Polymer Process Modeling

with Aspen Polymers

Nattapol A., Engineering Business Consultant
Aspen Polymers

• Aspen Polymers extends Aspen Plus, Aspen Plus Dynamics, and Aspen Custom
Modeler to simulate Polymerization Processes

• Key features:
– Property databases specific to polymers
– Thermodynamics models
– Rate-based reaction models
– Polymer characterization
– Polymer reaction kinetics

• Over 20 years of proven benefits

• Used by hundreds of companies

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Simulating Polymer Processes With Aspen Plus
Phase Equilibrium Aspen Polymers Molecular Structure
• Copolymer PC-SAFT with • Copolymer composition
association & polar terms Typical benefits: • Branching (LCB & SCB)
• SAFT 5-10% capacity increase • Moments (MWD & PSD)
• Polymer NRTL Improved product quality • Mole Weight Distribution
• Sanchez-Lacombe Rapid recipe development curves for addition polymers
• Flory-Huggins • Tacticity

Databanks Reactions
• Polymers • Free-Radical
• Segments • Ziegler-Natta / metallocene
• Initiator rate constants • Ionic (anionic & cationic)
• Functional Groups • Emulsion polymerization
• PC-SAFT parameters • Step growth condensation
• Segment-based power law

Physical Properties
• Transition temperatures Scope
• Polymer viscosity model Process Models Completely integrated with:
• Van-Krevelen group • HDPE, LDPE, LLDPE
contribution model • Polypropylene • Aspen Plus
• Special mixing rules for • Polystyrene, SBR • Aspen Plus Dynamics
polymer/solvent systems • PVC, PVAc • Aspen Custom Modeler
• PET, PBT, nylon
• Polycarbonate
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Polymer Modeling Best Practices
Work Processes for Developing a Model

Identify and Select Verify Pure

Fit / Verify Phase
Characterize Property Component
Properties

Equilibrium Data
Components Option Set Properties

Develop User Property Routine (MI, MFR, ρ, etc)

Kinetics

Determine Side Verify Model (Use

Define
Rate Reactions if batch data if
Reactions
Constants necessary available)

Close Recycle Add Details Test Model

Build “open”
Flowsheet

and Control (heat transfer,

Flow sheet
Loops etc)
Apply Model
May be necessary to return
To previous step to improve model

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Work Process for Building a Polymerization Model

Characterize Components

Set Up Properties

Set Up Chemical Reactions

Build Steady-State Model

Run Model & Analyze Results

Build Dynamic Model

(optional)

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Aspen Polymers Extends Aspen Plus with Additional
Component Types

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Aspen Polymers extends Aspen Plus with additional classes

Run Model & Analyze Results of components including polymers, oligomers, and
segments.

Build Dynamic Model Segments are the basic building blocks of polymers. For
(optional)
example polypropylene is made up of propylene segments.

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Characterizing Components

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Component Attributes Characterize Polymer Properties

Characterize Components

Set Up Property Methods

Set Up Reactions

Build Steady-State Model

Polymer components are characterized through component

Run Model & Analyze Results
Build Dynamic Model
(optional)
attributes. These track conserved quantities including
segment flow rates and the moments of the molecular weight
distribution, branching distribution, and many other
characteristics used to track the state of the polymer.

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Component Attributes Characterize Polymer Properties
Method of Moments
Pn = Flow Rate of polymer molecules with “n” segments

∞
Zeroth Moment λ 0 = ∑ n 0 [Pn ] Total flow rate of polymer molecules
n =1
∞
First Moment λ 1= ∑ n1[Pn ] Total flow rate of polymer segments
n =1

∞
2nd Moment λ 2 = ∑ n 2 [Pn ] Higher moments are also conserved
n =1
∞
3rd Moment λ3= ∑ n 3[Pn ]
n =1

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Component Attributes Characterize Polymer Properties
Average Chain Length & Molecular Weight

• DPN – number-average degree of polymerization

Multiply by average segment mole
– DPn = l1 / l0 weight to get average molecular
weights (Mn, Mw, Mz)
• DPW – weight-average degree of polymerization
– DPw = l2 / l1

• DPZ – “Z”-average degree of polymerization

– DPz = l3 / l2

• PDI – polydispersity index

– PDI = DPw / DPn

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Many Other Attributes to Track Polymer Structure

Terminal & Pendant

Double Bonds

Short & Long Chain Tacticity Cis/Trans/Vinyl and

Branching (Atactic Fraction) Cross-Links

• Average Block Length • Association / Dissociation

• Dyads (AA, AB, BB) • Particle Size Distributions

• Live, Dead, Inactive sites • Head-to-Head v Head-to-Tail

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Catalyst and Initiator States are Tracked with Attributes

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Component attributes are also used to track

Run Model & Analyze Results states (dormant, live, inhibited, dead) of
Ziegler catalyst and Ionic initiators
Build Dynamic Model
(optional)

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Aspen Polymers Tracks and Displays the Polymer Molecular
Weight Distribution

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Run Model & Analyze Results

Can track molecular weight distribution for
Build Dynamic Model most types of polymers (not for step-growth or
(optional) ionic polymers – reversible kinetics)

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Molecular Weight Distributions are Reported for Blocks and Streams
Block CSTR-1: Local Chain Length Distrib ution
0.50
Composite
0.45 Distribution Moments Site1
DPN = 1181.11 1174.19 Site2
DPW = 4264.52 4202.65 Site3
0.40

0.35
PDI = 3.6106
Area = 1.0022
3.5792
Site4
Block results
0.30
show local MWD
Weight fraction

0.25

0.20

0.15
formed in each
0.10 reactor
0.05

0.00
1 2 5 10 20 50 100 200 500 1000 2000 5000 10000 20000 50000
Degree of polymerization

