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Aspen Polymers Unit Operations and Reaction Models
Version Number: V8.2 May 2013 Copyright (c) 1981-2013 by Aspen Technology, Inc. All rights reserved. Aspen Polymers™, Aspen Custom Modeler®, Aspen Dynamics®, Aspen Plus®, Aspen Properties®, aspenONE, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered trademarks of Aspen Technology, Inc., Burlington, MA. All other brand and product names are trademarks or registered trademarks of their respective companies. This software includes NIST Standard Reference Database 103b: NIST Thermodata Engine Version 7.1 This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of the software and the application of the results obtained. Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION, ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE. Aspen Technology, Inc. 200 Wheeler Road Burlington, MA 01803-5501 USA Phone: (1) (781) 221-6400 Toll Free: (1) (888) 996-7100 URL: http://www.aspentech.com
Contents Introducing Aspen Polymers ...................................................................................1 About This Documentation Set ...........................................................................1 Related Documentation.....................................................................................2 Technical Support ............................................................................................3 1 Polymer Manufacturing Process Overview...........................................................5 About Aspen Polymers ......................................................................................5 Overview of Polymerization Processes.................................................................6 Polymer Manufacturing Process Steps .......................................................6 Issues of Concern in Polymer Process Modeling....................................................7 Monomer Synthesis and Purification .........................................................8 Polymerization .......................................................................................8 Recovery / Separation ............................................................................9 Polymer Processing ................................................................................9 Summary ..............................................................................................9 Aspen Polymers Tools .......................................................................................9 Component Characterization.................................................................. 10 Polymer Physical Properties ................................................................... 10 Polymerization Kinetics ......................................................................... 10 Modeling Data...................................................................................... 11 Process Flowsheeting............................................................................ 11 Defining a Model in Aspen Polymers ................................................................. 12 References .................................................................................................... 14 2 Polymer Structural Characterization .................................................................15 Polymer Structure .......................................................................................... 15 Polymer Structural Properties .......................................................................... 19 Characterization Approach............................................................................... 19 Component Attributes........................................................................... 20 References .................................................................................................... 20 3 Component Classification ..................................................................................21 Component Categories.................................................................................... 21 Conventional Components ..................................................................... 22 Polymers............................................................................................. 22 Oligomers ........................................................................................... 23 Segments............................................................................................ 24 Site-Based .......................................................................................... 24 Component Databanks.................................................................................... 25 Pure Component Databank.................................................................... 25 PC-SAFT Databank ............................................................................... 26 POLYPCSF Databank ............................................................................. 26 Contents iii
INITIATO Databank .............................................................................. 26 Segment Databank............................................................................... 26 Polymer Databank................................................................................ 27 Segment Methodology .................................................................................... 27 Specifying Components................................................................................... 28 Selecting Databanks ............................................................................. 28 Defining Component Names and Types ................................................... 28 Specifying Segments ............................................................................ 29 Specifying Polymers ............................................................................. 29 Specifying Oligomers ............................................................................ 30 Specifying Site-Based Components......................................................... 30 References .................................................................................................... 31 4 Polymer Structural Properties ...........................................................................33 Structural Properties as Component Attributes................................................... 33 Component Attribute Classes ........................................................................... 34 Component Attribute Categories ...................................................................... 35 Polymer Component Attributes............................................................... 35 Site-Based Species Attributes ................................................................ 44 User Attributes .................................................................................... 45 Component Attribute Initialization .................................................................... 46 Attribute Initialization Scheme ............................................................... 47 Component Attribute Scale Factors................................................................... 50 Specifying Component Attributes ..................................................................... 51 Specifying Polymer Component Attributes ............................................... 51 Specifying Site-Based Component Attributes ........................................... 51 Specifying Conventional Component Attributes ........................................ 52 Initializing Component Attributes in Streams or Blocks.............................. 52 Specifying Component Attribute Scaling Factors....................................... 53 References .................................................................................................... 53 5 Structural Property Distributions ......................................................................55 Property Distribution Types ............................................................................. 55 Distribution Functions ..................................................................................... 56 Schulz-Flory Most Probable Distribution................................................... 56 Stockmayer Bivariate Distribution .......................................................... 58 Distributions in Process Models ........................................................................ 58 Average Properties and Moments ........................................................... 58 Method of Instantaneous Properties........................................................ 60 Copolymerization ................................................................................. 64 Mechanism for Tracking Distributions................................................................ 65 Distributions in Kinetic Reactors ............................................................. 65 Distributions in Process Streams ............................................................ 67 Verifying the Accuracy of Distribution Calculations.................................... 68 Requesting Distribution Calculations ................................................................. 69 Selecting Distribution Characteristics ...................................................... 69 Displaying Distribution Data for a Reactor ............................................... 70 Displaying Distribution Data for Streams ................................................. 70 References .................................................................................................... 71 iv Contents
6 End-Use Properties............................................................................................73 Polymer Properties ......................................................................................... 73 Prop-Set Properties ........................................................................................ 73 End-Use Properties......................................................................................... 74 Relationship to Molecular Structure ........................................................ 75 Method for Calculating End-Use Properties ........................................................ 76 Intrinsic Viscosity ................................................................................. 77 Zero-Shear Viscosity ............................................................................ 77 Density of Copolymer ........................................................................... 78 Melt Index........................................................................................... 78 Melt Index Ratio................................................................................... 79 Calculating End-Use Properties ........................................................................ 79 Selecting an End-Use Property............................................................... 79 Adding an End-Use Property Prop-Set ..................................................... 79 References .................................................................................................... 79 7 Polymerization Reactions ..................................................................................81 Polymerization Reaction Categories .................................................................. 81 Step-Growth Polymerization .................................................................. 83 Chain-Growth Polymerization................................................................. 83 Polymerization Process Types .......................................................................... 84 Aspen Polymers Reaction Models...................................................................... 85 Built-in Models..................................................................................... 85 User Models......................................................................................... 86 References .................................................................................................... 86 8 Step-Growth Polymerization Model ...................................................................89 Summary of Applications................................................................................. 89 Step-Growth Processes ................................................................................... 90 Polyesters ........................................................................................... 90 Nylon-6............................................................................................... 96 Nylon-6,6............................................................................................ 98 Polycarbonate.................................................................................... 100 Reaction Kinetic Scheme ............................................................................... 101 Nucleophilic Reactions ........................................................................ 101 Polyester Reaction Kinetics.................................................................. 105 Nylon-6 Reaction Kinetics.................................................................... 111 Nylon-6,6 Reaction Kinetics ................................................................. 115 Melt Polycarbonate Reaction Kinetics .................................................... 122 Model Features and Assumptions ................................................................... 124 Model Predictions ............................................................................... 124 Phase Equilibria ................................................................................. 126 Reaction Mechanism........................................................................... 126 Model Structure ........................................................................................... 127 Reacting Groups and Species............................................................... 127 Reaction Stoichiometry Generation....................................................... 132 Model-Generated Reactions ................................................................. 133 User Reactions................................................................................... 138 User Subroutines ............................................................................... 140 Specifying Step-Growth Polymerization Kinetics ............................................... 155 Accessing the Step-Growth Model......................................................... 155 Contents v
Specifying the Step-Growth Model........................................................ 156 Specifying Reacting Components.......................................................... 156 Listing Built-In Reactions..................................................................... 157 Specifying Built-In Reaction Rate Constants........................................... 157 Assigning Rate Constants to Reactions.................................................. 158 Including User Reactions ..................................................................... 158 Adding or Editing User Reactions.......................................................... 159 Specifying Rate Constants for User Reactions ........................................ 159 Assigning Rate Constants to User Reactions........................................... 159 Selecting Report Options..................................................................... 160 Selecting the Reacting Phase ............................................................... 160 Specifying Units of Measurement for Pre-Exponential Factors................... 160 Including a User Kinetic Subroutine ...................................................... 161 Including a User Rate Constant Subroutine............................................ 161 Including a User Basis Subroutine ........................................................ 161 References .................................................................................................. 161 9 Free-Radical Bulk Polymerization Model..........................................................163 Summary of Applications............................................................................... 163 Free-Radical Bulk/Solution Processes.............................................................. 164 Reaction Kinetic Scheme ............................................................................... 165 Initiation ........................................................................................... 171 Propagation....................................................................................... 176 Chain Transfer to Small Molecules ........................................................ 178 Termination....................................................................................... 179 Long Chain Branching ......................................................................... 181 Short Chain Branching ........................................................................ 182 Beta-Scission..................................................................................... 183 Reactions Involving Diene Monomers.................................................... 183 Model Features and Assumptions ................................................................... 185 Calculation Method ............................................................................. 185 Quasi-Steady-State Approximation (QSSA) ........................................... 188 Phase Equilibrium............................................................................... 188 Gel Effect .......................................................................................... 188 Polymer Properties Calculated........................................................................ 190 Specifying Free-Radical Polymerization Kinetics................................................ 193 Accessing the Free-Radical Model ......................................................... 193 Specifying the Free-Radical Model ........................................................ 193 Specifying Reacting Species................................................................. 194 Listing Reactions ................................................................................ 194 Adding Reactions ............................................................................... 194 Editing Reactions ............................................................................... 195 Assigning Rate Constants to Reactions.................................................. 195 Adding Gel-Effect ............................................................................... 196 Selecting Calculation Options............................................................... 196 Specifying User Profiles....................................................................... 197 References .................................................................................................. 197 10 Emulsion Polymerization Model .....................................................................199 Summary of Applications............................................................................... 199 Emulsion Polymerization Processes................................................................. 200 Reaction Kinetic Scheme ............................................................................... 200 vi Contents
