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COP YRI G H T 19811999 Aspen Techn ology, In c.ALL RIG HTS RE SE RVED
The flowsheet graphics and plot components of Aspen Plus were developed by MY-Tech, Inc.
Aspen Aerotran Aspen Pinch ADVENT Aspen B -J AC Aspen Custom Modeler AspenDynamics Aspen H etra n Aspen P lus , AspenTech , B -J AC B ioP rocess Simulat or (B P S) ,DynaPlus , ModelManager , Plantelligence , the P lan telligence logo , Polymers Plus , PropertiesP lus , S P E E D U P , an d the a spen leaf logo ar e either registered tra demarks, or tra demarks of AspenTechnology, I nc., in th e U nited S ta tes a nd/or other countries.
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The License Man a ger portion of this product is ba sed on:
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U se of Aspen P lus a nd This Ma nua l
This manual is intended as a guide to using Aspen Plus process modeling software. This documentation containsAspenTech proprieta ry a nd confidentia l informa tion a nd ma y not be disclosed, used, or copied wit hout t he priorconsent of AspenTech or a s set fort h in t he a pplica ble license ag reement. U sers a re solely r esponsible for the
proper use of Aspen Plus and the application of the results obtained.
Although AspenTech ha s tested t he softw ar e and review ed the documenta tion, the sole wa rra nty for Aspen P lusmay be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NOWARRANTY OR REPRESENTATION, EITHER EXPRESS OR IMPLIED, WITH RESPECT TO THIS
DOCUMENTATION, ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A
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PREFACE
ABOUT THIS USER GUIDE
This U ser G uide documents features unique t o Polymers P lus. It a ssumes priorknowledge of basic Aspen P lus capa bilities or user a ccess to the Aspen P lusdocumenta tion set. If you a re using P olymers P lus w ith Aspen Cust om Modeler,
plea se refer to the Aspen Cust om Modeler document a tion set.
The first cha pter in th e User G uide provides an in tr oduction to the use ofmodeling for polymer processes. S ubsequent chapters discuss specific PolymersP lus ca pabilities. The fea tur es covered include methodologies for cat egorizingchemica l components a nd for tra cking th eir properties, physica l properties an dphase equilibria, polymerization kinetic models, and steady-state flowsheeting. Avolume devoted to simulat ion examples and steady-sta te a nd dyna mica pplica tions is provided as a complement to this U ser G uide. See th e PolymersPlu s Examples& Appl i cati on Case Book. These exam ples a re designed t o giveyou an overall understa nding of the steps involved in using P olymers P lus tomodel specific systems.
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CONTENTS AND ORGANIZATION
The User Guide is divided into two volumes. The main chapters contained in each volumeare described below.
Chapter Description
Volume 1
Chapter 1 - Introduction This chapter describes the basics of polymer process modeling and the
steps involved in defining a model in Polymers Plus.
Chapter 2 - Polymer Structural Characterization This chapter describes the methods used for characterizing
components. Included are the methodologies for calculating distributions
and features for tracking end-use properties.
Chapter 3 - Thermodynamic Properties This chapter describes the physical property methods available in
Polymers Plus. An overview of the key issues for polymer systems is
also given.
Chapter 4 - Polymerization Reactions This chapter describes the polymerization kinetic models. An overview
of the various categories of polymerization kinetic schemes is given.
Volume 2
Chapter 5 - Steady-State Flowsheeting This chapter provides an overview of capabilities used in constructing a
polymer process flowsheet model. For example, the unit operation
models, data fitting tools, and analysis tools, such as sensitivity studies,
etc.
Chapter 6 - Run-Time Environment This chapter covers issues concerning the run-time environment
including installation issues and troubleshooting tips.
Appendices For the most part the appendices contain data tables referred to in other
sections of the manual.
Input Language Reference This section is a tabular summary of the input language for Polymers
Plus features.
Glossary This is a compilation of specialized terminology used in polymer process
modeling and their definition.
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OTHER INFORMATION SOURCES
Parts of this User Guide refer to the Polymers Plus Examples &Applications Case Book, acomplement to this manual. In addition, for information regarding Aspen Plus capabilities
not covered in this User Guide, you may need to refer to theAspen Plus User Guide and
Reference Manuals series for:
N
Unit Operation Models
N
Physical Property Methods and Models
N
Physical Property Data
N User Models
N
System Management
PRODUCT SUPPORT SERVICES
World Wide Web For additional information about AspenTech products and services,check the AspenTech World Wide Web home page on the Internet at:
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Approximately three days after registering, you will receive a confirmation e-mail and
you will then be able to access this information.
The most current Hotline contact information is listed. Other information includes:
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Frequently asked questions
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Product training courses
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Technical tips
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PREFACE
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AspenTechHotline If you need help from an AspenTech Customer Supportengineer, contact our Hotline for any of the following locations :
If you are located in: Phone Number Fax Number E-Mail Address
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needs. To help us reach this goal, forward your comments and suggestions to
Aspen Technology, Inc.Attn: Polymer Technology CoordinatorTen Canal ParkCambridge, Massachusetts 02141USATelefax: +1-617/949-1030
For your convenience, a Comments form is included at the end of the User Guide.
