effect specification 15
free-radical polymerization 120
global options
number average molecular
defining unit-sets 8
weight 128
overriding values 17
report options 9
experimental data 44
specifying 8
group contribution method 29
F
feed flow rate H
effect on ethylene conversion
HDPE
174
conversion results 174
effect on extraction value 218
effect on hydrogen concentration
175
effect on melt index 176
example model 16583
effect on Mn 174, 217
effect on Mw 175
effect on number average
example results 174
molecular weight 101
hydrogen concentration results
effect on polydispersity 102, 176
175, 177
effect on recycle rate 102
melt index results 176
effect on styrene conversion 100
Mn results 174
effect on weight average
molecular weight distribution 178
molecular weight 101
Mw results 175
feed streams specification 12
polydispersity results 176
fitting
stream summary 178
input summary example 67
heat capacity
flory-Huggins model 70
predicting 29
flow rate See feed flow rate
high-density polyethylene See
flowsheets
HDPE
creating 6
hydrogen 166
distribution data 22
hydrogen concentration 175, 177
placing blocks 6
placing streams 7
renaming blocks 7 I
renaming streams 7 inhibitors 109
Fortran subroutines 83, 90 initiation
fractionation results 66
example 7082 thermal 93105
input summary 80 initiators
free-radical polymerization ammonium persulfate 145
of ethylene 184202 decomposition vs reactor length
of expanded polystyrene 12029 193
of methyl methacrylate 22131 methyl peroxide 52
of polystyrene 93105 input summary
of styrene butadiene 14456 for data regression example 49
of styrene ethyl acrylate 13044 for end-use properties example
90
for expanded polystyrene
polymerization 124
250 Index
for fitting kinetic parameters reactant temperature profiles
example 67 193
for HDPE polymerization 168 reactor temperature profiles 194
for LDPE polymerization 188 stream summary 195
for methyl methacrylate live plots 23
polymerization 224 low-density polyethylene See LDPE
for nylon 6 caprolactam
polymerization 212 M
for oligomer fractionation 80
for polypropylene polymerization mass fraction crystallinity 34
237 melt index 83
for polystyrene bulk methanol 52
polymerization 96 methyl methacrylate
for polystyrene with styrene example flowsheet 223
monomer distillation 109 example input summary 224
for predicting physical properties example kinetics 224
example 38 example process conditions 223
for styrene ethyl acrylate example process studies 224
copolymerization 136 example results 226
for styrene-butadiene emulsion flow vs time 226
copolymerization 150 free-radical polymerization 222
for styrene-butadiene ionic heat duty 229
polymerization 160 MWn vs temperature 228
intrinsic viscosity 83 MWw vs temperature 229
ionic polymerization number-average molecular
of styrene butadiene 15764 weight vs time 227
polydispersity 229
polymerization in ethyl acetate
K
22131
kinetics reaction time for monomer
fitting parameters 5269 conversion 227
modifying reactions 13 methyl peroxide 52
polymerization 58 mixers 18
specifying 13 mixtures
specifying gel effect 15 ethylene-polyethylene 41
molecular structure 33
L molecular weight distribution
HDPE example 178
LDPE
coolant temperature profiles 193
N
DPn and DPw vs reactor length
192 n-hexane 166
ethylene mole fraction 194 n-pentane 121
example flowsheet 185 nylon 6
example input summary 188 caprolactam conversion 217
example kinetics 187 caprolactam polymerization 202
example model 184202 21
example process conditions 186 example flowsheet 204
example process studies 188 example input summary 212
example results 192 example kinetics 206
free-radical polymerization 184 example process conditions 205
initiator decomposition vs reactor example process studies 212
length 193 example results 217
Index 251
example stream summary 218 of polystyrene by thermal
extraction value results 218 initiation 93105
Mn results 217 of styrene butadiene 14456,
step-growth polymerization 203 15764
of styrene ethyl acrylate 13044
O solution 16583, 22131
suspension 12029, 23250
OLE linking 27 polymers
oligomers 2,6 dimethyl phenol 30
characterizing 10 characterizing 10
fractionation example 7082 end-use properties 8392
ethylene-polyethylene 40
P fractionation example 7082
polystyrene 70
parameters
predicting formation during
binary interaction 40
styrene distillation 10619
entering pure component 57
specifying mass fraction
fitting kinetic 5269
drystallinity 34
fitting mixture 4051
vinyl acetate 52
Flory-Huggins 70
polymethyl methacrylate See
for polypropylene example 236
methyl methacrylate
regression for styrene ethyl
polyolefins 41
acrylate example 133
polypropylene
specifying 47
specifying binary interaction 76
specifying custom 11
physical properties
example parameters 236
predicting parameters 2939
regressing parameters 4051
example results 242
plots
distributions 22
gas phase polymerization 232
live plots 23
50
manually 25
process types 232
multiple simulations 25
polystyrene See also expanded
poly(phenylene oxide) 30
polystyrene
polydispersity 70
bulk polymerization 93105
polyethylene
HDPE polymerization 16583
intrinsic viscosity 83
example kinetics 96
LDPE polymerization 184202
melt index 83
zero-shear viscosity 84
example results 100
Ziegler-Natta polymerization 165
polymerization
fractionation 70
emulsion 14456
fractionation results 79
gas-phase 23250
free-radical polymerization 93
ionic 15764
number average molecular
of expanded polystyrene 12029
weight 101
of HDPE 16583
polydispersity 70, 102
of LDPE 184202
recycle rate 102
of methyl methacrylate 22131
styrene monomer distillation
of nylon 6 caprolactam 20221