Micellar Nucleation ............................................................................. 201 Homogeneous Nucleation .................................................................... 204 Particle Growth .................................................................................. 206 Radical Balance.................................................................................. 207 Kinetics of Emulsion Polymerization...................................................... 211 Model Features and Assumptions ................................................................... 215 Model Assumptions............................................................................. 215 Thermodynamics of Monomer Partitioning ............................................. 215 Polymer Particle Size Distribution ......................................................... 216 Polymer Particle Properties Calculated ............................................................ 218 User Profiles ...................................................................................... 218 Specifying Emulsion Polymerization Kinetics .................................................... 219 Accessing the Emulsion Model.............................................................. 219 Specifying the Emulsion Model ............................................................. 219 Specifying Reacting Species................................................................. 220 Listing Reactions ................................................................................ 220 Adding Reactions ............................................................................... 221 Editing Reactions ............................................................................... 221 Assigning Rate Constants to Reactions.................................................. 221 Selecting Calculation Options............................................................... 222 Adding Gel-Effect ............................................................................... 222 Specifying Phase Partitioning ............................................................... 222 Specifying Particle Growth Parameters .................................................. 223 References .................................................................................................. 223 11 Ziegler-Natta Polymerization Model ..............................................................225 Summary of Applications............................................................................... 225 Ziegler-Natta Processes ................................................................................ 226 Catalyst Types ................................................................................... 226 Ethylene Process Types....................................................................... 227 Propylene Process Types ..................................................................... 228 Reaction Kinetic Scheme ............................................................................... 230 Catalyst Pre-Activation........................................................................ 237 Catalyst Site Activation ....................................................................... 237 Chain Initiation .................................................................................. 237 Propagation....................................................................................... 238 Chain Transfer to Small Molecules ........................................................ 239 Site Deactivation................................................................................ 239 Site Inhibition.................................................................................... 240 Cocatalyst Poisoning........................................................................... 240 Terminal Double Bond Polymerization ................................................... 240 Model Features and Assumptions ................................................................... 243 Phase Equilibria ................................................................................. 243 Rate Calculations ............................................................................... 243 Polymer Properties Calculated........................................................................ 243 Specifying Ziegler-Natta Polymerization Kinetics .............................................. 244 Accessing the Ziegler-Natta Model ........................................................ 244 Specifying the Ziegler-Natta Model ....................................................... 244 Specifying Reacting Species................................................................. 245 Listing Reactions ................................................................................ 245 Adding Reactions ............................................................................... 246 Editing Reactions ............................................................................... 246 Contents vii
Assigning Rate Constants to Reactions.................................................. 246 References .................................................................................................. 247 12 Ionic Polymerization Model ...........................................................................249 Summary of Applications............................................................................... 249 Ionic Processes ............................................................................................ 250 Reaction Kinetic Scheme ............................................................................... 250 Formation of Active Species................................................................. 254 Chain Initiation .................................................................................. 255 Propagation....................................................................................... 255 Association or Aggregation .................................................................. 256 Exchange .......................................................................................... 256 Equilibrium with Counter-Ion ............................................................... 256 Chain Transfer ................................................................................... 257 Chain Termination.............................................................................. 257 Coupling ........................................................................................... 258 Model Features and Assumptions ................................................................... 258 Phase Equilibria ................................................................................. 258 Rate Calculations ............................................................................... 258 Polymer Properties Calculated........................................................................ 259 Specifying Ionic Polymerization Kinetics .......................................................... 260 Accessing the Ionic Model ................................................................... 260 Specifying the Ionic Model................................................................... 260 Specifying Reacting Species................................................................. 260 Listing Reactions ................................................................................ 261 Adding Reactions ............................................................................... 261 Editing Reactions ............................................................................... 261 Assigning Rate Constants to Reactions.................................................. 262 References .................................................................................................. 262 13 Segment-Based Reaction Model ....................................................................265 Summary of Applications............................................................................... 265 Step-Growth Addition Processes........................................................... 266 Polymer Modification Processes ............................................................ 266 Segment-Based Model Allowed Reactions ........................................................ 267 Conventional Species.......................................................................... 268 Side Group or Backbone Modifications................................................... 269 Chain Scission ................................................................................... 269 Depolymerization ............................................................................... 269 Propagation....................................................................................... 270 Combination ...................................................................................... 270 Branch Formation............................................................................... 270 Cross Linking..................................................................................... 270 Kinetic Rate Expression....................................................................... 270 Model Features and Assumptions ................................................................... 272 Polymer Properties Calculated........................................................................ 273 User Subroutines ............................................................................... 274 Specifying Segment-Based Kinetics ................................................................ 285 Accessing the Segment-Based Model .................................................... 285 Specifying the Segment-Based Model ................................................... 285 Specifying Reaction Settings................................................................ 285 Building A Reaction Scheme ................................................................ 287 viii Contents
Adding or Editing Reactions ................................................................. 287 Specifying Reaction Rate Constants ...................................................... 288 Assigning Rate Constants to Reactions.................................................. 288 Including a User Rate Constant Subroutine............................................ 289 Including a User Basis Subroutine ........................................................ 289 References .................................................................................................. 289 14 Steady-State Flowsheeting............................................................................291 Polymer Manufacturing Flowsheets ................................................................. 291 Monomer Synthesis ............................................................................ 292 Polymerization ................................................................................... 293 Recovery / Separations ....................................................................... 293 Polymer Processing ............................................................................ 293 Modeling Polymer Process Flowsheets ............................................................. 293 Steady-State Modeling Features..................................................................... 294 Unit Operations Modeling Features ....................................................... 294 Plant Data Fitting Features .................................................................. 294 Process Model Application Tools ........................................................... 294 References .................................................................................................. 294 15 Steady-State Unit Operation Models..............................................................295 Summary of Aspen Plus Unit Operation Models ................................................ 295 Dupl ................................................................................................. 296 Flash2............................................................................................... 298 Flash3............................................................................................... 298 FSplit................................................................................................ 299 Heater .............................................................................................. 299 Mixer ................................................................................................ 299 Mult.................................................................................................. 299 Pump................................................................................................ 300 Pipe.................................................................................................. 300 Sep .................................................................................................. 301 Sep2 ................................................................................................ 301 Distillation Models ........................................................................................ 301 RadFrac ............................................................................................ 301 Reactor Models ............................................................................................ 302 Mass-Balance Reactor Models ........................................................................ 302 RStoic............................................................................................... 302 RYield............................................................................................... 303 Equilibrium Reactor Models............................................................................ 304 REquil ............................................................................................... 304 RGibbs.............................................................................................. 304 Kinetic Reactor Models.................................................................................. 304 RCSTR .............................................................................................. 304 RPlug................................................................................................ 317 RBatch.............................................................................................. 327 Treatment of Component Attributes in Unit Operation Models ............................ 335 References .................................................................................................. 338 16 Plant Data Fitting ..........................................................................................339 Data Fitting Applications ............................................................................... 339 Contents ix
Data Fitting For Polymer Models..................................................................... 340 Data Collection and Verification............................................................ 341 Literature Review............................................................................... 341 Preliminary Parameter Fitting............................................................... 342 Preliminary Model Development ........................................................... 343 Trend Analysis ................................................................................... 343 Model Refinement .............................................................................. 344 Steps for Using the Data Regression Tool ........................................................ 345 Identifying Flowsheet Variables............................................................ 346 Manipulating Variables Indirectly.......................................................... 347 Entering Point Data ............................................................................ 349 Entering Profile Data........................................................................... 350 Entering Standard Deviations .............................................................. 351 Defining Data Regression Cases ........................................................... 352 Sequencing Data Regression Cases ...................................................... 352 Interpreting Data Regression Results.................................................... 352 Troubleshooting Convergence Problems ................................................ 353 17 User Models...................................................................................................359 User Unit Operation Models ........................................................................... 359 User Unit Operation Models Structure ................................................... 359 User Unit Operation Model Calculations ................................................. 360 User Unit Operation Report Writing....................................................... 365 User Kinetic Models ...................................................................................... 365 User Physical Property Models........................................................................ 370 References .................................................................................................. 373 18 Application Tools...........................................................................................375 Example Applications for a Simulation Model ................................................... 375 Application Tools Available in Aspen Polymers.................................................. 376 CALCULATOR..................................................................................... 376 DESIGN-SPEC.................................................................................... 377 SENSITIVITY ..................................................................................... 377 OPTIMIZATION .................................................................................. 377 Model Variable Accessing .............................................................................. 378 References .................................................................................................. 380 19 Run-Time Environment..................................................................................381 Aspen Polymers Architecture ......................................................................... 381 Installation Issues ........................................................................................ 382 Hardware Requirements...................................................................... 382 Installation Procedure ......................................................................... 382 Configuration Tips ........................................................................................ 382 Startup Files...................................................................................... 382 Simulation Templates ......................................................................... 382 User Fortran ................................................................................................ 383 User Fortran Templates....................................................................... 383 User Fortran Linking ........................................................................... 383 Troubleshooting Guide .................................................................................. 383 User Interface Problems...................................................................... 383 Simulation Engine Run-Time Problems ................................................. 385 x Contents
References .................................................................................................. 386 A Component Databanks ....................................................................................387 Pure Component Databank............................................................................ 387 POLYMER Databank ...................................................................................... 387 POLYMER Property Parameters............................................................. 387 POLYMER Databank Components.......................................................... 388 SEGMENT Databank ..................................................................................... 391 SEGMENT Property Parameters ............................................................ 391 SEGMENT Databank Components ......................................................... 392 B Kinetic Rate Constant Parameters...................................................................431 Initiator Decomposition Rate Parameters......................................................... 431 Solvent Dependency........................................................................... 431 Concentration Dependency.................................................................. 432 Temperature Dependency ................................................................... 432 Pressure Dependency ......................................................................... 433 References .................................................................................................. 444 C Fortran Utilities ...............................................................................................445 D Input Language Reference..............................................................................447 Specifying Components................................................................................. 447 Naming Components .......................................................................... 447 Specifying Component Characterization Inputs........................................ 448 Specifying Component Attributes ................................................................... 451 Specifying Characterization Attributes................................................... 451 Specifying Conventional Component Attributes ...................................... 451 Initializing Attributes in Streams .......................................................... 451 Specifying Attribute Scaling Factors................................................................ 453 Specifying Component Attribute Scale Factors ....................................... 453 Requesting Distribution Calculations ............................................................... 454 Calculating End Use Properties....................................................................... 454 Specifying Physical Property Inputs ................................................................ 456 Specifying Property Methods................................................................ 456 Specifying Property Data..................................................................... 458 Estimating Property Parameters ........................................................... 459 Specifying Step-Growth Polymerization Kinetics ............................................... 460 Specifying Free-Radical Polymerization Kinetics................................................ 467 Specifying Emulsion Polymerization Kinetics .................................................... 477 Specifying Ziegler-Natta Polymerization Kinetics .............................................. 484 Specifying Ionic Polymerization Kinetics .......................................................... 494 Specifying Segment-Based Polymer Modification Reactions................................ 501 References .................................................................................................. 505 Index ..................................................................................................................507 Contents xi