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CONTENTS
VOLUME 1
Chapter 1 Introduction
About P olymers P lus................................................................................................. 1 1
Overview of P olymerizat ion P rocesses .................................................................... 1 2
P olymer Ma nufa cturing P rocess S teps ................................................................. 1 2
Issu es of Concern in P olymer P rocess Modeling..................................................... 1 4
Monomer S ynt hesis a nd P urificat ion....................................................................1 5
P olymerizat ion........................................................................................................ 1 5
Recovery /Separa tion ............................................................................................ 1 6P olymer P rocessing ................................................................................................1 6
Sum ma ry................................................................................................................. 1 6
P olymers P lus Tools ..................................................................................................1 7
Component Ch ar a cterizat ion................................................................................. 1 7
P olymer P hysica l P ropert ies.................................................................................. 1 8
P olymerizat ion Kinetics .........................................................................................1 8
Modeling Da ta ........................................................................................................ 1 8
P rocess Flowsh eeting ............................................................................................. 1 9
Defining a Model in P olymers P lus........................................................................ 1 10
References ...............................................................................................................1 12
Chapter 2 Polymer Structural CharacterizationP olymer St ructur e..................................................................................................... 2 2
Polymer Structural Properties.................................................................................2 5
Ch a ra cterizat ion Approa ch ...................................................................................... 2 5
Component Att ributes ............................................................................................ 2 6
References .................................................................................................................2 6
Section 2.1 Component Classification
Component Ca tegories.............................................................................................. 2 7
Convent iona l Components ..................................................................................... 2 8
P olymers ................................................................................................................. 2 9
Oligomers ................................................................................................................ 2 9Segment s............................................................................................................... 2 10
Site-Based .............................................................................................................2 10
Component Da ta ban ks ........................................................................................... 2 11
P ure Component D a ta ba nk .................................................................................2 11
Segment Da ta ba nk ............................................................................................... 2 12
P olymer Da ta ba nk................................................................................................ 2 12
Segment Methodology..............................................................................................2-13
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Specifying Components...........................................................................................2 13
Selecting Da ta ba nks .............................................................................................2 14
Defining Component Na mes a nd Types..............................................................2 14
Specifying Segment s.............................................................................................2 15
Specifying P olymers .............................................................................................2 15Specifying Oligomers ............................................................................................2 16
Specifying Sit e-B a sed Components .....................................................................2 17
References................................................................................................................2 18
Section 2.2 Polymer Structural Properties
St ructur al P ropert ies a s Component Attribut es ...................................................2 19
Component Att ribute Cla sses.................................................................................2 20
Component Att ribut e Ca tegories ...........................................................................2 21
P olymer Component Att ribut es ...........................................................................2 21
Sit e-B a sed Species Att ributes ..............................................................................2 32
U ser Att ribut es .....................................................................................................2 33
Component Att ribut e I nitia lizat ion .......................................................................2 34Att ribut e Init ializa tion Scheme ...........................................................................2 34
Specifying Component Att ribut es ..........................................................................2 39
Specifying P olymer C omponent Att ribut es ........................................................2 39
Specifying S ite-B a sed C omponent Att ribut es ....................................................2 39
Specifying C onventional Component Att ribut es ................................................2 39
Initializing Component Attributes in Streams or Blocks ..................................2 40
References................................................................................................................2 40
Section 2.3 Structural Property Distributions
P ropert y Dist ribut ion Types...................................................................................2 41
Dist ribution Fun ctions ............................................................................................2 43Schulz-Flory Most P robable Dist ribut ion ...........................................................2 43
St ockma yer B ivar iat e Dist ribution .....................................................................2 44
Dist ributions in P rocess Models .............................................................................2 45
Avera ge P roperties a nd Moments .......................................................................2 45
Method of Ins ta nta neous P roperties ...................................................................2 47
Co-polymerization.................................................................................................2 50
Mechanism for Tra cking Dist ributions ..................................................................2 51
Dist ributions in Kinetic Rea ctors ........................................................................2 51
Dist ributions in P rocess St rea ms ........................................................................2 53
Request ing Dist ribut ion C alcula tions....................................................................2 54
Selecting Dist ribution C ha ra cteristics ................................................................2 54
Displa ying Dist ribut ion Da ta for a Reactor ........................................................2 54Displaying Distribution Data for Streams..........................................................2 55
References................................................................................................................2 56
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Section 2.4 End-Use Properties
P olymer P ropert ies .................................................................................................2 59
En d-U se P ropert ies................................................................................................. 2 60
Relat ionship to Molecula r St ructur e................................................................... 2 60
Method for Ca lculatin g En d-U se Pr operties ......................................................... 2 62Int rinsic Viscosity................................................................................................. 2 63
Zero-Shear Viscosity ............................................................................................2 63
Densit y of Copolymer ...........................................................................................2 64
Melt Ind ex............................................................................................................. 2 64
Melt Ind ex Ra tio................................................................................................... 2 65
Ca lculatin g E nd-U se P roperties ............................................................................ 2 65
Selecting a n En d-U se P ropert y ........................................................................... 2 65
Adding an En d-U se P ropert y P rop-Set ...............................................................2 66
References ...............................................................................................................2 67
Chapter 3 Thermodynamic Properties
P ropert ies of Int erest in P rocess S imula tion ..........................................................3 2
P roperties for E quilibrium, Ma ss an d Energy B ala nces . . . . . . .. . . .. . . .. . . .. . . .. . . .. . . .. . . .. . 3 2
P roperties for D eta iled Eq uipment D esign...........................................................3 3
Summary of Important Properties for Modeling..................................................3 3
Differences Bet w een Polymers an d Non-polymers .................................................3 4
Modeling Phase Equilibria in Polymer-Containing Mixtures................................3 6
Modeling Ot her Thermophysical P ropert ies of P olymers .................................... 3 10
Property Models Available in Polymers Plus........................................................3 11
Activity Coefficient Models .................................................................................. 3 12
Eq ua tions-of-St a te................................................................................................ 3 13
Oth er Thermophysical Models ............................................................................ 3 14
P ropert y Methods....................................................................................................3 15Thermodyn a mic Da ta for P olymers .......................................................................3 17
References ...............................................................................................................3 18
Section 3.1 Van Krevelen Property Models
Sum ma ry of Applicability .......................................................................................3 21
Van Krevelen Models.............................................................................................. 3 22