10619
of polypropylene 23250
252 Index
weight average molecular weight cases 46, 64
101 for styrene ethyl acrylate
polystyrene distillation example 133
example flowsheet 106 reports
example input summary 109 defining options 9
example kinetics 109 displaying a prop-set 58
example process conditions 107 results
example results 114 chain length distribution (SBR)
example stream summary 116 155
inhibitor 109 for expanded polystyrene
polymer production results 115 polymerization 128
profitability results 116 for HDPE polymerization 174
sensitivity study 115 for initiation 66
process models See simulations for LDPE polymerization 192
propagation results 66 for methyl methacrylate
properties polymerization 226
creating property sets 34 for nylon 6 caprolactam
creating property tables 35 polymerization 217
end-use 8392 for polymer heat capacity 36
estimating 30 for polypropylene polymerization
predicting 29 242
specifying calculations 77 for polystyrene bulk
specifying custom parameters 11 polymerization 100
specifying parameters 47, 76 for polystyrene with styrene
property distillation 114
methods 11, 43 for propagation 66
property analysis 30 for styrene ethyl acrylate
property method copolymerization 140
POLYSL 43 for styrene-butadiene emulsion
property parameters copolymerization 153
pure components 47 for styrene-butadiene ionic
property sets 34 polymerization 162
property tables 35 fractionation of polystyrene 79
prop-sets plotting 22
defining 58 reviewing 18
Fortran subroutines 83 saving 28
pseudo-component approach 70 run types
pure components data regression 41
constant 75 property analysis 31
parameters 57 runs
predicting properties for 2939 new 5
starting 18
R
S
rate constants
example input screen 14 Sanchez-Lacombe 40
for styrene-butadiene emulsion SBR See styrene butadiene
example 149 segments
reactions characterizing 10
modifying 13 defining molecular structure 33
rate constants 14 sensitivity tables 88
reactor distribution data 22 setup options
regression adding descriptions 9
Index 253
adding titles 8 solution polymerization 16583,
defining unit-sets 8 22131
report options 9 solvents
specifying 8 benzene 70, 106
specifying time limits 9 methanol 52
simulations n-hexane 166
calculating end-use properties toluene 106
8392 species characterization 10
creating flowsheets 6 sstyrene distillation
creating models 528 example stream summary 116
creating new runs 5 step-growth polymerization of
defining report options 9 caprolactam 20221
defining unit-sets 8 stream summary
entering descriptions for 9 for HDPE polymerization 178
entering time limits 9 for LDPE polymerization 195
entering titles for 8 for nylon 6 caprolactam
examples 592 polymerization 218
expanded polystyrene for polypropylene polymerization
suspension polymerization 242
12029 for polystyrene bulk
fitting kinetic parameters 5269 polymerization 103
fractionating oligomers 7082 for polystyrene with styrene
HDPE polymerization 16583 distillation 116
LDPE polymerization 184202 streams
methyl methacrylate distribution data 22
polymerization 22131 entering conditions 61
nylon 6 caprolactam in flowsheets 7
polymerization 20221 renaming 7
plotting multiple 25 report options 58
polypropylene gas phase specifying 12
polymerization 23250 styrene
polystyrene bulk polymerization bulk polymerization 93105
93105 butadiene emulsion
polystyrene with styrene copolymerization 14456
monomer distillation 10619 butadiene ionic polymerization
predicting physical properties 15764
2939 conversion results 100
regressing property parameters ethyl acrylate copolymerization
4051 13044
results 18 example flowsheet 94
running 18, 36 example input summary 96
saving 28 example kinetics 96
styrene butadiene emulsion example process conditions 94
copolymerization 14456 example process studies 96
styrene butadiene ionic example results 100
polymerization 15764 example stream summary 103
styrene ethyl acrylate free-radical polymerization 93
copolymerization 13044 monomer distillation of
templates 6 polystyrene 10619
site-based species characterization number average molecular
10 weight 101
sodium lauryl sulfate 145 polydispersity 102
recycle rate 102
254 Index
suspension polymerization 120 T
weight average molecular weight
templates
101
for simulations 6
styrene distillation
tertiary dodecyl mercaptane 145
thermal conductivity
predicting 29
time limits 9
titles for simulations 8
example results 114
toluene 106
inhibitor 109
polymer production results 115
profitability results 116 U
sensitivity study 115 UNIPOL flowsheet 233
styrene ethyl acrylate unit operation blocks specification
copolymerization example 130 16
44 unit-sets
example flowsheet 131 defining 8
V
example results 140 Van Krevelen group contribution 29
molecular weight 142 vapor-liquid equilibrium 40
monomer conversion 141 vinyl acetate 52
parameter regression 133 viscosity
styrene-butadiene intrinsic 84
chain length distribution 155 zero-shear 84
copolymer composition 163 VK column 203
degree of polymerization 164
example flowsheet 146, 158 Z
example input summary 150,
160 zero-shear viscosity 83
example kinetics 148, 159 Ziegler-Natta catalysts 165
example process conditions 147, Ziegler-Natta polymerization
159 of ethylene 16583
example process studies 150 of polypropylene 23250
example rate constants 149
example results 153, 162
monomer mass 154
particle growth 153
particle nucleation 153
phase volumes 154
polymer composition 155
polymer mass 154
polymer properties 154
rate of consumption 162
styrene-butadiene rubber See
styrene-butadiene
subroutines
Fortran 83
user 90
suspension polymerization 12029,
23250
Index 255