xii Contents
Introducing Aspen Polymers Aspen Polymers (formerly known as Aspen Polymers Plus) is a general-purpose process modeling system for the simulation of polymer manufacturing processes. The modeling system includes modules for the estimation of thermophysical properties, and for performing polymerization kinetic calculations and associated mass and energy balances. Also included in Aspen Polymers are modules for:  Characterizing polymer molecular structure  Calculating rheological and mechanical properties  Tracking these properties throughout a flowsheet There are also many additional features that permit the simulation of the entire manufacturing processes. About This Documentation Set The Aspen Polymers User Guide is divided into two volumes. Each volume documents features unique to Aspen Polymers. This User Guide assumes prior knowledge of basic Aspen Plus capabilities or user access to the Aspen Plus documentation set. If you are using Aspen Polymers with Aspen Dynamics, please refer to the Aspen Dynamics documentation set. Volume 1 provides an introduction to the use of modeling for polymer processes and discusses specific Aspen Polymers capabilities. Topics include:  Polymer manufacturing process overview - describes the basics of polymer process modeling and the steps involved in defining a model in Aspen Polymers.  Polymer structural characterization - describes the methods used for characterizing components. Included are the methodologies for calculating distributions and features for tracking end-use properties.  Polymerization reactions - describes the polymerization kinetic models, including: step-growth, free-radical, emulsion, Ziegler-Natta, ionic, and segment based. An overview of the various categories of polymerization kinetic schemes is given.  Steady-state flowsheeting - provides an overview of capabilities used in constructing a polymer process flowsheet model. For example, the unit Introducing Aspen Polymers 1
operation models, data fitting tools, and analysis tools, such as sensitivity studies.  Run-time environment - covers issues concerning the run-time environment including configuration and troubleshooting tips. Volume 2 describes methodologies for tracking chemical component properties, physical properties, and phase equilibria. It covers the physical property methods and models available in Aspen Polymers. Topics include:  Thermodynamic properties of polymer systems – describes polymer thermodynamic properties, their importance to process modeling, and available property methods and models.  Equation-of-state (EOS) models – provides an overview of the properties calculated from EOS models and describes available models, including: Sanchez-Lacombe, polymer SRK, SAFT, and PC-SAFT.  Activity coefficient models – provides an overview of the properties calculated from activity coefficient models and describes available models, including: Flory-Huggins, polymer NRTL, electrolyte-polymer NRTL, polymer UNIFAC.  Thermophysical properties of polymers – provides and overview of the thermophysical properties exhibited by polymers and describes available models, including: Aspen ideal gas, Tait liquid molar volume, pure component liquid enthalpy, and Van Krevelen liquid and solid, melt and glass transition temperature correlations, and group contribution methods.  Polymer viscosity models – describes polymer viscosity model implementation and available models, including: modified Mark- Houwink/van Krevelen, Aspen polymer mixture, and van Krevelen polymer solution.  Polymer thermal conductivity models - describes thermal conductivity model implementation and available models, including: modified van Krevelen and Aspen polymer mixture. Related Documentation A volume devoted to simulation and application examples for Aspen Polymers is provided as a complement to this User Guide. These examples are designed to give you an overall understanding of the steps involved in using Aspen Polymers to model specific systems. In addition to this document, a number of other documents are provided to help you learn and use Aspen Polymers, Aspen Plus, and Aspen Dynamics applications. The documentation set consists of the following: Installation Guides Aspen Engineering Suite Installation Guide Aspen Polymers Guides Aspen Polymers User Guide, Volume 1 2 Introducing Aspen Polymers
Aspen Polymers User Guide, Volume 2 (Physical Property Methods & Models) Aspen Polymers Examples & Applications Case Book Aspen Plus Guides Aspen Plus User Guide Aspen Plus Getting Started Guides Aspen Physical Property System Guides Aspen Physical Property System Physical Property Methods and Models Aspen Physical Property System Physical Property Data Aspen Dynamics Guides Aspen Dynamics Examples Aspen Dynamics User Guide Aspen Dynamics Reference Guide Help Aspen Polymers has a complete system of online help and context-sensitive prompts. The help system contains both context-sensitive help and reference information. For more information about using Aspen Polymers help, see the Aspen Plus User Guide. Third-Party More detailed examples are available in Step-Growth Polymerization Process Modeling and Product Design by Kevin Seavey and Y. A. Liu, ISBN: 978-0- 470-23823-3, Wiley, 2008. Technical Support AspenTech customers with a valid license and software maintenance agreement can register to access the online AspenTech Support Center at: http://support.aspentech.com This Web support site allows you to:  Access current product documentation  Search for tech tips, solutions and frequently asked questions (FAQs)  Search for and download application examples  Search for and download service packs and product updates  Submit and track technical issues  Send suggestions  Report product defects Introducing Aspen Polymers 3
 Review lists of known deficiencies and defects Registered users can also subscribe to our Technical Support e-Bulletins. These e-Bulletins are used to alert users to important technical support information such as:  Technical advisories  Product updates and releases Customer support is also available by phone, fax, and email. The most up-to-date contact information is available at the AspenTech Support Center at http://support.aspentech.com. 4 Introducing Aspen Polymers
1 Polymer Manufacturing Process Overview This chapter provides an overview of the issues related to polymer manufacturing process modeling and their handling in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include:  About Aspen Polymers, 5  Overview of Polymerization Processes, 6  Issues of Concern in Polymer Process Modeling, 7  Aspen Polymers Tools, 9  Defining a Model in Aspen Polymers, 12 About Aspen Polymers Aspen Polymers is a general-purpose process modeling system for the simulation of polymer manufacturing processes. The modeling system includes modules for the estimation of thermophysical properties, and for performing polymerization kinetic calculations and associated mass and energy balances. Also included in Aspen Polymers are modules for:  Characterizing polymer molecular structure  Calculating rheological and mechanical properties  Tracking these properties throughout a flowsheet There are also many additional features that permit the simulation of the entire manufacturing processes. 1 Polymer Manufacturing Process Overview 5
Overview of Polymerization Processes Polymer Definition A polymer is a macromolecule made up of many smaller repeating units providing linear and 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 Bonds Polymer 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 processing characteristics and properties must be taken into account in the production of polymers (Dotson, 1996). Polymer Manufacturing Process 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 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). 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). The following figure illustrates the important stages for each of the four polymer production steps. The main issues of concern for each of these steps are described next. 6 1 Polymer Manufacturing Process Overview
Issues of Concern in Polymer Process Modeling There are modeling issues associated with each step in the production of polymers. The following table summarizes these issues along with the required tools: 1 Polymer Manufacturing Process Overview 7
Step Modeling Issues/Concerns Tools Required Monomer synthesis and purification Feedstock purity Monomer degradation Emissions Waste disposal Unit operations: separators Reaction kinetics Phase equilibria Polymerization Temperature control Molecular weight control, polymer specifications Conversion yield Reaction medium viscosity Residence time Reactor stability Waste minimization Characterization Reaction kinetics Phase equilibria Heat transfer Unit operations: reactors Transport phenomena Process dynamics Process control Recovery / Separation Solvent removal Monomer recovery Unit operations: separators Phase equilibria Heat and mass transfer Polymer processing Solvent removal Solids handling Heat and mass transfer Unit operations: separators Monomer Synthesis and Purification 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:  Poisoning catalysts  Depleting initiators  Causing undesirable chain transfer or branching reactions 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 polymer product with specified properties such as:  Molecular weight distribution  Melt index  Composition  Crystallinity/density  Viscosity 8 1 Polymer Manufacturing Process Overview
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 and semi-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 that 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. 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. Polymer Processing 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 to environmental 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. Aspen Polymers Tools Aspen Polymers provides the tools that allow polymer manufacturers to capture the benefits of process modeling. 1 Polymer Manufacturing Process Overview 9
Aspen Polymers can be used to build models for representing processes in two modes: with Aspen Plus for steady-state models, and with Aspen Dynamics or Aspen Custom Modeler™ for dynamic models. In both cases, the tools used specifically for representing polymer systems fall into four categories:  Polymer characterization  Physical properties  Reaction kinetics  Data Through Aspen Plus, Aspen Dynamics and Aspen Custom Modeler, Aspen Polymers provides robust and efficient algorithms for handling:  Flowsheet convergence and optimization  Complex separation and reaction problems  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. Aspen Polymers provides a flexible methodology for characterizing polymer components (U.S. Patent No. 5,687,090). 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. Polymer Physical Properties Correlative and predictive models are available in Aspen Polymers 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. Polymerization Kinetics The polymerization step represents the most important stage in polymer processes. In this step, kinetics play a crucial role. Aspen Polymers 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 10 1 Polymer Manufacturing Process Overview
validated against data during modeling projects of industrial polymerization reactors. There are also models for representing polymer modification reactions, and for modeling standard 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. Modeling Data 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, Aspen Polymers has property parameter databanks available. These include:  Polymer databank containing parameters independent of chain length  Segment databank containing parameters to which composition and chain length are applied for polymer property calculations  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, Aspen Polymers 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. Process Flowsheeting Aspen Polymers 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 flowsheet modeling are available such as:  Mixers  Flow splitters  Flash tanks  Devolatilization units Flowsheet connectivity and sequencing is handled in a straightforward manner. Several analysis tools are available for applying the simulation models developed. These include tools for:  Process optimization 1 Polymer Manufacturing Process Overview 11
 Examining process alternatives  Analyzing the sensitivities of key process variables on polymer product properties  Fitting process variables to meet design specifications Defining a Model in Aspen Polymers In order to build a model of a polymer process you must already be familiar with Aspen Plus. 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 Aspen Polymers are as follows: Step 1. Specifying Global Simulation Options The first step in defining the model is the specification of:  Global simulation options, i.e. simulation type  Units to be used for simulation inputs and results  Basis for flowrates  Maximum simulation times  Diagnostic options Step 2. Defining the Flowsheet For a full flowsheet model, the next step is the flowsheet definition. Here you would specify the unit operation models contained in the flowsheet and define their connectivity. Chapter 4 describes the unit operation models available for building a flowsheet. Step 3. Defining Components Most simulation types require a definition of the component system. You must correctly identify polymers, polymer segments, and oligomers as such. All other components are considered conventional by default. Chapter 2 provides information on defining components. Step 4. Characterizing Components Conventional components in the system are categorized by type. Additional characterization information is required for other than conventional components. You must specify the:  Component attributes to be tracked for polymers  Type of segments present  Structure of oligomers  Type and activity of catalysts In addition, you may wish to request tracking of molecular weight distribution. Component characterization is discussed in Chapter 2. 12 1 Polymer Manufacturing Process Overview
Step 5. Specifying Property Models You must select the models to be used to represent the physical properties of your system. The Aspen Polymers User Guide, Volume 2, Aspen Polymers Physical Property Methods and Models, describes the options available for specifying physical property models. Step 6. Defining Polymerization Kinetics Once you have made selections out of the built-in polymerization kinetic models to represent your reaction system, you need to choose specific reactions from the sets available and enter rate constant parameters for these reactions. Chapter 3 describes the models available and provides descriptions of the input options. Step 7. Defining Feed Streams For flowsheet simulations, you must enter the conditions of the process feed streams. If the feed streams contain polymers, you must initialize the polymer attributes. Polymer attribute definition in streams is discussed in a separate section of Chapter 2. Step 8. Specifying UOS Model Operating Conditions You must specify the configuration and operating condition for unit operation models contained in the flowsheet. In the case of reactors, you have the option of assigning kinetic models defined in step 6 to specific reactors. Chapter 4 provides some general information regarding the use of unit operation models. Step 9. Specifying Additional Simulation Options For a basic simulation the input information you are required to enter in steps 1-8 is sufficient. However, there are many more advanced simulation options you may wish to add in order to refine or apply your model. These include setting up the model for plant data fitting, sensitivity analyses, etc. Many of these options are described in a separate section of Chapter 4. Information for building dynamic models is given in the Aspen Dynamics and Aspen Custom Modeler documentation sets. Note that for building dynamic models, users must first build a steady-state model containing:  Definition of the polymer system in terms of components present  Physical property models  Polymerization kinetic models Note: Aspen Polymers setup and configuration instructions are given in Chapter 5. 1 Polymer Manufacturing Process Overview 13
References Dotson, N. A., Galván, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization Process Modeling. New York: VCH Publishers. Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall. Odian, George. (1991). Principles of Polymerization (3rd Ed.). New York: John Wiley and Sons. 14 1 Polymer Manufacturing Process Overview
2 Polymer Structural Characterization One of the fundamental aspects of modeling polymer systems is the handling of the molecular structure information of polymers. This chapter discusses the approaches used to address this issue in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include:  Polymer Structure, 15  Polymer Structural Properties, 19  Characterization Approach, 19 Included in this manual are several sections devoted to the specification of polymer structural characterization information.  3 Component Classification, 21  Polymer Structural Properties, 33  Structural Property Distributions, 55  End-Use Properties, 73 Polymer Structure Polymers can be defined as large molecules or macromolecules where a smaller constituting structure repeats itself along a chain. For this reason, polymers tend to exhibit different physical behavior than small molecules also called monomers. Synthetic polymers are produced when monomers bond together through polymerization and become the repeating structure or segment within a chain. When two or more monomers bond together, a polymer is formed. Small polymer chains containing 20 or less repeating units are usually called oligomers. The fact that identifiable segments are found repeatedly along a polymer chain, provides convenient ways to categorize polymers. Polymers can be classified based on segment composition or sequence:  Homopolymers - containing one type of repeating unit which can be mapped into one segment 2 Polymer Structural Characterization 15
 Copolymers - which have two or more repeating units. Copolymers can be in a random, alternating, block, or graft configuration If we consider the arrangement of a given chain, another classification arises. Polymers may be:  Linear  Branched (with short or long chains)  Star  Ladder  Network Another classification that results from polymer structure has to do with physical state. A solid polymer may be:  Amorphous - when the chains are not arranged in a particular pattern  Crystalline - when the chains are arranged in a regular pattern A related classification divides polymers by thermal and mechanical properties into:  Thermoplastics (may go from solid to melt and vice versa)  Thermosets (remain solid through heating)  Elastomers (which have elastic properties) Finally, polymers can be categorized based on the form they are manufactured into: plastics, fibers, film, coatings, adhesives, foams, and composites. Polymer Types by Physical Structure The following figure illustrates the various polymer types based on chain structure: 16 2 Polymer Structural Characterization
2 Polymer Structural Characterization 17
Polymer Types by Property The following table illustrates the various polymer types based on properties: Classification Type Physical Property Thermal / Mechanical properties Thermoplastics Thermosets Elastomers Can melt and solidify again Remain solid through heating Have elastic properties Fabrication Plastics Fibers Coatings Adhesives Foams Composites Elastomers Very versatile in terms of application Most commonly used as textiles Used for both decorative and protective purposes Used for their bonding properties Used as packaging, upholstery, insulation, etc. Can be tailored to many applications Used for their elastic properties In addition to these classifications, polymers can be categorized based on the type of constituting atoms on the chains. Homochains produced through chain-growth polymerization have only carbon atoms on the polymer backbone. Heterochains produced through step-growth polymerization have other types of atom incorporated into the polymer backbone. Polymer Categories by Chemical Structure The following table lists various homochain and heterochain polymers based on the type of atoms on the polymer backbone or the substituted side groups: Polymer Category Description Examples Polymers with carbon-carbon backbone Polyacrylics Ethylene backbone with one acrylic acid (or derivative) as side group per ethylene Polyacrylic acid, polymethyl methacrylate, polyacrylonitrile, polyacrylamide Polydienes One double bond per repeat unit Polybutadiene Polyhalogen Fluorine or chlorine side group per hydrocarbons ethylene Polyvinyl fluoride, polyvinylidene fluoride, polyvinylchloride, Polyolefins Alphatic or aromatic substituents Polyethylene, polypropylene, polyisobutylene, polystyrene Polyvinyls From vinyl monomers Polyvinyl acetate, polyvinyl alcohol Polymers with carbon-nitrogen backbone Polyamides Amide group on backbone Nylon 6, nylon 6,6 Polyurethanes Urethane group on backbone Polyurethane foams Polyureas Urea group on backbone Polyurea resins 18 2 Polymer Structural Characterization