Liqu id En tha lpy Model........................................................................................... 3 23
Liquid Enthalpy Model Parameters....................................................................3 24
Solid En tha lpy Model ............................................................................................. 3 26
Solid En th alpy M odel P a ra meters ...................................................................... 3 27
Liqu id G ibbs Fr ee Energy Model...........................................................................3 29
Liquid Gibbs Free Energy Model Parameters....................................................3 30Solid G ibbs Free En ergy Model.............................................................................. 3 32
Solid Gibbs Free Energy Model Parameters ......................................................3 33
Liqu id Molar Volume Model...................................................................................3 35
Liqu id Molar Volume Model Pa ra meters............................................................ 3 37
Solid Molar Volume Model .....................................................................................3 38
Solid Molar Volume Model P a ra meters .............................................................. 3 39
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G las s Tra nsit ion Temperat ure C orrelat ion...........................................................3 41
Glass Transition Correlation Parameters...........................................................3 41
Melt Tra nsition Temperat ure Correla tion ............................................................3 42
Melt Tra nsition Model P a ra meters .....................................................................3 42
Van Krevelen Property Parameter Estimation.....................................................3 43Specifying P hysica l P ropert ies ...............................................................................3 44
Selecting P hysica l P roperty Met hods..................................................................3 44
Creating Customized Physical Property Methods..............................................3 45
Ent ering P ar am eters for a P hysical P roperty Model . . . .. . . .. . . .. . . .. . . .. . . .. . . .. . . .. . . .. . . ..3 46
Ent ering a P hysical P roperty P ar am eter Est imat ion Method .. . . .. . . .. . . .. . . .. . . .. . . ..3 47
Ent ering Molecular St ructure for a P hysical P roperty E stima tion .. . . .. . . .. . . .. . . ..3 48
Ent ering Da ta for P hysical P roperties Pa ra meter Optimization . . . .. . . .. . . .. . . .. . . .. .3 49
References................................................................................................................3 50
Section 3.2 Tait Molar Volume Model
Sum ma ry of Applicability .......................................................................................3 51
Tait Molar Volume Model.......................................................................................3 52Ta it Model P a ra meters.........................................................................................3 53
Specifying the Ta it Molar Volume Model ..............................................................3 53
References................................................................................................................3 54
Section 3.3 Polymer Viscosity Models
Sum ma ry of Applicability .......................................................................................3 55
P ure P olymer Modified Ma rk-Houw ink Model .....................................................3 56
Modified Ma rk-Houw ink Model P a ra meters ......................................................3 58
Van Kr evelen Viscosity-Temperat ure Correla tion .............................................3 59
Van Krevelen Correlation Parameters................................................................3 63
Concentra ted P olymer Solution Viscosity Model ..................................................3 64Qua si-B ina ry Sy stem ...........................................................................................3 64
P ropert ies of P seudo-Components .......................................................................3 65
Solution Viscosity Model P a ra meters..................................................................3 67
P olymer S olution Viscosity Es tima tion ...............................................................3 67
P olymer S olution G las s Tra nsit ion Temperat ure ..............................................3 69
Polymer Viscosity At Mixture Glass Transition Temperature..........................3 69
True Solvent Dilution Effect ................................................................................3 70
Specifying the Viscosity Models .............................................................................3 70
References................................................................................................................3 71
Section 3.4 Flory-Huggins Activity Coefficient Model
Sum ma ry of Applicability .......................................................................................3 73Flory-Huggins Model ..............................................................................................3 74
Flory-Hu ggins Model P a ra meters .......................................................................3 77
Specifying the Flory-Hu ggins Model......................................................................3 77
References................................................................................................................3 78
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Section 3.5 NRTL Activity Coefficient Models
Sum ma ry of Applicability .......................................................................................3 79
P olymer NRTL Model O verview ............................................................................ 3 80
P olymer NRTL Model............................................................................................. 3 81
Ra ndom Copolymer NRTL Model.......................................................................... 3 83P a ra meters for t he NR TL Models ....................................................................... 3 85
Compa risons of th e P olymer N RTL Models .......................................................... 3 86
Sim ilar ities ...........................................................................................................3 86
Differences ............................................................................................................3 86
Specifying the P olymer NRTL Models................................................................... 3 86
References ...............................................................................................................3 87
Section 3.6 UNIFAC Activity Coefficient Model
Sum ma ry of Applicability .......................................................................................3 89
P olymer U NIF AC Model ........................................................................................ 3 90
Polymer UNIFAC Model Parameters .................................................................3 92Specifying the U NIF AC Model...............................................................................3 92
References ...............................................................................................................3 93
Section 3.7 Polymer UNIFAC Free Volume Model
Sum ma ry of Applicability .......................................................................................3 95
P olymer U NIF AC Free Volume Model .................................................................. 3 96
Polymer UNIFAC Free Volume Model Parameters...........................................3 97
Specifying th e P olymer U NIF AC Fr ee Volume Model ......................................... 3 97
References ...............................................................................................................3 98
Section 3.8 Polymer Ideal Gas Property Model
Sum ma ry of Applicability .......................................................................................3 99
Polymer Ideal Gas Property Model......................................................................3 100
Polymer Ideal Gas Model Parameters ..............................................................3 102
Specifying t he I deal G a s Model............................................................................ 3 102
References .............................................................................................................3 103
Section 3.9 Sanchez-Lacombe EOS Model
Sum ma ry of Applicability ..................................................................................... 3 105
Sa nchez-La combe Model ...................................................................................... 3 108
P ure Fluids ......................................................................................................... 3 108
Fluid Mixtures .................................................................................................... 3 110
P olymer Sy stems ................................................................................................ 3 111Sa nchez-La combe Model P a ra meters ............................................................... 3 112
Specifying t he S a nchez-La combe E OS Model ..................................................... 3 112
References .............................................................................................................3 113
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Section 3.10 Polymer SRK EOS Model
Sum ma ry of Applicability .....................................................................................3 116
P olymer SR K EOS Model .....................................................................................3 117
Polymer SRK EOS Model Parameters ..............................................................3 119
Specifying th e P olymer S RK EOS Model ............................................................3 122References..............................................................................................................3 122
Section 3.11 SAFT Equation-of-State Model
Sum ma ry of Applicability .....................................................................................3 123
SAFT EOS Model ..................................................................................................3 124
Ext ension to Fluid Mixtures ..............................................................................3 128
Application of SAFT..............................................................................................3 130
SAFT EOS Model P a ra meters ...........................................................................3 132
Specifying the SAFT EOS Model .........................................................................3 132
References..............................................................................................................3 133
Chapter 4 Polymerization Reactions
P olymerizat ion R eaction Ca tegories ........................................................................4 2
St ep-G rowt h P olymerizat ion .................................................................................4 4
Ch a in-G rowt h P olymerizat ion...............................................................................4 5
P olymerizat ion P rocess Types ..................................................................................4 6
P olymers P lus React ion Models ...............................................................................4 7
