Polymers Plus User Guide Volume 1

7/22/2019 Polymers Plus User Guide Volume 1

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U s e r G u i d e

P O L Y M E R P R O C E S S M O D E L I N G

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Polymers Plus7


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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.

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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

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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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PREFACE

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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:

http://www.aspentech.com/

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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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Our goal is to provide you with Polymers Plus documentation that meets your information

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


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


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


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


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


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


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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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



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


P ha se Eq uilibria .................................................................................................4 186

Ra te Ca lculations ............................................................................................... 4 186


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



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



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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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INTRODUCTION Overview

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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.



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



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.



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.



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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