Polymer Category Description Examples Polymers with carbon-oxygen backbone Polyacetals Acetal group on backbone Polyacetate Polyethers Ether group on backbone Polyethylene oxide, polyphenylene oxide Polyesters Ester group on backbone Polycarbonate polyethylene therephthalate, polybutylene therephthalate polylactide Polymers with carbon-sulfur backbone Polysulfides Sulfide group on backbone Polysulfide fibers Polymer Structural Properties All the methods of categorizing polymers point to certain key characteristics that must be taken into account in order to fully define polymer molecules. Typical information needed to capture the structure and behavior of polymers includes:  Chemical structure of segments: segment type, and configuration  Chain size for the mixture of polymer chains  Crystallinity  Additional structural, thermal, and mechanical characteristics Characterization Approach Aspen Polymers allows for the different types of chemical species that may be found in a polymer system:  Monomers  Solvents  Catalysts  Oligomers  Polymers Polymer segments are introduced to identify the chemical structure of the polymer or oligomer repeat unit. In addition, they are used as building blocks within polymerization reactions, and in the determination of thermodynamic properties. More than the chemical structure of the segments is needed in order to define a polymer. Also needed is the segment composition of the chains. In addition, properties related to size are needed: degree of polymerization or number of segments. 2 Polymer Structural Characterization 19
Component Attributes Within Aspen Polymers, component attributes are used to define these structural characteristics. Component attributes are available to track segment composition, degree of polymerization, molecular weight, etc. Because the polymer is a mixture of chains, there is normally a distribution of these structural characteristics. The component attributes are used to track the averages. There are additional attributes used to track information about the distribution of chain sizes. These are the moments of chain length distribution. For detailed information about component attributes, see Polymer Structural Properties on page 33. In addition to the component attributes, users have the option within Aspen Polymers to examine polymer molecular weight distribution. This feature is based on a method of instantaneous properties. For more information, see Method of Instantaneous Properties on page 60. References Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall. Munk, P. (1989). Introduction to Macromolecular Science. New York: John Wiley and Sons. Odian, G. (1991). Principles of Polymerization (3rd Ed.). New York: John Wiley and Sons. Rudin, A. (1982). The Elements of Polymer Science and Engineering. Orlando: Academic Press. 20 2 Polymer Structural Characterization
3 Component Classification This section discusses the specification of components in a simulation model. Topics covered include:  Component Categories, 21  Component Databanks, 25  Segment Methodology, 27  Specifying Components, 28 Component Categories When developing a simulation model in Aspen Polymers (formerly known as Aspen Polymers Plus), users must assign components present in process flow streams to one of the following categories:  Conventional  Polymer  Oligomer  Segment  Site-based The following figure illustrates the different categories of components and their input requirements: 3 Component Classification 21
22 Conventional Components Standard conventional components are molecular components such as water. These components have a fixed molecular structure and participate in phase equilibrium. Components falling into this category include:  Monomers  Initiators  Chain transfer agents  Solvents  Catalysts In order to fully specify conventional c component data required for the phase equilibrium calculations. This data may be entered or retrieved from component databanks. Note: Ziegler-Natta catalysts and ionic initiators require additional characterization inf Polymers In Aspen Polymers, polymer components represent a distribution of polymeric species. The average size and composition of the molecules in this distribution 3 Component Classification quilibrium. components, you need only specify pure information. omponents,
can change throughout the simulation. Each polymer molecule is considered to be made up of repeating units or segments. Typically, the segments correspond to the monomers that are used to grow the polymer. The structure of polymers depends on the number and type of segments they contain and the arrangement of segments in linear, branched, or cross-linked forms. Component attributes are used to track polymer structural properties (U.S. Patent No. 5,687,090) such as:  Segment composition  Copolymer composition and average sequence length  Degree of polymerization  Molecular weight  Branching  Moments of molecular weight distribution  Molecular architecture (physical arrangement of segments within the polymer molecule) Segments are specified independently from polymers. For each polymer, you must select the types of component attributes to be included in the simulation model. If the polymer is present in the process feed streams, you must provide its properties by initializing the component attributes while specifying input data for these feed streams. For more information on component attribute specification, see Polymer Structural Properties on page 33. Oligomers By convention, oligomers are defined as components with two or more segments and a fixed molecular structure. They can be defined as volatile or non-volatile. Typically, the oligomer feature is used to allow users to track the loss of volatile short-chain polymers. In order to specify oligomers, you must specify their composition in terms of the number and type of segments they contain. Oligomers do not require component attributes. For this reason, you may treat a polymer as an oligomer in cases where you want to process the polymer within a unit operation model which cannot handle polymer component attribute data. When using oligomer components, you may specify addition properties through the following unary property parameters: Parameter Definition Default POLDP Number-average chain length Calculated * POLPDI Polydispersity index 1 ** POLCRY Mass fraction crystallinity * Calculated from the number of segments in the oligomer as specified in the Polymers form Oligomers subform. ** Used to calculate DPW and MWW. 3 Component Classification 23
Note: Not all kinetic models track oligomers as separate components. If a model does not provide fields for specifying oligomers on its input forms, then these components are not tracked. Segments Segments are the structural units of a polymer or oligomer and are specified independently from these components. Their structure is fixed throughout a simulation. Segments typically correspond to the monomers used to grow the polymer. They are divided into types depending on their location on the polymer chain:  Repeat units  End groups  Branch point (attached to three or four branches) Site-Based Site-based components pertain to multisite reaction kinetic models (Ziegler- Natta and Ionic). Site-based components include Ziegler-Natta catalysts and ionic initiators. Ziegler-Natta Catalysts Ziegler-Natta catalysts are often used to initiate polymer chain formation in chain-growth polymerization reactions. Catalysts can be treated as standard conventional components. Ziegler-Natta catalysts or metallocene catalysts involve one or more polymerization site types which may be in an activated or deactivated state. In order to use Ziegler-Natta catalysts, you must specify the number of site types and the catalyst properties to be tracked, that is, the site activity. Catalyst properties are defined as component attributes. You must initialize the catalyst properties while specifying input data for the streams containing the catalysts. For more information on component attribute specification, see Polymer Structural Properties on page 33. Ionic Initiators Ionic initiators are used in anionic and cationic polymerization. The ionic initiators can be treated as standard conventional components. The propagating species in ionic polymerization can be:  Free-ions  Ion-pairs  Dormant esters 24 3 Component Classification
In Aspen Polymers, these different species are modeled as different sites of an ionic initiator. Three different site-based attributes are tracked for an ionic initiator. For more information, see Ionic Initiator Attributes on page 45. Component Databanks The thermodynamic and transport property models needed to perform the physical property and phase equilibrium calculations during a simulation require pure component property data. These include:  Molecular weight  Heat capacity  Heat of formation  Heat of vaporization  Vapor pressure  Density Enter that information while selecting and specifying physical property models. Normally, you would make use of the pure component databanks and retrieve data from them for each of the components present in the simulation model:  Data for conventional components are retrieved from the Pure Component databank  Data for free-radical initiators are retrieved from the INITIATOR databank  Data for polymers are retrieved from the POLYMER databank  Data for oligomers are retrieved either from the pure component databank or from the POLYMER databank  Data for segments are retrieved from the SEGMENT databank  Data for PC-SAFT are retrieved from the PC-SAFT databank  Data for POLYPCSF are retrieved from the POLYPCSF databank Descriptions of the databanks, and the parameters they contain are given in Appendix A. Pure Component Databank In the Pure Component databank, components are named using a nomenclature developed for Aspen Plus. Each component is given an alias summarizing the number of each type of atom: C, H, O, N, P, S, CL, F, etc. (e.g. C2H4 for ethylene). For cases where the same alias matches several components, a counter is added to make the distinction (e.g. C2H4O2-1 for acetic acid). Note: Catalysts are often solid components and may not be found in the PURE11 databank. Normally, you do not need a rigorous representation of these components. 3 Component Classification 25
An acceptable approach is to assign a monomer alias to the catalyst and then provide the correct molecular weight and certain parameters which will prevent the catalyst from vaporizing. If an activity coefficient model is being used for phase equilibrium representation, the catalysts can be assumed to be non-volatile by specifying -40 as the first Antoine parameter (PLXANT(1) = - 40). PC-SAFT Databank The PC-SAFT databank contains pure and binary parameters used with the PC-SAFT property method. The parameters are taken from the literature, including many normal compounds, polar compounds and associating compounds. POLYPCSF Databank The POLYPCSF databank contains pure and binary parameters used with the POLYPCSF property method. The parameters are taken from the literature, including many normal compounds, but excluding polar compounds and associating compounds. INITIATO Databank The INITIATO databank contains data for initiator components. Rate constants in this databank are derived from half-life data in vendor datasheets published on public web sites. These datasheets generally contain data at several temperatures, allowing the activation energy and prefactor to be determined. These rate constants depend on the reaction environment, and may vary between polar and non-polar solvents. Where multiple sets of data were available, the data from monomer or organic solvents were used in preference to data from aqueous solutions. Molecular weight and other parameters are calculated from structure using estimation methods from Aspen Plus, except in those few cases where vapor pressure data was provided in the datasheets. In the INITIATO databank, components are named using industry-standard acronyms. Each component is given an alias summarizing the number of each type of atom: C, H, O, N, P, S, CL, F, etc. For cases where the same alias matches several components, a counter is added to make the distinction (e.g. –1,-2, etc). Segment Databank In the Segment Databank, a segment name comes from the name of the monomer from which it originates. Therefore, in this databank component names and aliases follow the same conventions as those for the Pure Component Databank. A label is added to the monomer name to identify the segment as either a repeat unit,-R, an end group,-E, or a branch point, -B (e.g. for butadiene segments: C4H6R1or BUTADIENER1 corresponding to the repeat unit – 26 3 Component Classification
CH2–CH=CH–CH2, C4H5E1 or BUTADIENEE1 corresponding to the end group –CH=CH–CH=CH2 and C4H5B or BUTADIENEB corresponding to the branch segment CH2 CH CH CH ). Polymer Databank The Polymer Databank does not follow the conventional nomenclature. The polymer aliases are the typical acronyms used in industry or academia, and the polymer names consist of the repeat unit name enclosed in parentheses and preceded by the prefix Poly (e.g. PS or POLY(STYRENE) for polystyrene). Note: The MW property parameter used to store molecular weights in the component databanks is the true molecular weight for all component types except polymers. For polymers, the true polymer molecular weight is normally tracked as a component attribute only. The molecular weight stored in the databank is the apparent molecular weight calculated as the average segment molecular weight (See Appendix A). Segment Methodology The segment approach to characterizing components is a fundamental methodology which affects almost every functionality within Aspen Polymers. Segments are used as the building blocks for polymers. Once you have specified the types of segments in the polymer, the segment composition and degree of polymerization defined as component attributes may be used to define the size and composition of the polymer. For oligomers, although component attributes are not used, the number of each segment must be specified directly. Most of the Aspen Polymers physical property models calculate polymer and oligomer properties from segment properties. This is done by taking into account the degree of polymerization and the segment composition. The calculated properties should be the same for both oligomers and polymers, assuming that the oligomer structure and molecular weight were specified correctly. Note that this is true for mass-based properties only. Mole-based properties will be different between polymer and oligomer if their apparent molecular weights are different. Within the polymerization reaction models, segments also play a key role. As polymerization progresses, the models map the reacting monomers into the corresponding segments and return rates of change for the segment composition. 3 Component Classification 27
Specifying Components To specify components within your model you need to know the following: Item For Component types All the species in your system Property parameter databank The species in the system selections IUPAC names All conventional components or you need their physical properties (molecular weight, boiling point, Antoine constants, etc.) Segment structure All polymers and oligomers (define whether you want to include any end groups or branch points) Polymer properties to be tracked All polymers, that is, degree of polymerization, segment composition Additional characteristics All additional characteristics for catalysts, or ionic initiators Selecting Databanks For an Aspen Polymers simulation, you generally retrieve physical property data from the following databanks:  Pure component databank (PURE12)  Polymer databank (POLYMER)  Polymer segment databank (SEGMENT)  Initiator databank (INITIATOR) You can also use other Aspen Plus databanks, user databanks, or in-house databanks. Appendix A provides descriptions of the polymer and segment databanks and the parameters they contain. If you selected a polymer template to start your simulation, the correct databanks are already specified. If you did not select a polymer template, or if you want to modify the databank selection: 1 From the Data Browser, click Components. 2 From the Components folder, click Specifications. 3 On the Selection sheet, click the Databanks tab to open the databank selection form. Defining Component Names and Types You must specify a:  Name and a type for each component in the simulation  Component name or identifier  Databank name or alias that sets the pure component properties for the component 28 3 Component Classification
 Component type that sets the category to which the component belongs and determines the treatment of that component To access the components specifications input sheet: 1 From the Data Browser, click Components. 2 From the Components folder, click Specifications. 3 On the Selection sheet, click the Databanks tab to set the databanks to be searched for pure component properties. To define component names and types: 1 On the Selection sheet, in the Component ID field, specify an ID for each component. This ID is used to refer to the component in all subsequent input, and is also used to identify the component in the simulation report. 2 For polymers, oligomers, and segments, specify the component type in the Type field. By default, all components are assumed to be standard conventional components. For Aspen Polymers simulation you must correctly identify the component types: Use For Conventional Standard conventional components Polymer Homo and copolymers Oligomer Short chain polymer molecules Segment Polymer or oligomer repeat units 3 If component property data is being retrieved from databanks, you must also supply either the databank alias in the Alias field, or the databank name in the Component name field. Specifying Segments The Type of each polymer or oligomer segment must be specified on the Polymer Characterization Segments sheet. Segments can be repeat units, end groups or branch points attached to three or four branches. To access the segments definition input form: 1 From the Data Browser, click Components. 2 From the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. To define segments:  On the Segments sheet, assign a type to the segments from the Type field. Specifying Polymers For each polymer you must define the component attributes to be tracked. All components specified Polymer in the Components Specifications folder require component attributes. 3 Component Classification 29
To access the polymer input specifications: 1 From the Data Browser, click Components. 2 From the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the Characterization form, click the Polymers tab. To specify component attributes for the polymers in your simulation: 1 In the Polymer ID field, select the polymer. 2 If you want to retrieve a predefined set of component attributes, in Built-in attribute group select a grouping. The attribute summary table is filled in. For a complete discussion of Aspen Polymers component attributes, see Polymer Structural Properties on page 33.  or  If you do not want to use a predefined set of attributes, or if you want to change the attribute selection for a given group, click the attribute table or click Edit to open the attribute list. 3 Click specific attributes to add or remove them from the list. Repeat these steps for each polymer. Specifying Oligomers For each oligomer you must specify an ID and a structure in terms of number and name of contained segments. To access the oligomers definition input form: 1 From the Data Browser, click Components. 2 From the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the Characterization form, click the Oligomers tab. To define oligomers: 1 In the Oligomer field, select the oligomer. 2 In the Segment field, enter the name of a segment contained in the oligomer. 3 Repeat these steps for each oligomer. You can define as many segments as needed for an oligomer. Specifying Site-Based Components Specify the structure and activity of site-based catalytic species such as Ziegler-Natta catalysts and ionic initiators. To access the site-based species definition form: 1 From the Data Browser, click Components. 2 From the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the Characterization form, click the Site-Based Species tab. 30 3 Component Classification
To specify site-based species characteristics: 1 Select the component type: Ziegler-Natta catalyst, ionic initiator, etc. 2 In the Comp ID field, specify the component name. 3 Specify the number of site types in Number of sites for the component. For Ziegler-Natta catalysts, you must also specify the moles of sites per gram of catalyst. 4 Select the list of properties or component attributes to be tracked for that component. Click the attribute list table or Edit to open the attribute list. 5 Click specific attributes to add or remove them from the list for the component. References Bailey, J., & Ollis, D. F. (1986) Biochemical Engineering Fundamentals (2nd Ed.). New York: McGraw-Hill. Brandrup, J., & Immergut, E. H. (Eds.). (1989). Polymer Handbook (3rd Ed.). New York: John Wiley & Sons. Danner R. P., & High, M. S. (1992). Handbook of Polymer Solution Thermodynamics. New York: American Institute of Chemical Engineers. Kroschwitz, J. (Ed.). (1990). Concise Encyclopedia of Polymer Science and Engineering. New York: John Wiley and Sons. 3 Component Classification 31