Built-in Models .......................................................................................................4 7
User Models ............................................................................................................4 8
References..................................................................................................................4 9
Section 4.1 Step-Growth Polymerization Model
Sum ma ry of Applicat ions .......................................................................................4 12
St ep-G rowt h P rocesses ...........................................................................................4 12
P olyesters ..............................................................................................................4 12
Nylon-6..................................................................................................................4 19
Nylon-6,6...............................................................................................................4 20
P olyca rbonat e .......................................................................................................4 23
Rea ction Kinetic Scheme ........................................................................................4 25
Overview ...............................................................................................................4 25
P olyester Reaction Kinetics .................................................................................4 30
Nylon-6 Reaction Kinetics....................................................................................4 37
Nylon-6,6 Reaction Kinetics.................................................................................4 41
Melt P olyca rbona te Reaction Kinet ics ................................................................4 49Model Fea tur es a nd Assumpt ions..........................................................................4 52
Model Predictions .................................................................................................4 52
P ha se Eq uilibria ...................................................................................................4 52
Rea ction Mecha nism ............................................................................................4 53
Model St ructur e ......................................................................................................4 53
Rea cting G roups an d Species...............................................................................4 53
Rea ction S toichiometr y G enera tion ....................................................................4 60
Model-G enerat ed Rea ctions .................................................................................4 61
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U ser Reactions ...................................................................................................... 4 67
U ser Subr outines.................................................................................................. 4 69
Specifying Step-Growth Polymerization Kinetics.................................................4 87
Accessing th e St ep-G rowt h Model....................................................................... 4 87
Specifying the St ep-G rowt h Model .....................................................................4 88Specifying Rea cting Components ........................................................................ 4 89
List ing B uilt-In Reactions....................................................................................4 89
Specifying Built-In Reaction Rate Constants.....................................................4 90
Assigning Ra te C onsta nts to Rea ctions ..............................................................4 90
Including U ser Rea ctions ..................................................................................... 4 91
Adding or E diting U ser R eactions....................................................................... 4 92
Assigning R a te Const a nts to U ser Rea ctions .....................................................4 92
Selecting Report Options .....................................................................................4 92
Including a U ser K inetic Subr outine .................................................................. 4 93
Including a User Rat e Const a nt Subroutin e ...................................................... 4 93
Including a U ser B as is Su broutine ..................................................................... 4 93
References ...............................................................................................................4 94
Section 4.2 Free-Radical Bulk Polymerization
Sum ma ry of Applicat ions .......................................................................................4 96
Fr ee-Ra dica l B ulk/Solut ion P rocesses .............. ............... ............... .............. ......... 4 97
Rea ction Kinet ic Scheme ........................................................................................4 97
Init iat ion ............................................................................................................. 4 102
P ropaga tion......................................................................................................... 4 104
Ch a in Tra nsfer to S ma ll Molecules...................................................................4 105
Termination ........................................................................................................4 105
Short and Long Chain Branching .....................................................................4 106
B eta -Scission.......................................................................................................4 107
Model Fea tur es a nd Assumpt ions........................................................................ 4 107
Ca lculation Method ............................................................................................ 4 108
Qua si-St eady -St a te Approxima tion (QSS A).....................................................4 109
P ha se Eq uilibrium..............................................................................................4 109
Gel Effect ............................................................................................................4 109
P olymer P ropert ies C a lculated ............................................................................4 112
Specifying Free-Ra dical P olymerizat ion Kinetics............................................... 4 115
Accessing th e Free-Ra dical Model..................................................................... 4 115
Specifying the Free-Ra dical Model....................................................................4 115
Specifying React ing Species............................................................................... 4 116
List ing Rea ctions ................................................................................................ 4 116
Adding Reactions ................................................................................................ 4
117
Ed iting Reactions ............................................................................................... 4 117
Assigning Ra te C onsta nts to Rea ctions ............................................................ 4 118
Selecting Ca lculation Options ........................................................................... 4 118
Adding Gel-Effect ...............................................................................................4 118
References .............................................................................................................4 119
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Section 4.3 Emulsion Polymerization Model
Sum ma ry of Applicat ions .....................................................................................4 122
Em ulsion P olymeriza tion P rocesses ....................................................................4 123
Rea ction Kinetic Scheme ......................................................................................4 123
Micellar Nucleation ............................................................................................4 124H omogeneous Nucleation...................................................................................4 128
P a rt icle G rowt h ..................................................................................................4 130
Ra dical B ala nce ..................................................................................................4 131
Kinet ics of Em ulsion P olymerizat ion ................................................................4 136
Model Fea tur es a nd Assumpt ions........................................................................4 139
Model Assumptions ............................................................................................4 139
Thermodyn a mics of Monomer P a rt itioning ......................................................4 139
P olymer P a rt icle Size D istr ibution....................................................................4 140
P olymer P a rt icle P ropert ies Ca lculated ..............................................................4 142
U ser P rofiles .......................................................................................................4 143
Specifying E mulsion P olymerizat ion Kinetics ....................................................4 144
Accessing the Emulsion Model ..........................................................................4 144Specifying the Em ulsion Model .........................................................................4 144
Specifying Reactin g Species...............................................................................4 145
List ing Rea ctions ................................................................................................4 145
Adding Reactions ................................................................................................4 146
Ed iting Reactions ...............................................................................................4 146
Assigning Ra te C onsta nt s t o Reactions ............................................................4 147
Selecting Ca lculation Options............................................................................4 147
Adding Gel-Effect ...............................................................................................4 147
Specifying P ha se P ar tit ioning ...........................................................................4 148
Specifying Particle Growth Parameters............................................................4 148
References..............................................................................................................4 149
Section 4.4 Ziegler-Natta Polymerization Model
Sum ma ry of Applicat ions .....................................................................................4 152
Ziegler-Na tt a P rocesses ........................................................................................4 152
Ca ta lyst Types ....................................................................................................4 153
Et hylene P rocess Types......................................................................................4 153
P ropylene P rocess Types ....................................................................................4 154
Rea ction Kinetic Scheme ......................................................................................4 157
Ca ta lyst Sit e Activat ion .....................................................................................4 164
Ch a in Init iat ion ..................................................................................................4 165