Cumulative Chain Lengt h Distribution

0.50
R1PROD
0.45
R2PROD

0.40

0.35

0.30

Weight fraction
Stream results show cumulative 0.25

MWD – note how MWD has shifted 0.20

0.15

from one reactor to the next 0.10

0.05

0.00
1 2 5 10 20 50 100 200 500 1000 2000 5000 10000 20000 50000
Degree of polymerization

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Aspen Polymers includes Databases for Polymer
Components and Properties

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Aspen Polymers included databases for

Run Model & Analyze Results
polymers, segments, initiators and binary
parameters for PC-SAFT model.
Build Dynamic Model
(optional)

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Aspen Polymers Includes State-of-Art Property Models

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Special property methods for polymers

Run Model & Analyze Results
Build Dynamic Model
(optional)
• Polymer NRTL for highly non-ideal systems
(polyesters, nylons, polycarbonate, silicone)
• PC-SAFT for high-pressure systems
(polyolefins – PP, HDPE, LDPE)

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Polymerization Reactions

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Reaction models for all types of commercial
polymerization processes
Run Model & Analyze Results
The reaction models can be used in the batch,
Build Dynamic Model CSTR, and plug-flow reactor models in Aspen Plus.
(optional) They can be combined with standard power-law
models to account for side reactions.
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 Sweet Spots
Types of Polymerization Processes
• Free-radical polymerization (bulk, solution, suspension, or emulsion)
– Polystyrene, LDPE, SBR, PVC, PVAc

• Ziegler-Natta/coordination catalysis
– Polypropylene (PP), HDPE, LLDPE

• Living polymerization (ionic and group transfer polymerization)

– polyethylene oxide (PEO), polyoxyethylene (POE), and polyethylene glycol (PEG)

• Step-growth polymerization
– Condensation (generates a by-product such as water)
– Polyester, nylon-6,6, polycarbonate, silicone
– Pseudo-condensation (does not generate a byproduct)
– Unsaturated polyesters, polyurethanes
– Ring addition polymerization (monomer is a cyclic molecule)
– Nylon-6, poly(lactide)

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The Reaction Models Include Expert Systems to Help You

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Identify reacting species

Run Model & Analyze Results
Associate monomers with segments
Build Dynamic Model
(optional)

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Reactions Are Generated Automatically By the Expert System
Option to Add or Remove Reactions

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Run Model & Analyze Results

Automatically generate common reactions.

Build Dynamic Model
(optional) Options to include additional reactions

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The Reaction Models Are Designed For Ease of Use

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Run Model & Analyze Results The reaction rate constants can be fit to
lab or plant data using standard data
Build Dynamic Model regression tools built into Aspen Plus.
(optional)

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Use Standard Features of Aspen Plus to Build Your
Flowsheet

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Run Model & Analyze Results Build flowsheet in Aspen Plus.

Complex reactors, such as LDPE tubular
Build Dynamic Model reactors, can be represented using a series of
(optional) CSTR or plug-flow reactors.

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Aspen Polymers Includes A Wide Range of Industrial
Process Models

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Run Model & Analyze Results

Aspen Polymers includes sample models of many common
industrial processes for polyolefins, styrene-based polymers,
polyester, nylons, PVC, and many other commodity polymers.
Build Dynamic Model
(optional) AspenTech also offers modeling services to help you build and
validate models of your processes.

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Several Examples are Delivered with Aspen Plus

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Aspen Polymers Makes it Easy to Visualize MWD

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Run Model & Analyze Results

The user can generate multiple plots very easily:
• Degree of polymerization vs weight fraction
Build Dynamic Model
• Molecular weight distribution vs weight fraction
(optional)

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Aspen Polymers Is Compatible with Aspen Dynamics and
Custom Modeler

Characterize Components

Set Up Property Methods

Set Up Chemical Reactions

Build Steady-State Model

Run Model & Analyze Results

Build Dynamic Model

(optional)

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 Aspen Plus V8.8
Optimize the Whole Polymer Process

Solid Polymers
Solid unit operations
extended for polymers

Reduce Energy Costs

by up to 20%

Reduce capital cost

by avoiding overdesign

Increase product
quality
Single environment

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 Example: Suspension Polymerization of Polyacrylate
Challenge:
High operating costs due to
relatively high utility costs

Opportunity:
Optimize operating cost while
maintaining product quality
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AspenTech’s Polymer Modeling Experience

• AspenTech has a long history of modeling polymerization processes

• Have executed over 200 polymer modeling projects covering a wide range of polymers
and processes.
– Polyolefins: LDPE, LLDPE, HDPE, PP, EPR, EPDM, PB (Polybutylene)
– Polyesters: PET (Polyethylene terephthalate), PBT (Polybutylene Terephthalate)
– Polyamides: Nylons
– Others: Polycarbonates, PVC, SBR, Silicones, PS, SAN (Styrene acrylonitrile), Acrylates, Emulsion
polymers, Elastomers

• AspenTech has several patents and has developed many best practices for polymer
modeling

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Polymerization Process Modeling Applications

Steady State Modeling:

• Optimize monomer yield and throughput

• Shorten development time/plant trials for new grades

• Shorten time/plant trials for new catalyst upgrade

• Debottleneck existing plants and design new plants

• Trouble shoot plant operations

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Polymerization Process Modeling Applications
Dynamics Modeling:
• Analyzing safety issues, design pressure relief

• Improving grade transitions to reduce off spec production

• Train operators to improve their response to plant upsets

Online Modeling:
• Setup an online decision support/performance monitoring systems

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Q&A

Join the AspenTech Community

www.aspentech.com/community

Nattapol A.
Nattapol.akkarachaneeyakorn@asp
entech.com

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