32 3 Component Classification
4 Polymer Structural Properties This section discusses the use of component attributes for tracking polymer structural properties in a simulation model. Topics covered include:  Structural Properties as Component Attributes, 33  Component Attribute Classes, 34  Component Attribute Categories, 35  Component Attribute Initialization, 46  Component Attribute Scale Factors, 50  Specifying Component Attributes, 51 Structural Properties as Component Attributes Component attributes provide a convenient framework to associate structural characterization data to components in a flow stream. They are carried throughout the flowsheet along with state and composition information, and effectively extend the stream structure. Aspen Polymers (formerly known as Aspen Polymers Plus) uses component attributes as a vehicle for tracking important modeling information for polymers, ionic initiators and Ziegler-Natta catalysts (U.S. Patent No. 5,687,090). For example, there are component attributes to store:  Segment composition (segment fraction or segment flow)  Copolymer composition and average sequence length  Degree of polymerization (number, weight, and z-average)  Molecular weight (number, weight, and z-average)  Degree of branching (long and short)  Degree of cross-linking (cross-link density)  Molecular architecture (physical arrangement of segments within the polymer molecule) 4 Polymer Structural Properties 33
 Live polymer properties  Aggregate polymer properties In the case of multi-site-type Ziegler-Natta catalyst polymerization, the attributes provide the structure to store the properties by site. Examples of catalyst attributes include the fraction of dead and potential sites. The catalyst attributes are used to track catalyst activity. There are also component attributes available to track user defined data. The complete list of available attributes is given in the Polymer Component Attributes, Site-Based Species Attributes, and User Attributes sections of this chapter (pages 35 through 45). Component Attribute Classes Component attributes are divided into classes to reflect the nature of various structural properties carried in process streams:  Class 0 component attributes are derived quantities from other attributes. They are therefore recalculated from these attributes after they are updated. For example, number average degree of polymerization is a Class 0 component attribute. It is computed from the zeroth and the first moments of chain length distribution.  Class 1 component attributes are structural properties per unit mass. They are not used for polymers.  Class 2 component attributes are structural properties per unit time. Examples are zeroth and first moments of chain length distribution The following table lists the differences between the Aspen Polymers component attribute classes: Class Conserved Quantity Convergence Treatment Unit of Measurement Examples 0 N/A Recalculated Varies Degree of polymerization 1 Attribute  component mass Direct substitution Attribute / component mass None for polymers 2 Attribute Accelerated convergence Attribute / time Segment flows, moments of chain length distribution For a typical polymer process simulation, Class 0 and Class 2 component attributes are used. Since Class 0 component attributes are calculated from Class 2 attributes, users have the option of entering either of the two types for simulation models where polymer is present in the process feed streams. For this reason, an attribute initialization scheme has been designed. For more information, see Component Attribute Initialization on page 46. 34 4 Polymer Structural Properties
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Aspen polymersunitopsv8 2-usr

  • 1. Aspen Polymers Unit Operations and Reaction Models
  • 2. Version Number: V8.2 May 2013 Copyright (c) 1981-2013 by Aspen Technology, Inc. All rights reserved. Aspen Polymers™, Aspen Custom Modeler®, Aspen Dynamics®, Aspen Plus®, Aspen Properties®, aspenONE, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered trademarks of Aspen Technology, Inc., Burlington, MA. All other brand and product names are trademarks or registered trademarks of their respective companies. This software includes NIST Standard Reference Database 103b: NIST Thermodata Engine Version 7.1 This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of the software and the application of the results obtained. Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION, ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE. Aspen Technology, Inc. 200 Wheeler Road Burlington, MA 01803-5501 USA Phone: (1) (781) 221-6400 Toll Free: (1) (888) 996-7100 URL: http://www.aspentech.com
  • 3. Contents Introducing Aspen Polymers ...................................................................................1 About This Documentation Set ...........................................................................1 Related Documentation.....................................................................................2 Technical Support ............................................................................................3 1 Polymer Manufacturing Process Overview...........................................................5 About Aspen Polymers ......................................................................................5 Overview of Polymerization Processes.................................................................6 Polymer Manufacturing Process Steps .......................................................6 Issues of Concern in Polymer Process Modeling....................................................7 Monomer Synthesis and Purification .........................................................8 Polymerization .......................................................................................8 Recovery / Separation ............................................................................9 Polymer Processing ................................................................................9 Summary ..............................................................................................9 Aspen Polymers Tools .......................................................................................9 Component Characterization.................................................................. 10 Polymer Physical Properties ................................................................... 10 Polymerization Kinetics ......................................................................... 10 Modeling Data...................................................................................... 11 Process Flowsheeting............................................................................ 11 Defining a Model in Aspen Polymers ................................................................. 12 References .................................................................................................... 14 2 Polymer Structural Characterization .................................................................15 Polymer Structure .......................................................................................... 15 Polymer Structural Properties .......................................................................... 19 Characterization Approach............................................................................... 19 Component Attributes........................................................................... 20 References .................................................................................................... 20 3 Component Classification ..................................................................................21 Component Categories.................................................................................... 21 Conventional Components ..................................................................... 22 Polymers............................................................................................. 22 Oligomers ........................................................................................... 23 Segments............................................................................................ 24 Site-Based .......................................................................................... 24 Component Databanks.................................................................................... 25 Pure Component Databank.................................................................... 25 PC-SAFT Databank ............................................................................... 26 POLYPCSF Databank ............................................................................. 26 Contents iii
  • 4. INITIATO Databank .............................................................................. 26 Segment Databank............................................................................... 26 Polymer Databank................................................................................ 27 Segment Methodology .................................................................................... 27 Specifying Components................................................................................... 28 Selecting Databanks ............................................................................. 28 Defining Component Names and Types ................................................... 28 Specifying Segments ............................................................................ 29 Specifying Polymers ............................................................................. 29 Specifying Oligomers ............................................................................ 30 Specifying Site-Based Components......................................................... 30 References .................................................................................................... 31 4 Polymer Structural Properties ...........................................................................33 Structural Properties as Component Attributes................................................... 33 Component Attribute Classes ........................................................................... 34 Component Attribute Categories ...................................................................... 35 Polymer Component Attributes............................................................... 35 Site-Based Species Attributes ................................................................ 44 User Attributes .................................................................................... 45 Component Attribute Initialization .................................................................... 46 Attribute Initialization Scheme ............................................................... 47 Component Attribute Scale Factors................................................................... 50 Specifying Component Attributes ..................................................................... 51 Specifying Polymer Component Attributes ............................................... 51 Specifying Site-Based Component Attributes ........................................... 51 Specifying Conventional Component Attributes ........................................ 52 Initializing Component Attributes in Streams or Blocks.............................. 52 Specifying Component Attribute Scaling Factors....................................... 53 References .................................................................................................... 53 5 Structural Property Distributions ......................................................................55 Property Distribution Types ............................................................................. 55 Distribution Functions ..................................................................................... 56 Schulz-Flory Most Probable Distribution................................................... 56 Stockmayer Bivariate Distribution .......................................................... 58 Distributions in Process Models ........................................................................ 58 Average Properties and Moments ........................................................... 58 Method of Instantaneous Properties........................................................ 60 Copolymerization ................................................................................. 64 Mechanism for Tracking Distributions................................................................ 65 Distributions in Kinetic Reactors ............................................................. 65 Distributions in Process Streams ............................................................ 67 Verifying the Accuracy of Distribution Calculations.................................... 68 Requesting Distribution Calculations ................................................................. 69 Selecting Distribution Characteristics ...................................................... 69 Displaying Distribution Data for a Reactor ............................................... 70 Displaying Distribution Data for Streams ................................................. 70 References .................................................................................................... 71 iv Contents
  • 5. 6 End-Use Properties............................................................................................73 Polymer Properties ......................................................................................... 73 Prop-Set Properties ........................................................................................ 73 End-Use Properties......................................................................................... 74 Relationship to Molecular Structure ........................................................ 75 Method for Calculating End-Use Properties ........................................................ 76 Intrinsic Viscosity ................................................................................. 77 Zero-Shear Viscosity ............................................................................ 77 Density of Copolymer ........................................................................... 78 Melt Index........................................................................................... 78 Melt Index Ratio................................................................................... 79 Calculating End-Use Properties ........................................................................ 79 Selecting an End-Use Property............................................................... 79 Adding an End-Use Property Prop-Set ..................................................... 79 References .................................................................................................... 79 7 Polymerization Reactions ..................................................................................81 Polymerization Reaction Categories .................................................................. 81 Step-Growth Polymerization .................................................................. 83 Chain-Growth Polymerization................................................................. 83 Polymerization Process Types .......................................................................... 84 Aspen Polymers Reaction Models...................................................................... 85 Built-in Models..................................................................................... 85 User Models......................................................................................... 86 References .................................................................................................... 86 8 Step-Growth Polymerization Model ...................................................................89 Summary of Applications................................................................................. 89 Step-Growth Processes ................................................................................... 90 Polyesters ........................................................................................... 90 Nylon-6............................................................................................... 96 Nylon-6,6............................................................................................ 98 Polycarbonate.................................................................................... 100 Reaction Kinetic Scheme ............................................................................... 101 Nucleophilic Reactions ........................................................................ 101 Polyester Reaction Kinetics.................................................................. 105 Nylon-6 Reaction Kinetics.................................................................... 111 Nylon-6,6 Reaction Kinetics ................................................................. 115 Melt Polycarbonate Reaction Kinetics .................................................... 122 Model Features and Assumptions ................................................................... 124 Model Predictions ............................................................................... 124 Phase Equilibria ................................................................................. 126 Reaction Mechanism........................................................................... 126 Model Structure ........................................................................................... 127 Reacting Groups and Species............................................................... 127 Reaction Stoichiometry Generation....................................................... 132 Model-Generated Reactions ................................................................. 133 User Reactions................................................................................... 138 User Subroutines ............................................................................... 140 Specifying Step-Growth Polymerization Kinetics ............................................... 155 Accessing the Step-Growth Model......................................................... 155 Contents v
  • 6. Specifying the Step-Growth Model........................................................ 156 Specifying Reacting Components.......................................................... 156 Listing Built-In Reactions..................................................................... 157 Specifying Built-In Reaction Rate Constants........................................... 157 Assigning Rate Constants to Reactions.................................................. 158 Including User Reactions ..................................................................... 158 Adding or Editing User Reactions.......................................................... 159 Specifying Rate Constants for User Reactions ........................................ 159 Assigning Rate Constants to User Reactions........................................... 159 Selecting Report Options..................................................................... 160 Selecting the Reacting Phase ............................................................... 160 Specifying Units of Measurement for Pre-Exponential Factors................... 160 Including a User Kinetic Subroutine ...................................................... 161 Including a User Rate Constant Subroutine............................................ 161 Including a User Basis Subroutine ........................................................ 161 References .................................................................................................. 161 9 Free-Radical Bulk Polymerization Model..........................................................163 Summary of Applications............................................................................... 163 Free-Radical Bulk/Solution Processes.............................................................. 164 Reaction Kinetic Scheme ............................................................................... 165 Initiation ........................................................................................... 171 Propagation....................................................................................... 176 Chain Transfer to Small Molecules ........................................................ 178 Termination....................................................................................... 179 Long Chain Branching ......................................................................... 181 Short Chain Branching ........................................................................ 182 Beta-Scission..................................................................................... 183 Reactions Involving Diene Monomers.................................................... 183 Model Features and Assumptions ................................................................... 185 Calculation Method ............................................................................. 185 Quasi-Steady-State Approximation (QSSA) ........................................... 188 Phase Equilibrium............................................................................... 188 Gel Effect .......................................................................................... 188 Polymer Properties Calculated........................................................................ 190 Specifying Free-Radical Polymerization Kinetics................................................ 193 Accessing the Free-Radical Model ......................................................... 193 Specifying the Free-Radical Model ........................................................ 193 Specifying Reacting Species................................................................. 194 Listing Reactions ................................................................................ 194 Adding Reactions ............................................................................... 194 Editing Reactions ............................................................................... 195 Assigning Rate Constants to Reactions.................................................. 195 Adding Gel-Effect ............................................................................... 196 Selecting Calculation Options............................................................... 196 Specifying User Profiles....................................................................... 197 References .................................................................................................. 197 10 Emulsion Polymerization Model .....................................................................199 Summary of Applications............................................................................... 199 Emulsion Polymerization Processes................................................................. 200 Reaction Kinetic Scheme ............................................................................... 200 vi Contents