P ropaga tion .........................................................................................................4 165
Ch a in Tra nsfer to S ma ll Molecules ...................................................................4 166Sit e Dea ctivat ion ................................................................................................4 166
Sit e Inh ibition .....................................................................................................4 167
Cocat aly st P oisoning ..........................................................................................4 167
Long Ch ain B ra nching Rea ctions......................................................................4 167
Model Fea tur es a nd Assumpt ions........................................................................4 168
P ha se Eq uilibria .................................................................................................4 168
Ra te Ca lculations................................................................................................4 168
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P olymer P ropert ies C a lculated ............................................................................4 169
Specifying Ziegler-Na tt a P olymerizat ion Kinetics .............................................4 170
Accessing th e Ziegler-Na tt a Model ................................................................... 4 170
Specifying the Ziegler-Na tt a Model ..................................................................4 170
Specifying React ing Species............................................................................... 4 171List ing Rea ctions ................................................................................................ 4 171
Adding Reactions ................................................................................................ 4 172
Ed iting Reactions ............................................................................................... 4 172
Assigning Ra te C onsta nts to Rea ctions ............................................................ 4 173
References .............................................................................................................4 174
Section 4.5 Ionic Polymerization Model
Sum ma ry of Applicat ions ..................................................................................... 4 176
Ionic Processes ......................................................................................................4 177
Rea ction Kinet ic Scheme ...................................................................................... 4 178
Forma tion of Active Species ..............................................................................4 182
Ch a in Init iat ion R eactions................................................................................. 4 183P ropaga tion Reaction .........................................................................................4 183
Associa tion or Aggrega tion Rea ction ................................................................ 4 184
Excha nge Reactions ........................................................................................... 4 184
Eq uilibrium w ith Count er-Ion Rea ctions ......................................................... 4 184
Ch a in Tra nsfer Reactions .................................................................................. 4 185
Ch a in Termina tion Reactions ............................................................................ 4 185
Model Fea tur es a nd Assumpt ions........................................................................ 4 186
P ha se Eq uilibria .................................................................................................4 186
Ra te Ca lculations ............................................................................................... 4 186
P olymer P ropert ies C a lculated ............................................................................4 187
Specifying I onic Polymeriza tion K inetics ............................................................ 4 188
Accessing the Ionic Model..................................................................................4 188
Specifying the Ionic Model................................................................................. 4 188
Specifying React ing Species............................................................................... 4 189
List ing Rea ctions ................................................................................................ 4 189
Adding Reactions ................................................................................................ 4 190
Ed iting Reactions ............................................................................................... 4 190
Assigning Ra te C onsta nts to Rea ctions ............................................................ 4 191
References .............................................................................................................4 192
Section 4.6 Segment-Based Reaction Model
Sum ma ry of Applicat ions ..................................................................................... 4 193
P olymer Modificat ion P rocesses...........................................................................4 194Segment -B as ed Model Allowed Reactions........................................................... 4 195
Convent iona l Species Reactions ........................................................................ 4 196
Side G roup or B a ckbone Modifications ............................................................. 4 196
Ch a in Scission .................................................................................................... 4 196
De-polymerization ..............................................................................................4 197
Combina tion Reactions ...................................................................................... 4 197
Kinetic Ra te Expression..................................................................................... 4 198
Model Fea tur es a nd Assumpt ions........................................................................ 4 199
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P olymer P roperties C a lculated.............................................................................4 199
Specifying Segment -B a sed P olymer Modificat ion Reactions .............................4 200
Accessing the Segment - B a sed Model ...............................................................4 200
Specifying t he S egment- Ba sed Model ..............................................................4 200
Specifying Reaction Sett ings .............................................................................4 201B uilding a Reaction Scheme ..............................................................................4 201
Adding or Ed iting React ions ..............................................................................4 202
Assigning Ra te C onsta nt s t o Reactions ............................................................4 202
References..............................................................................................................4 203
VOLUME 2
Chapter 5 Steady-State Flowsheeting
P olymer Ma nufa cturing Flowsh eets ........................................................................5 2Monomer Sy nth esis ................................................................................................5 4
P olymer Sy nth esis ..................................................................................................5 4
Recovery /Separa tions ...........................................................................................5 4
P olymer P rocessing ................................................................................................5 5
Modeling P olymer P rocess Flowsh eets ....................................................................5 5
St eady -St a te Modeling Fea tur es..............................................................................5 5
U nit Operat ions Modeling Fea tur es......................................................................5 6
Plant Data Fitting Features ..................................................................................5 6
Process Model Application Tools ...........................................................................5 6
References..................................................................................................................5 6
Section 5.1 Steady-State Unit Operation ModelsSum ma ry of Aspen P lus U nit Operat ion Models ....................................................5 8
Dupl.........................................................................................................................5 9
Fla sh2 ....................................................................................................................5 11
Fla sh3 ....................................................................................................................5 11
FSplit .....................................................................................................................5 12
Hea ter....................................................................................................................5 12
Mixer .....................................................................................................................5 13
Mult .......................................................................................................................5 14
Pump .....................................................................................................................5 15
Pipe........................................................................................................................5 15
S ep ................. .................. .................. ................... .................. .................. ............. 5 15Sep2.......................................................................................................................5 15
Dist illat ion Models ..................................................................................................5 16
Ra dFr a c .................................................................................................................5 16
Reactor Models ........................................................................................................5 16
Ma ss-B a lan ce Reactor Models ................................................................................5 17
RStoic ....................................................................................................................5 17
RYield .................. .................. ................... .................. .................. .................. ....... 5 18
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Eq uilibrium Reactor Models .................................................................................. 5 19
RE quil ...................................................................................................................5 19
RG ibbs ...................................................................................................................5 19
Kinetic Rea ctor Models........................................................................................... 5 20
RCSTR...................................................................................................................5 20RP lug..................................................................................................................... 5 35
RB a tch................................................................................................................... 5 46
Trea tm ent of Component Att ribut es in Un it Opera tion Models .........................5 57