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Aspen Polymers

Examples & Applications

Aspen Technology, Inc.

A1 Creating a Simulation Model..............................................................................5

A2 Predicting Physical Properties.........................................................................28

A3 Regressing Property Parameters.....................................................................39

A4 Fitting Kinetic Parameters...............................................................................51

A5 Fractionating Oligomers ..................................................................................69

A6 Calculating End-Use Properties .......................................................................82

B1 Polystyrene Bulk Polymerization by Thermal Initiation...................................92

B2 Polystyrene with Styrene Monomer Distillation.............................................104

B3 Expanded Polystyrene Suspension Polymerization........................................118

B4 Styrene Ethyl Acrylate Free-Radical Copolymerization Process .....................128

B6 Styrene Butadiene Ionic Polymerization Processes .......................................154

B7 High-Density Polyethylene High Temperature Solution Process ....................162

B8 Low-Density Polyethylene High Pressure Process .........................................181

B9 Nylon 6 Caprolactam Polymerization Process................................................200

B11 Polypropylene Gas Phase Polymerization Processes ...................................229

Aspen Polymers (formerly known as Aspen Polymers Plus) is a general-

About This Manual

Introducing Aspen Polymers 1

Note: Dynamic process applications are available in the Aspen Dynamics

2 Introducing Aspen Polymers

Aspen Polymers Guides

Aspen Plus Guides

Aspen Dynamics Guides

Introducing Aspen Polymers 3

4 Introducing Aspen Polymers

This example describes how to construct a polymer simulation model. It

Creating a New Run

A1 Creating a Simulation Model 5

Creating the Process Flowsheet

Placing Blocks and Streams

6 A1 Creating a Simulation Model

Renaming Blocks and Streams

Specifying Setup and Global

A1 Creating a Simulation Model 7

Entering a Simulation Title

Entering a Simulation Description

8 A1 Creating a Simulation Model

A1 Creating a Simulation Model 9

To track distributions in your simulation in order to generate plots or tables,

10 A1 Creating a Simulation Model

Specifying Physical Properties

Specifying Feed Streams

A1 Creating a Simulation Model 11

12 A1 Creating a Simulation Model

6 Click the Comments button to add the description "Grade A SAN

A1 Creating a Simulation Model 13

14 A1 Creating a Simulation Model

Defining the Unit Operation

Entering Block Specifications

A1 Creating a Simulation Model 15

Note: This combination of parameters (step 2 and step 3) is recommended

16 A1 Creating a Simulation Model

Overriding Global Values

Entering Mixer Specifications

Running the Simulation

A1 Creating a Simulation Model 17

18 A1 Creating a Simulation Model