  • 7. Micellar Nucleation ............................................................................. 201 Homogeneous Nucleation .................................................................... 204 Particle Growth .................................................................................. 206 Radical Balance.................................................................................. 207 Kinetics of Emulsion Polymerization...................................................... 211 Model Features and Assumptions ................................................................... 215 Model Assumptions............................................................................. 215 Thermodynamics of Monomer Partitioning ............................................. 215 Polymer Particle Size Distribution ......................................................... 216 Polymer Particle Properties Calculated ............................................................ 218 User Profiles ...................................................................................... 218 Specifying Emulsion Polymerization Kinetics .................................................... 219 Accessing the Emulsion Model.............................................................. 219 Specifying the Emulsion Model ............................................................. 219 Specifying Reacting Species................................................................. 220 Listing Reactions ................................................................................ 220 Adding Reactions ............................................................................... 221 Editing Reactions ............................................................................... 221 Assigning Rate Constants to Reactions.................................................. 221 Selecting Calculation Options............................................................... 222 Adding Gel-Effect ............................................................................... 222 Specifying Phase Partitioning ............................................................... 222 Specifying Particle Growth Parameters .................................................. 223 References .................................................................................................. 223 11 Ziegler-Natta Polymerization Model ..............................................................225 Summary of Applications............................................................................... 225 Ziegler-Natta Processes ................................................................................ 226 Catalyst Types ................................................................................... 226 Ethylene Process Types....................................................................... 227 Propylene Process Types ..................................................................... 228 Reaction Kinetic Scheme ............................................................................... 230 Catalyst Pre-Activation........................................................................ 237 Catalyst Site Activation ....................................................................... 237 Chain Initiation .................................................................................. 237 Propagation....................................................................................... 238 Chain Transfer to Small Molecules ........................................................ 239 Site Deactivation................................................................................ 239 Site Inhibition.................................................................................... 240 Cocatalyst Poisoning........................................................................... 240 Terminal Double Bond Polymerization ................................................... 240 Model Features and Assumptions ................................................................... 243 Phase Equilibria ................................................................................. 243 Rate Calculations ............................................................................... 243 Polymer Properties Calculated........................................................................ 243 Specifying Ziegler-Natta Polymerization Kinetics .............................................. 244 Accessing the Ziegler-Natta Model ........................................................ 244 Specifying the Ziegler-Natta Model ....................................................... 244 Specifying Reacting Species................................................................. 245 Listing Reactions ................................................................................ 245 Adding Reactions ............................................................................... 246 Editing Reactions ............................................................................... 246 Contents vii
  • 8. Assigning Rate Constants to Reactions.................................................. 246 References .................................................................................................. 247 12 Ionic Polymerization Model ...........................................................................249 Summary of Applications............................................................................... 249 Ionic Processes ............................................................................................ 250 Reaction Kinetic Scheme ............................................................................... 250 Formation of Active Species................................................................. 254 Chain Initiation .................................................................................. 255 Propagation....................................................................................... 255 Association or Aggregation .................................................................. 256 Exchange .......................................................................................... 256 Equilibrium with Counter-Ion ............................................................... 256 Chain Transfer ................................................................................... 257 Chain Termination.............................................................................. 257 Coupling ........................................................................................... 258 Model Features and Assumptions ................................................................... 258 Phase Equilibria ................................................................................. 258 Rate Calculations ............................................................................... 258 Polymer Properties Calculated........................................................................ 259 Specifying Ionic Polymerization Kinetics .......................................................... 260 Accessing the Ionic Model ................................................................... 260 Specifying the Ionic Model................................................................... 260 Specifying Reacting Species................................................................. 260 Listing Reactions ................................................................................ 261 Adding Reactions ............................................................................... 261 Editing Reactions ............................................................................... 261 Assigning Rate Constants to Reactions.................................................. 262 References .................................................................................................. 262 13 Segment-Based Reaction Model ....................................................................265 Summary of Applications............................................................................... 265 Step-Growth Addition Processes........................................................... 266 Polymer Modification Processes ............................................................ 266 Segment-Based Model Allowed Reactions ........................................................ 267 Conventional Species.......................................................................... 268 Side Group or Backbone Modifications................................................... 269 Chain Scission ................................................................................... 269 Depolymerization ............................................................................... 269 Propagation....................................................................................... 270 Combination ...................................................................................... 270 Branch Formation............................................................................... 270 Cross Linking..................................................................................... 270 Kinetic Rate Expression....................................................................... 270 Model Features and Assumptions ................................................................... 272 Polymer Properties Calculated........................................................................ 273 User Subroutines ............................................................................... 274 Specifying Segment-Based Kinetics ................................................................ 285 Accessing the Segment-Based Model .................................................... 285 Specifying the Segment-Based Model ................................................... 285 Specifying Reaction Settings................................................................ 285 Building A Reaction Scheme ................................................................ 287 viii Contents
  • 9. Adding or Editing Reactions ................................................................. 287 Specifying Reaction Rate Constants ...................................................... 288 Assigning Rate Constants to Reactions.................................................. 288 Including a User Rate Constant Subroutine............................................ 289 Including a User Basis Subroutine ........................................................ 289 References .................................................................................................. 289 14 Steady-State Flowsheeting............................................................................291 Polymer Manufacturing Flowsheets ................................................................. 291 Monomer Synthesis ............................................................................ 292 Polymerization ................................................................................... 293 Recovery / Separations ....................................................................... 293 Polymer Processing ............................................................................ 293 Modeling Polymer Process Flowsheets ............................................................. 293 Steady-State Modeling Features..................................................................... 294 Unit Operations Modeling Features ....................................................... 294 Plant Data Fitting Features .................................................................. 294 Process Model Application Tools ........................................................... 294 References .................................................................................................. 294 15 Steady-State Unit Operation Models..............................................................295 Summary of Aspen Plus Unit Operation Models ................................................ 295 Dupl ................................................................................................. 296 Flash2............................................................................................... 298 Flash3............................................................................................... 298 FSplit................................................................................................ 299 Heater .............................................................................................. 299 Mixer ................................................................................................ 299 Mult.................................................................................................. 299 Pump................................................................................................ 300 Pipe.................................................................................................. 300 Sep .................................................................................................. 301 Sep2 ................................................................................................ 301 Distillation Models ........................................................................................ 301 RadFrac ............................................................................................ 301 Reactor Models ............................................................................................ 302 Mass-Balance Reactor Models ........................................................................ 302 RStoic............................................................................................... 302 RYield............................................................................................... 303 Equilibrium Reactor Models............................................................................ 304 REquil ............................................................................................... 304 RGibbs.............................................................................................. 304 Kinetic Reactor Models.................................................................................. 304 RCSTR .............................................................................................. 304 RPlug................................................................................................ 317 RBatch.............................................................................................. 327 Treatment of Component Attributes in Unit Operation Models ............................ 335 References .................................................................................................. 338 16 Plant Data Fitting ..........................................................................................339 Data Fitting Applications ............................................................................... 339 Contents ix
  • 10. Data Fitting For Polymer Models..................................................................... 340 Data Collection and Verification............................................................ 341 Literature Review............................................................................... 341 Preliminary Parameter Fitting............................................................... 342 Preliminary Model Development ........................................................... 343 Trend Analysis ................................................................................... 343 Model Refinement .............................................................................. 344 Steps for Using the Data Regression Tool ........................................................ 345 Identifying Flowsheet Variables............................................................ 346 Manipulating Variables Indirectly.......................................................... 347 Entering Point Data ............................................................................ 349 Entering Profile Data........................................................................... 350 Entering Standard Deviations .............................................................. 351 Defining Data Regression Cases ........................................................... 352 Sequencing Data Regression Cases ...................................................... 352 Interpreting Data Regression Results.................................................... 352 Troubleshooting Convergence Problems ................................................ 353 17 User Models...................................................................................................359 User Unit Operation Models ........................................................................... 359 User Unit Operation Models Structure ................................................... 359 User Unit Operation Model Calculations ................................................. 360 User Unit Operation Report Writing....................................................... 365 User Kinetic Models ...................................................................................... 365 User Physical Property Models........................................................................ 370 References .................................................................................................. 373 18 Application Tools...........................................................................................375 Example Applications for a Simulation Model ................................................... 375 Application Tools Available in Aspen Polymers.................................................. 376 CALCULATOR..................................................................................... 376 DESIGN-SPEC.................................................................................... 377 SENSITIVITY ..................................................................................... 377 OPTIMIZATION .................................................................................. 377 Model Variable Accessing .............................................................................. 378 References .................................................................................................. 380 19 Run-Time Environment..................................................................................381 Aspen Polymers Architecture ......................................................................... 381 Installation Issues ........................................................................................ 382 Hardware Requirements...................................................................... 382 Installation Procedure ......................................................................... 382 Configuration Tips ........................................................................................ 382 Startup Files...................................................................................... 382 Simulation Templates ......................................................................... 382 User Fortran ................................................................................................ 383 User Fortran Templates....................................................................... 383 User Fortran Linking ........................................................................... 383 Troubleshooting Guide .................................................................................. 383 User Interface Problems...................................................................... 383 Simulation Engine Run-Time Problems ................................................. 385 x Contents