References ...............................................................................................................5 60
Section 5.2 Plant Data Fitting
Da ta Fitt ing Applicat ions ....................................................................................... 5 62
Da ta Fitt ing F or P olymer Models ..........................................................................5 63
Da ta Collection a nd Verificat ion .........................................................................5 64
Litera tur e Review ................................................................................................5 65
Preliminary Parameter Fitting ...........................................................................5 65
P relimina ry Model Development ........................................................................ 5 67Trend Analysis......................................................................................................5 67
Model Refinement ................................................................................................5 68
St eps in U sing t he Da ta Regression Tool .............................................................. 5 69
Ident ifying Flowsh eet Va ria bles ......................................................................... 5 70
Ma nipulat ing Va ria bles Indir ectly ......................................................................5 72
En tering P oint Da ta ............................................................................................. 5 74
En tering P rofile Da ta ........................................................................................... 5 74
Entering Standard Deviations ............................................................................5 75
Defining Da ta Regression C a ses .........................................................................5 76
Seq uencing Da ta Regression Ca ses.....................................................................5 77
Int erpreting D a ta Regression Results ................................................................ 5 78
Troubleshooting Convergence P roblems.............................................................5 79
Section 5.3 User Models
U ser U nit Operat ion Models ..................................................................................5 85
U ser U nit Opera tion Models Str ucture .............................................................. 5 86
U ser U nit Opera tion Model Calcula tions ........................................................... 5 86
U ser U nit Operat ion Report Writin g .................................................................. 5 92
U ser Kinetic Models................................................................................................ 5 92
U ser P hysica l P ropert y Models..............................................................................5 97
References .............................................................................................................5 101
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Section 5.4 Application Tools
Exa mple Applica tions for a Sim ula tion Model....................................................5 103
Applicat ion Tools Ava ilable in P olymers P lus.....................................................5 104
Fortr a n ................................................................................................................5 105
DE SI G N-SP EC ...................................................................................................5 105SENSITIVITY.....................................................................................................5 105
CASE -STU DY .....................................................................................................5 106
OPTIMIZATION.................................................................................................5 106
Model Variable Accessing .....................................................................................5 106
References...............................................................................................................5-109
Chapter 6 Run-Time Environment
P olymers P lus Architecture ......................................................................................6 1
Ins ta llat ion Issues .....................................................................................................6 2
Ha rdw a re Requir ements ........................................................................................6 2
Ins ta llat ion P rocedure ............................................................................................6 2Configuration Tips ....................................................................................................6 3
St a rt up Files ...........................................................................................................6 3
Simulation Templates ............................................................................................6 3
U ser Fortr an ..............................................................................................................6 3
U ser Fortr an Templat es.........................................................................................6 3
U ser Fortr an Linking .............................................................................................6 4
Troubleshooting Guide..............................................................................................6 4
U ser Int erface P roblems ........................................................................................6 4
Sim ula tion En gine Run-Time P roblems ...............................................................6 7
Documenta tion a nd Online Help .............................................................................6 9
References..................................................................................................................6 9
Appendix A Component Databanks
P ure Component Da ta ba nk ..................................................................................... A 1
P OLYME R Da ta ba nk............................................................................................... A 2
SE G ME NT D at a ban k .............................................................................................. A 8
Appendix B Physical Property Methods
Appendix C Van Krevelen Functional Groups
Ca lculatin g Segment P ropert ies From Fun ctional G roups ................................... C 2
Hea t Ca pacity ........................................................................................................ C 2
Molar Volume ........................................................................................................ C 2En tha lpy of Forma tion .......................................................................................... C 2
G las s Tra nsition Temperat ure ............................................................................. C 3
Melt Tra nsition Temperat ure ............................................................................... C 3
Viscosity-Temperature Gradient .......................................................................... C 3
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Appendix D Tait Model Coefficients
Appendix E Mass Based Property Parameters
Appendix F Equation-of-State Parameters
Appendix G Kinetic Rate Constant Parameters
Init iat or Decomposition Ra te .................................................................................. G 2
Appendix H Fortran Utilities
Component Attribut e Ha ndling U tilities ............................................................... H 3
CAELI D.................................................................................................................. H 3
CAID.......................................................................................................................H 4
CAMIX ...................................................................................................................H 5
CASP LT ................................................................................................................. H
6
CASP SS .................................................................................................................. H 7
CAUP DT ................................................................................................................ H 8
COP YCA ................................................................................................................ H 9
GETCRY ..............................................................................................................H 10
G ETDP N .............................................................................................................. H 11
G ETMWN ................. .................. .................. .................. ................... .................. H 12
GETMWW............................................................................................................H 13
LC AOFF ............................................................................................................... H 14
LC ATT................... .................. .................. .................. .................. .................. ..... H 15
NC AVAR .................. .................. .................. ................... .................. .................. . H 16
Component H a ndling U tilities .............................................................................. H 17
CPACK .................................................................................................................H 17IF CMNC ............................................................................................................... H 18
ISCAT...................................................................................................................H 19
IS OLIG ................................................................................................................. H 20
IS P OLY ................................................................................................................ H 21
IS SE G ...................................................................................................................H 22
SC P ACK ............................................................................................................... H 23
XATOWT................................ ................... .................. .................. .................. ..... H 24
XATOXT................................. ................... .................. .................. .................. ..... H 25
General Stream Handling Utilities ......................................................................H 26
IPTYPE ................................................................................................................H 26
LOC ATS ................. .................. .................. .................. .................. .................. .... H 27
LP HASE ............................................................................................................... H 28NP HASE .............................................................................................................. H 29
NS VAR ................. .................. .................. .................. ................... .................. ..... H 30
SS COP Y ............................................................................................................... H 31
Oth er U tilities ........................................................................................................ H 32
VOLL....................................................................................................................H 32
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Input Language Reference
Specifying Components................................Input Error! Bookmark not defined.