  • 11. References .................................................................................................. 386 A Component Databanks ....................................................................................387 Pure Component Databank............................................................................ 387 POLYMER Databank ...................................................................................... 387 POLYMER Property Parameters............................................................. 387 POLYMER Databank Components.......................................................... 388 SEGMENT Databank ..................................................................................... 391 SEGMENT Property Parameters ............................................................ 391 SEGMENT Databank Components ......................................................... 392 B Kinetic Rate Constant Parameters...................................................................431 Initiator Decomposition Rate Parameters......................................................... 431 Solvent Dependency........................................................................... 431 Concentration Dependency.................................................................. 432 Temperature Dependency ................................................................... 432 Pressure Dependency ......................................................................... 433 References .................................................................................................. 444 C Fortran Utilities ...............................................................................................445 D Input Language Reference..............................................................................447 Specifying Components................................................................................. 447 Naming Components .......................................................................... 447 Specifying Component Characterization Inputs........................................ 448 Specifying Component Attributes ................................................................... 451 Specifying Characterization Attributes................................................... 451 Specifying Conventional Component Attributes ...................................... 451 Initializing Attributes in Streams .......................................................... 451 Specifying Attribute Scaling Factors................................................................ 453 Specifying Component Attribute Scale Factors ....................................... 453 Requesting Distribution Calculations ............................................................... 454 Calculating End Use Properties....................................................................... 454 Specifying Physical Property Inputs ................................................................ 456 Specifying Property Methods................................................................ 456 Specifying Property Data..................................................................... 458 Estimating Property Parameters ........................................................... 459 Specifying Step-Growth Polymerization Kinetics ............................................... 460 Specifying Free-Radical Polymerization Kinetics................................................ 467 Specifying Emulsion Polymerization Kinetics .................................................... 477 Specifying Ziegler-Natta Polymerization Kinetics .............................................. 484 Specifying Ionic Polymerization Kinetics .......................................................... 494 Specifying Segment-Based Polymer Modification Reactions................................ 501 References .................................................................................................. 505 Index ..................................................................................................................507 Contents xi
  • 13. Introducing Aspen Polymers Aspen Polymers (formerly known as Aspen Polymers Plus) is a general-purpose process modeling system for the simulation of polymer manufacturing processes. The modeling system includes modules for the estimation of thermophysical properties, and for performing polymerization kinetic calculations and associated mass and energy balances. Also included in Aspen Polymers are modules for:  Characterizing polymer molecular structure  Calculating rheological and mechanical properties  Tracking these properties throughout a flowsheet There are also many additional features that permit the simulation of the entire manufacturing processes. About This Documentation Set The Aspen Polymers User Guide is divided into two volumes. Each volume documents features unique to Aspen Polymers. This User Guide assumes prior knowledge of basic Aspen Plus capabilities or user access to the Aspen Plus documentation set. If you are using Aspen Polymers with Aspen Dynamics, please refer to the Aspen Dynamics documentation set. Volume 1 provides an introduction to the use of modeling for polymer processes and discusses specific Aspen Polymers capabilities. Topics include:  Polymer manufacturing process overview - describes the basics of polymer process modeling and the steps involved in defining a model in Aspen Polymers.  Polymer structural characterization - describes the methods used for characterizing components. Included are the methodologies for calculating distributions and features for tracking end-use properties.  Polymerization reactions - describes the polymerization kinetic models, including: step-growth, free-radical, emulsion, Ziegler-Natta, ionic, and segment based. An overview of the various categories of polymerization kinetic schemes is given.  Steady-state flowsheeting - provides an overview of capabilities used in constructing a polymer process flowsheet model. For example, the unit Introducing Aspen Polymers 1
  • 14. operation models, data fitting tools, and analysis tools, such as sensitivity studies.  Run-time environment - covers issues concerning the run-time environment including configuration and troubleshooting tips. Volume 2 describes methodologies for tracking chemical component properties, physical properties, and phase equilibria. It covers the physical property methods and models available in Aspen Polymers. Topics include:  Thermodynamic properties of polymer systems – describes polymer thermodynamic properties, their importance to process modeling, and available property methods and models.  Equation-of-state (EOS) models – provides an overview of the properties calculated from EOS models and describes available models, including: Sanchez-Lacombe, polymer SRK, SAFT, and PC-SAFT.  Activity coefficient models – provides an overview of the properties calculated from activity coefficient models and describes available models, including: Flory-Huggins, polymer NRTL, electrolyte-polymer NRTL, polymer UNIFAC.  Thermophysical properties of polymers – provides and overview of the thermophysical properties exhibited by polymers and describes available models, including: Aspen ideal gas, Tait liquid molar volume, pure component liquid enthalpy, and Van Krevelen liquid and solid, melt and glass transition temperature correlations, and group contribution methods.  Polymer viscosity models – describes polymer viscosity model implementation and available models, including: modified Mark- Houwink/van Krevelen, Aspen polymer mixture, and van Krevelen polymer solution.  Polymer thermal conductivity models - describes thermal conductivity model implementation and available models, including: modified van Krevelen and Aspen polymer mixture. Related Documentation A volume devoted to simulation and application examples for Aspen Polymers is provided as a complement to this User Guide. These examples are designed to give you an overall understanding of the steps involved in using Aspen Polymers to model specific systems. In addition to this document, a number of other documents are provided to help you learn and use Aspen Polymers, Aspen Plus, and Aspen Dynamics applications. The documentation set consists of the following: Installation Guides Aspen Engineering Suite Installation Guide Aspen Polymers Guides Aspen Polymers User Guide, Volume 1 2 Introducing Aspen Polymers
  • 15. Aspen Polymers User Guide, Volume 2 (Physical Property Methods & Models) Aspen Polymers Examples & Applications Case Book Aspen Plus Guides Aspen Plus User Guide Aspen Plus Getting Started Guides Aspen Physical Property System Guides Aspen Physical Property System Physical Property Methods and Models Aspen Physical Property System Physical Property Data Aspen Dynamics Guides Aspen Dynamics Examples Aspen Dynamics User Guide Aspen Dynamics Reference Guide Help Aspen Polymers has a complete system of online help and context-sensitive prompts. The help system contains both context-sensitive help and reference information. For more information about using Aspen Polymers help, see the Aspen Plus User Guide. Third-Party More detailed examples are available in Step-Growth Polymerization Process Modeling and Product Design by Kevin Seavey and Y. A. Liu, ISBN: 978-0- 470-23823-3, Wiley, 2008. Technical Support AspenTech customers with a valid license and software maintenance agreement can register to access the online AspenTech Support Center at: http://support.aspentech.com This Web support site allows you to:  Access current product documentation  Search for tech tips, solutions and frequently asked questions (FAQs)  Search for and download application examples  Search for and download service packs and product updates  Submit and track technical issues  Send suggestions  Report product defects Introducing Aspen Polymers 3
  • 16.  Review lists of known deficiencies and defects Registered users can also subscribe to our Technical Support e-Bulletins. These e-Bulletins are used to alert users to important technical support information such as:  Technical advisories  Product updates and releases Customer support is also available by phone, fax, and email. The most up-to-date contact information is available at the AspenTech Support Center at http://support.aspentech.com. 4 Introducing Aspen Polymers
  • 17. 1 Polymer Manufacturing Process Overview This chapter provides an overview of the issues related to polymer manufacturing process modeling and their handling in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include:  About Aspen Polymers, 5  Overview of Polymerization Processes, 6  Issues of Concern in Polymer Process Modeling, 7  Aspen Polymers Tools, 9  Defining a Model in Aspen Polymers, 12 About Aspen Polymers Aspen Polymers is a general-purpose process modeling system for the simulation of polymer manufacturing processes. The modeling system includes modules for the estimation of thermophysical properties, and for performing polymerization kinetic calculations and associated mass and energy balances. Also included in Aspen Polymers are modules for:  Characterizing polymer molecular structure  Calculating rheological and mechanical properties  Tracking these properties throughout a flowsheet There are also many additional features that permit the simulation of the entire manufacturing processes. 1 Polymer Manufacturing Process Overview 5
  • 18. Overview of Polymerization Processes Polymer Definition A polymer is a macromolecule made up of many smaller repeating units providing linear and 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 Bonds Polymer 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 processing characteristics and properties must be taken into account in the production of polymers (Dotson, 1996). Polymer Manufacturing Process 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 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). 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). The following figure illustrates the important stages for each of the four polymer production steps. The main issues of concern for each of these steps are described next. 6 1 Polymer Manufacturing Process Overview
  • 19. Issues of Concern in Polymer Process Modeling There are modeling issues associated with each step in the production of polymers. The following table summarizes these issues along with the required tools: 1 Polymer Manufacturing Process Overview 7
  • 20. Step Modeling Issues/Concerns Tools Required Monomer synthesis and purification Feedstock purity Monomer degradation Emissions Waste disposal Unit operations: separators Reaction kinetics Phase equilibria Polymerization Temperature control Molecular weight control, polymer specifications Conversion yield Reaction medium viscosity Residence time Reactor stability Waste minimization Characterization Reaction kinetics Phase equilibria Heat transfer Unit operations: reactors Transport phenomena Process dynamics Process control Recovery / Separation Solvent removal Monomer recovery Unit operations: separators Phase equilibria Heat and mass transfer Polymer processing Solvent removal Solids handling Heat and mass transfer Unit operations: separators Monomer Synthesis and Purification 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:  Poisoning catalysts  Depleting initiators  Causing undesirable chain transfer or branching reactions 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 polymer product with specified properties such as:  Molecular weight distribution  Melt index  Composition  Crystallinity/density  Viscosity 8 1 Polymer Manufacturing Process Overview
  • 21. 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 and semi-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 that 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. 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. Polymer Processing 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 to environmental 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. Aspen Polymers Tools Aspen Polymers provides the tools that allow polymer manufacturers to capture the benefits of process modeling. 1 Polymer Manufacturing Process Overview 9
  • 22. Aspen Polymers can be used to build models for representing processes in two modes: with Aspen Plus for steady-state models, and with Aspen Dynamics or Aspen Custom Modeler™ for dynamic models. In both cases, the tools used specifically for representing polymer systems fall into four categories:  Polymer characterization  Physical properties  Reaction kinetics  Data Through Aspen Plus, Aspen Dynamics and Aspen Custom Modeler, Aspen Polymers provides robust and efficient algorithms for handling:  Flowsheet convergence and optimization  Complex separation and reaction problems  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. Aspen Polymers provides a flexible methodology for characterizing polymer components (U.S. Patent No. 5,687,090). 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. Polymer Physical Properties Correlative and predictive models are available in Aspen Polymers 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. Polymerization Kinetics The polymerization step represents the most important stage in polymer processes. In this step, kinetics play a crucial role. Aspen Polymers 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 10 1 Polymer Manufacturing Process Overview
  • 23. validated against data during modeling projects of industrial polymerization reactors. There are also models for representing polymer modification reactions, and for modeling standard 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. Modeling Data 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, Aspen Polymers has property parameter databanks available. These include:  Polymer databank containing parameters independent of chain length  Segment databank containing parameters to which composition and chain length are applied for polymer property calculations  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, Aspen Polymers 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. Process Flowsheeting Aspen Polymers 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 flowsheet modeling are available such as:  Mixers  Flow splitters  Flash tanks  Devolatilization units Flowsheet connectivity and sequencing is handled in a straightforward manner. Several analysis tools are available for applying the simulation models developed. These include tools for:  Process optimization 1 Polymer Manufacturing Process Overview 11
  • 24.  Examining process alternatives  Analyzing the sensitivities of key process variables on polymer product properties  Fitting process variables to meet design specifications Defining a Model in Aspen Polymers In order to build a model of a polymer process you must already be familiar with Aspen Plus. 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 Aspen Polymers are as follows: Step 1. Specifying Global Simulation Options The first step in defining the model is the specification of:  Global simulation options, i.e. simulation type  Units to be used for simulation inputs and results  Basis for flowrates  Maximum simulation times  Diagnostic options Step 2. Defining the Flowsheet For a full flowsheet model, the next step is the flowsheet definition. Here you would specify the unit operation models contained in the flowsheet and define their connectivity. Chapter 4 describes the unit operation models available for building a flowsheet. Step 3. Defining Components Most simulation types require a definition of the component system. You must correctly identify polymers, polymer segments, and oligomers as such. All other components are considered conventional by default. Chapter 2 provides information on defining components. Step 4. Characterizing Components Conventional components in the system are categorized by type. Additional characterization information is required for other than conventional components. You must specify the:  Component attributes to be tracked for polymers  Type of segments present  Structure of oligomers  Type and activity of catalysts In addition, you may wish to request tracking of molecular weight distribution. Component characterization is discussed in Chapter 2. 12 1 Polymer Manufacturing Process Overview
  • 25. Step 5. Specifying Property Models You must select the models to be used to represent the physical properties of your system. The Aspen Polymers User Guide, Volume 2, Aspen Polymers Physical Property Methods and Models, describes the options available for specifying physical property models. Step 6. Defining Polymerization Kinetics Once you have made selections out of the built-in polymerization kinetic models to represent your reaction system, you need to choose specific reactions from the sets available and enter rate constant parameters for these reactions. Chapter 3 describes the models available and provides descriptions of the input options. Step 7. Defining Feed Streams For flowsheet simulations, you must enter the conditions of the process feed streams. If the feed streams contain polymers, you must initialize the polymer attributes. Polymer attribute definition in streams is discussed in a separate section of Chapter 2. Step 8. Specifying UOS Model Operating Conditions You must specify the configuration and operating condition for unit operation models contained in the flowsheet. In the case of reactors, you have the option of assigning kinetic models defined in step 6 to specific reactors. Chapter 4 provides some general information regarding the use of unit operation models. Step 9. Specifying Additional Simulation Options For a basic simulation the input information you are required to enter in steps 1-8 is sufficient. However, there are many more advanced simulation options you may wish to add in order to refine or apply your model. These include setting up the model for plant data fitting, sensitivity analyses, etc. Many of these options are described in a separate section of Chapter 4. Information for building dynamic models is given in the Aspen Dynamics and Aspen Custom Modeler documentation sets. Note that for building dynamic models, users must first build a steady-state model containing:  Definition of the polymer system in terms of components present  Physical property models  Polymerization kinetic models Note: Aspen Polymers setup and configuration instructions are given in Chapter 5. 1 Polymer Manufacturing Process Overview 13
  • 26. References Dotson, N. A., Galván, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization Process Modeling. New York: VCH Publishers. Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall. Odian, George. (1991). Principles of Polymerization (3rd Ed.). New York: John Wiley and Sons. 14 1 Polymer Manufacturing Process Overview