Na ming Components ...................................................................................... Input 2
Specifying Component Chara cterization Input s ............................................ In put 3
Specifying Component Att ribut es .................................................................... I nput 5Specifying Characterization Attributes............................................................ Input 5
Specifying C onventional Component Att ribut es .......................................... Input 5
Init ializing Att ribut es in St rea ms ................................................................. Input 5
Request ing D istr ibution C alcula tions.............................................................. Input 7
Ca lculatin g E nd U se P roperties....................................................................... Input 8
Specifying P hysica l P ropert y I nputs .............................................................. Input 10
Specifying P ropert y Methods ....................................................................... I nput 10
Specifying P ropert y Da ta ............................................................................. Input 12
Estimating Property Parameters ................................................................ Input 14
Specifying Step-Growth Polymerization Kinetics......................................... Input 15
Specifying Free-Ra dical P olymerizat ion Kinetics ......................................... Input 22
Specifying E mulsion P olymerizat ion K inetics .............................................. Input 30Specifying Ziegler-Na tt a P olymerizat ion Kinetics........................................ Input 38
Specifying Ionic P olymerizat ion K inetics ...................................................... I nput 50
Specifying Segment -B a sed P olymer Modifica tion Rea ctions ....................... Input 58
References........................................................................................................ Input 60
Glossary
Index
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1 INTRODUCTION
This chapter provides an overview of the issues related to polymer manufacturing process
modeling and their handling in Polymers Plus
.
Topics covered include:N
About Polymers Plus
N
Overview of Polymerization Processes
N
Issues of Concern in Polymer Process Modeling
N
Polymers Plus Tools
N
Defining a Model in Polymers Plus
ABOUT POLYMERS PLUS
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 Polymers Plus are modules for:
N
Characterizing polymer molecular structure
N
Calculating rheological and mechanical properties
N
Tracking these properties throughout a flowsheet
There are also many additional features that permit the simulation of the entiremanufacturing processes.
11
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OVERVIEW OF POLYMERIZATION PROCESSES
Polymer Definition
A polymer is a macromolecule made up of many smaller repeating units providing linearand branched chain structures. Although a wide variety of polymers are produced naturally,
synthetic or man-made polymers can be tailored to satisfy specific needs in the market
place, and affect our daily lives at an ever increasing rate. The worldwide production of
synthetic polymers, estimated at approximately 100 million tons annually, provides products
such as plastics, rubber, fibers, paints, and adhesives used in the manufacture of construction
and packaging materials, tires, clothing, and decorative and protective products.
Polymer Molecular
BondsPolymer molecules involve the same chemical bonds and intermolecular forces as other
smaller chemical species. However, the interactions are magnified due to the molecular
size of the polymers. Also important in polymer production are production rate
optimization, waste minimization and compliance to environmental constraints, yield
increases and product quality. In addition to these considerations, end-product processingcharacteristics and properties must be taken into account in the production of polymers
(Dotson, 1996).
PolymerManufacturingProcess Steps
Polymer manufacturing processes are usually divided into the following major steps:
1. Monomer synthesis and purification
2. Polymerization
3. Recovery/Separation
4. Polymer processing (physical and reactive)1.
The four steps may be carried out by the same manufacturer within a single integrated
plant, or specific companies may focus on one or more of these steps (Grulke, 1994).
Figure 1.1 illustrates the important stages for each of these four steps. The main issues of
concern for each of those steps are described next.
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Figure 1.1 Major Steps in Polymer Production Processes
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ISSUES OF CONCERN IN POLYMER PROCESS MODELING
There are modeling issues associated with each step in the production of polymers. Asummary of these issues along with the required tools is listed in Table 1.1.
Table 1.1 Summary of Polymer Modeling Issues/Concerns
Step Modeling Issues/Concerns Tools Required
Monomer synthesis and purification N Feedstock purity
N Monomer degradation
N Emissions
N Waste disposal
N
Unit operations: separators
N Reaction kinetics
N Phase equilibria
Polymerization N Temperature control
N Molecular weight control, polymerspecifications
N
Conversion yield
N Reaction medium viscosity
N
Residence time
N Reactor stability
N
Waste minimization
N
Characterization
N Reaction kinetics
N
Phase equilibria
N Heat transfer
N Unit operations: reactors
N Transport phenomena
N Process dynamics
N
Process control
Recovery / Separation N Solvent removal
N
Monomer recovery
N Unit operations: separators
N
Phase equilibria
N Heat and mass transfer
Polymer processing N Solvent removal
N Solids handling
N Heat and mass transfer
N Unit operations: separators
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MonomerSynthesisandPurification
During monomer synthesis and purification, the engineer is concerned with purity. This is
because the presence of contaminants, such as water or dissolved gases for example, may
adversely affect the subsequent polymerization stage by:
N
Poisoning catalystsN
Depleting initiators
N
Causing undesirable chain transfer or branching reactionsN
Another concern of this step is the prevention of monomer degradation through proper
handling or the addition of stabilizers. Control of emissions, and waste disposal are also
important factors in this step.
Polymerization The polymerization step is usually the most important step in terms of the economic
viability of the manufacturing process. The desired outcome for this step is a polymerproduct with specified properties such as:
N
Molecular weight distribution
N
Melt index
N
Composition
N
Crystallinity/density
N
Viscosity
The obstacles that must be overcome to reach this goal depend on both the mechanism of
polymer synthesis (chain growth or step growth), and on the polymerization process used.
Polymerization processes may be batch, semi-batch or continuous. In addition, they may
be carried out in bulk, solution, slurry, gas-phase, suspension or emulsion. Batch andsemi-batch processes are preferred for specialty grade polymers. Continuous processes are
usually used to manufacture large volume commodity polymers. Productivity depends on
heat removal rates and monomer conversion levels achieved. Viscosity of polymer
solutions, and polymer particle suspensions and mixing are important considerations.
These factors influence the choice of, for example, bulk versus solution versus slurry
polymerization. Another example is the choice of emulsion polymerization that is often
dictated by the form of the end-use product, water-based coating or adhesive. Other
important considerations may include health, safety and environmental impact.
Most polymerizations are highly exothermic, some involve monomers which are known
carcinogens and others may have to deal with contaminated water.In summary, for the polymerization step, the reactions which occur usually cause dramatic
changes in the reaction medium (e.g. significant viscosity increases may occur), which in
turn make high conversion kinetics, residence-time distribution, agitation and heat
transfer the most important issues for the majority of process types.
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Recovery /Separation
The recovery/separation step can be considered the step where the desired polymer
produced is further purified or isolated from by-products or residual reactants. In this step,
monomers and solvents are separated and purified for recycle or resale. The important
concerns for this step are heat and mass transfer.
PolymerProcessing
The last step, polymer processing, can also be considered a recovery step. In this step, the
polymer slurry is turned into solid pellets or chips. Heat of vaporization is an important
factor in this step (Grulke, 1994).
Summary In summary, production rate optimization, waste minimization and compliance toenvironmental constraints, yield increase, and product quality are also important issues in
the production of polymers. In addition, process dynamics and stability constitute
important factors primarily for reactors.
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POLYMERS PLUS TOOLS
Polymers Plus provides the tools that allow polymer manufacturers to capture the benefits ofprocess modeling.
Polymers Plus can be used to build models for representing processes in two modes: with
Aspen Plus
for steady-state models, and with Aspen Custom Modeler for dynamic
models. In both cases, the tools used specifically for representing polymer systems fall
into four categories:
1. Polymer characterization
2. Physical properties
3. Reaction kinetics
4. Data
Through Aspen Plus and Aspen Custom Modeler, Polymers Plus provides robust and
efficient algorithms for handling:
N
Flowsheet convergence and optimization
N
Complex separation and reaction problems
N
User customization through an open architecture
Component
Characterization
Characterization of a polymer component poses some unique challenges. For example, the
polymer component is not a single species but a mixture of many species. Properties such
as molecular weight and copolymer composition are not necessarily constant and may
vary throughout the flowsheet and with time. Polymers Plus provides a flexible
methodology for characterizing polymer components.
Each polymer is considered to be made up of a series of segments. Segments have a fixed
structure. The changing nature of the polymer is accounted for by the specification of the
number and type of segments it contains at a given processing step.
Each polymer component has associated attributes used to store information on molecular
structure and distributions, product properties, and particle size when necessary. The
polymer attributes are solved/integrated together with the material and energy balances in
the unit operation models.
_________ U.S. Patent No. 5,687,090
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PolymerPhysical
Properties
Correlative and predictive models are available in Polymers Plus for representing the
thermophysical properties of a polymer system, the phase equilibrium, and the transport
phenomena. Several physical property methods combining these models are available. In
addition to the built-in thermodynamic models, the open-architecture design allows users
to override the existing models with their own in-house models.
PolymerizationKinetics
The polymerization step represents the most important stage in polymer processes. In this
step, kinetics play a crucial role. Polymers Plus provides built-in kinetic mechanisms for
several chain-growth and step-growth type polymerization processes. The mechanisms are
based on well established sources from the open literature, and have been extensively
used and validated against data during modeling projects of industrial polymerization
reactors.
There are also models for representing polymer modification reactions, and for modelingstandard chemical kinetics. In addition to the built-in kinetic mechanisms, the open-
architecture design allows users to specify additional reactions, or to override the built-in
mechanisms.
ModelingData
A key factor in the development of a successful simulation model is the use of accurate
thermodynamic data for representing the physical properties of the system, and of kinetic
rate constant data which provide a good match against observed trends.
In order to provide the physical property models with the parameters necessary for
property calculations, Polymers Plus has property parameter databanks available. These
include:
N
Polymer databank containing parameters independent of chain length
N
Segment databank containing parameters to which composition and chain length are
applied for polymer property calculations
N
Functional group databank containing parameters for models using a group contribution
approach is also included
This User Guide contains several tabulated parameters which may be used as starting
values for specific property models. Property data packages are also being compiled for
some polymerization processes and will be made available in future versions.
In addition to physical property data, Polymers Plus provides users with ways of
estimating missing reaction rate constant data. For example, the data regression tool can
be used to fit rate constants against molecular weight data.
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ProcessFlowsheeting
Polymers Plus provides unit operation models, flowsheeting options, and analysis tools
for a complete representation of a process.
Models for batch, semi-batch and continuous reactors with mixing extremes of plug flow
to backmix are available. In addition, other unit operation models essential for flowsheetmodeling are available such as:
N
Mixers
N
Flow splitters
N
Flash tanks
N
Devolatilization units
Flowsheet connectivity and sequencing is handled in a straight forward manner.
Several analysis tools are available for applying the simulation models developed. These
include tools for:
N
Process optimization
N
Examining process alternatives as case studies
N
Analyzing the sensitivities of key process variables on polymer product properties
N
Fitting process variables to meet design specifications
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DEFINING A MODEL IN POLYMERS PLUS
In order to build a model of a polymer process you must already be familiar with AspenPlus. Therefore, only the steps specific to polymer systems will be described in detail later in
this User Guide. The steps for defining a model in Polymers Plus are as follows:
Step 1. Sp
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