  • 27. 2 Polymer Structural Characterization One of the fundamental aspects of modeling polymer systems is the handling of the molecular structure information of polymers. This chapter discusses the approaches used to address this issue in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include:  Polymer Structure, 15  Polymer Structural Properties, 19  Characterization Approach, 19 Included in this manual are several sections devoted to the specification of polymer structural characterization information.  3 Component Classification, 21  Polymer Structural Properties, 33  Structural Property Distributions, 55  End-Use Properties, 73 Polymer Structure Polymers can be defined as large molecules or macromolecules where a smaller constituting structure repeats itself along a chain. For this reason, polymers tend to exhibit different physical behavior than small molecules also called monomers. Synthetic polymers are produced when monomers bond together through polymerization and become the repeating structure or segment within a chain. When two or more monomers bond together, a polymer is formed. Small polymer chains containing 20 or less repeating units are usually called oligomers. The fact that identifiable segments are found repeatedly along a polymer chain, provides convenient ways to categorize polymers. Polymers can be classified based on segment composition or sequence:  Homopolymers - containing one type of repeating unit which can be mapped into one segment 2 Polymer Structural Characterization 15
  • 28.  Copolymers - which have two or more repeating units. Copolymers can be in a random, alternating, block, or graft configuration If we consider the arrangement of a given chain, another classification arises. Polymers may be:  Linear  Branched (with short or long chains)  Star  Ladder  Network Another classification that results from polymer structure has to do with physical state. A solid polymer may be:  Amorphous - when the chains are not arranged in a particular pattern  Crystalline - when the chains are arranged in a regular pattern A related classification divides polymers by thermal and mechanical properties into:  Thermoplastics (may go from solid to melt and vice versa)  Thermosets (remain solid through heating)  Elastomers (which have elastic properties) Finally, polymers can be categorized based on the form they are manufactured into: plastics, fibers, film, coatings, adhesives, foams, and composites. Polymer Types by Physical Structure The following figure illustrates the various polymer types based on chain structure: 16 2 Polymer Structural Characterization
  • 29. 2 Polymer Structural Characterization 17
  • 30. Polymer Types by Property The following table illustrates the various polymer types based on properties: Classification Type Physical Property Thermal / Mechanical properties Thermoplastics Thermosets Elastomers Can melt and solidify again Remain solid through heating Have elastic properties Fabrication Plastics Fibers Coatings Adhesives Foams Composites Elastomers Very versatile in terms of application Most commonly used as textiles Used for both decorative and protective purposes Used for their bonding properties Used as packaging, upholstery, insulation, etc. Can be tailored to many applications Used for their elastic properties In addition to these classifications, polymers can be categorized based on the type of constituting atoms on the chains. Homochains produced through chain-growth polymerization have only carbon atoms on the polymer backbone. Heterochains produced through step-growth polymerization have other types of atom incorporated into the polymer backbone. Polymer Categories by Chemical Structure The following table lists various homochain and heterochain polymers based on the type of atoms on the polymer backbone or the substituted side groups: Polymer Category Description Examples Polymers with carbon-carbon backbone Polyacrylics Ethylene backbone with one acrylic acid (or derivative) as side group per ethylene Polyacrylic acid, polymethyl methacrylate, polyacrylonitrile, polyacrylamide Polydienes One double bond per repeat unit Polybutadiene Polyhalogen Fluorine or chlorine side group per hydrocarbons ethylene Polyvinyl fluoride, polyvinylidene fluoride, polyvinylchloride, Polyolefins Alphatic or aromatic substituents Polyethylene, polypropylene, polyisobutylene, polystyrene Polyvinyls From vinyl monomers Polyvinyl acetate, polyvinyl alcohol Polymers with carbon-nitrogen backbone Polyamides Amide group on backbone Nylon 6, nylon 6,6 Polyurethanes Urethane group on backbone Polyurethane foams Polyureas Urea group on backbone Polyurea resins 18 2 Polymer Structural Characterization
  • 31. Polymer Category Description Examples Polymers with carbon-oxygen backbone Polyacetals Acetal group on backbone Polyacetate Polyethers Ether group on backbone Polyethylene oxide, polyphenylene oxide Polyesters Ester group on backbone Polycarbonate polyethylene therephthalate, polybutylene therephthalate polylactide Polymers with carbon-sulfur backbone Polysulfides Sulfide group on backbone Polysulfide fibers Polymer Structural Properties All the methods of categorizing polymers point to certain key characteristics that must be taken into account in order to fully define polymer molecules. Typical information needed to capture the structure and behavior of polymers includes:  Chemical structure of segments: segment type, and configuration  Chain size for the mixture of polymer chains  Crystallinity  Additional structural, thermal, and mechanical characteristics Characterization Approach Aspen Polymers allows for the different types of chemical species that may be found in a polymer system:  Monomers  Solvents  Catalysts  Oligomers  Polymers Polymer segments are introduced to identify the chemical structure of the polymer or oligomer repeat unit. In addition, they are used as building blocks within polymerization reactions, and in the determination of thermodynamic properties. More than the chemical structure of the segments is needed in order to define a polymer. Also needed is the segment composition of the chains. In addition, properties related to size are needed: degree of polymerization or number of segments. 2 Polymer Structural Characterization 19
  • 32. Component Attributes Within Aspen Polymers, component attributes are used to define these structural characteristics. Component attributes are available to track segment composition, degree of polymerization, molecular weight, etc. Because the polymer is a mixture of chains, there is normally a distribution of these structural characteristics. The component attributes are used to track the averages. There are additional attributes used to track information about the distribution of chain sizes. These are the moments of chain length distribution. For detailed information about component attributes, see Polymer Structural Properties on page 33. In addition to the component attributes, users have the option within Aspen Polymers to examine polymer molecular weight distribution. This feature is based on a method of instantaneous properties. For more information, see Method of Instantaneous Properties on page 60. References Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall. Munk, P. (1989). Introduction to Macromolecular Science. New York: John Wiley and Sons. Odian, G. (1991). Principles of Polymerization (3rd Ed.). New York: John Wiley and Sons. Rudin, A. (1982). The Elements of Polymer Science and Engineering. Orlando: Academic Press. 20 2 Polymer Structural Characterization
  • 33. 3 Component Classification This section discusses the specification of components in a simulation model. Topics covered include:  Component Categories, 21  Component Databanks, 25  Segment Methodology, 27  Specifying Components, 28 Component Categories When developing a simulation model in Aspen Polymers (formerly known as Aspen Polymers Plus), users must assign components present in process flow streams to one of the following categories:  Conventional  Polymer  Oligomer  Segment  Site-based The following figure illustrates the different categories of components and their input requirements: 3 Component Classification 21
  • 34. 22 Conventional Components Standard conventional components are molecular components such as water. These components have a fixed molecular structure and participate in phase equilibrium. Components falling into this category include:  Monomers  Initiators  Chain transfer agents  Solvents  Catalysts In order to fully specify conventional c component data required for the phase equilibrium calculations. This data may be entered or retrieved from component databanks. Note: Ziegler-Natta catalysts and ionic initiators require additional characterization inf Polymers In Aspen Polymers, polymer components represent a distribution of polymeric species. The average size and composition of the molecules in this distribution 3 Component Classification quilibrium. components, you need only specify pure information. omponents,
  • 35. can change throughout the simulation. Each polymer molecule is considered to be made up of repeating units or segments. Typically, the segments correspond to the monomers that are used to grow the polymer. The structure of polymers depends on the number and type of segments they contain and the arrangement of segments in linear, branched, or cross-linked forms. Component attributes are used to track polymer structural properties (U.S. Patent No. 5,687,090) such as:  Segment composition  Copolymer composition and average sequence length  Degree of polymerization  Molecular weight  Branching  Moments of molecular weight distribution  Molecular architecture (physical arrangement of segments within the polymer molecule) Segments are specified independently from polymers. For each polymer, you must select the types of component attributes to be included in the simulation model. If the polymer is present in the process feed streams, you must provide its properties by initializing the component attributes while specifying input data for these feed streams. For more information on component attribute specification, see Polymer Structural Properties on page 33. Oligomers By convention, oligomers are defined as components with two or more segments and a fixed molecular structure. They can be defined as volatile or non-volatile. Typically, the oligomer feature is used to allow users to track the loss of volatile short-chain polymers. In order to specify oligomers, you must specify their composition in terms of the number and type of segments they contain. Oligomers do not require component attributes. For this reason, you may treat a polymer as an oligomer in cases where you want to process the polymer within a unit operation model which cannot handle polymer component attribute data. When using oligomer components, you may specify addition properties through the following unary property parameters: Parameter Definition Default POLDP Number-average chain length Calculated * POLPDI Polydispersity index 1 ** POLCRY Mass fraction crystallinity * Calculated from the number of segments in the oligomer as specified in the Polymers form Oligomers subform. ** Used to calculate DPW and MWW. 3 Component Classification 23
  • 36. Note: Not all kinetic models track oligomers as separate components. If a model does not provide fields for specifying oligomers on its input forms, then these components are not tracked. Segments Segments are the structural units of a polymer or oligomer and are specified independently from these components. Their structure is fixed throughout a simulation. Segments typically correspond to the monomers used to grow the polymer. They are divided into types depending on their location on the polymer chain:  Repeat units  End groups  Branch point (attached to three or four branches) Site-Based Site-based components pertain to multisite reaction kinetic models (Ziegler- Natta and Ionic). Site-based components include Ziegler-Natta catalysts and ionic initiators. Ziegler-Natta Catalysts Ziegler-Natta catalysts are often used to initiate polymer chain formation in chain-growth polymerization reactions. Catalysts can be treated as standard conventional components. Ziegler-Natta catalysts or metallocene catalysts involve one or more polymerization site types which may be in an activated or deactivated state. In order to use Ziegler-Natta catalysts, you must specify the number of site types and the catalyst properties to be tracked, that is, the site activity. Catalyst properties are defined as component attributes. You must initialize the catalyst properties while specifying input data for the streams containing the catalysts. For more information on component attribute specification, see Polymer Structural Properties on page 33. Ionic Initiators Ionic initiators are used in anionic and cationic polymerization. The ionic initiators can be treated as standard conventional components. The propagating species in ionic polymerization can be:  Free-ions  Ion-pairs  Dormant esters 24 3 Component Classification
  • 37. In Aspen Polymers, these different species are modeled as different sites of an ionic initiator. Three different site-based attributes are tracked for an ionic initiator. For more information, see Ionic Initiator Attributes on page 45. Component Databanks The thermodynamic and transport property models needed to perform the physical property and phase equilibrium calculations during a simulation require pure component property data. These include:  Molecular weight  Heat capacity  Heat of formation  Heat of vaporization  Vapor pressure  Density Enter that information while selecting and specifying physical property models. Normally, you would make use of the pure component databanks and retrieve data from them for each of the components present in the simulation model:  Data for conventional components are retrieved from the Pure Component databank  Data for free-radical initiators are retrieved from the INITIATOR databank  Data for polymers are retrieved from the POLYMER databank  Data for oligomers are retrieved either from the pure component databank or from the POLYMER databank  Data for segments are retrieved from the SEGMENT databank  Data for PC-SAFT are retrieved from the PC-SAFT databank  Data for POLYPCSF are retrieved from the POLYPCSF databank Descriptions of the databanks, and the parameters they contain are given in Appendix A. Pure Component Databank In the Pure Component databank, components are named using a nomenclature developed for Aspen Plus. Each component is given an alias summarizing the number of each type of atom: C, H, O, N, P, S, CL, F, etc. (e.g. C2H4 for ethylene). For cases where the same alias matches several components, a counter is added to make the distinction (e.g. C2H4O2-1 for acetic acid). Note: Catalysts are often solid components and may not be found in the PURE11 databank. Normally, you do not need a rigorous representation of these components. 3 Component Classification 25
  • 38. An acceptable approach is to assign a monomer alias to the catalyst and then provide the correct molecular weight and certain parameters which will prevent the catalyst from vaporizing. If an activity coefficient model is being used for phase equilibrium representation, the catalysts can be assumed to be non-volatile by specifying -40 as the first Antoine parameter (PLXANT(1) = - 40). PC-SAFT Databank The PC-SAFT databank contains pure and binary parameters used with the PC-SAFT property method. The parameters are taken from the literature, including many normal compounds, polar compounds and associating compounds. POLYPCSF Databank The POLYPCSF databank contains pure and binary parameters used with the POLYPCSF property method. The parameters are taken from the literature, including many normal compounds, but excluding polar compounds and associating compounds. INITIATO Databank The INITIATO databank contains data for initiator components. Rate constants in this databank are derived from half-life data in vendor datasheets published on public web sites. These datasheets generally contain data at several temperatures, allowing the activation energy and prefactor to be determined. These rate constants depend on the reaction environment, and may vary between polar and non-polar solvents. Where multiple sets of data were available, the data from monomer or organic solvents were used in preference to data from aqueous solutions. Molecular weight and other parameters are calculated from structure using estimation methods from Aspen Plus, except in those few cases where vapor pressure data was provided in the datasheets. In the INITIATO databank, components are named using industry-standard acronyms. Each component is given an alias summarizing the number of each type of atom: C, H, O, N, P, S, CL, F, etc. For cases where the same alias matches several components, a counter is added to make the distinction (e.g. –1,-2, etc). Segment Databank In the Segment Databank, a segment name comes from the name of the monomer from which it originates. Therefore, in this databank component names and aliases follow the same conventions as those for the Pure Component Databank. A label is added to the monomer name to identify the segment as either a repeat unit,-R, an end group,-E, or a branch point, -B (e.g. for butadiene segments: C4H6R1or BUTADIENER1 corresponding to the repeat unit – 26 3 Component Classification
  • 39. CH2–CH=CH–CH2, C4H5E1 or BUTADIENEE1 corresponding to the end group –CH=CH–CH=CH2 and C4H5B or BUTADIENEB corresponding to the branch segment CH2 CH CH CH ). Polymer Databank The Polymer Databank does not follow the conventional nomenclature. The polymer aliases are the typical acronyms used in industry or academia, and the polymer names consist of the repeat unit name enclosed in parentheses and preceded by the prefix Poly (e.g. PS or POLY(STYRENE) for polystyrene). Note: The MW property parameter used to store molecular weights in the component databanks is the true molecular weight for all component types except polymers. For polymers, the true polymer molecular weight is normally tracked as a component attribute only. The molecular weight stored in the databank is the apparent molecular weight calculated as the average segment molecular weight (See Appendix A). Segment Methodology The segment approach to characterizing components is a fundamental methodology which affects almost every functionality within Aspen Polymers. Segments are used as the building blocks for polymers. Once you have specified the types of segments in the polymer, the segment composition and degree of polymerization defined as component attributes may be used to define the size and composition of the polymer. For oligomers, although component attributes are not used, the number of each segment must be specified directly. Most of the Aspen Polymers physical property models calculate polymer and oligomer properties from segment properties. This is done by taking into account the degree of polymerization and the segment composition. The calculated properties should be the same for both oligomers and polymers, assuming that the oligomer structure and molecular weight were specified correctly. Note that this is true for mass-based properties only. Mole-based properties will be different between polymer and oligomer if their apparent molecular weights are different. Within the polymerization reaction models, segments also play a key role. As polymerization progresses, the models map the reacting monomers into the corresponding segments and return rates of change for the segment composition. 3 Component Classification 27
  • 40. Specifying Components To specify components within your model you need to know the following: Item For Component types All the species in your system Property parameter databank The species in the system selections IUPAC names All conventional components or you need their physical properties (molecular weight, boiling point, Antoine constants, etc.) Segment structure All polymers and oligomers (define whether you want to include any end groups or branch points) Polymer properties to be tracked All polymers, that is, degree of polymerization, segment composition Additional characteristics All additional characteristics for catalysts, or ionic initiators Selecting Databanks For an Aspen Polymers simulation, you generally retrieve physical property data from the following databanks:  Pure component databank (PURE12)  Polymer databank (POLYMER)  Polymer segment databank (SEGMENT)  Initiator databank (INITIATOR) You can also use other Aspen Plus databanks, user databanks, or in-house databanks. Appendix A provides descriptions of the polymer and segment databanks and the parameters they contain. If you selected a polymer template to start your simulation, the correct databanks are already specified. If you did not select a polymer template, or if you want to modify the databank selection: 1 From the Data Browser, click Components. 2 From the Components folder, click Specifications. 3 On the Selection sheet, click the Databanks tab to open the databank selection form. Defining Component Names and Types You must specify a:  Name and a type for each component in the simulation  Component name or identifier  Databank name or alias that sets the pure component properties for the component 28 3 Component Classification
  • 41.  Component type that sets the category to which the component belongs and determines the treatment of that component To access the components specifications input sheet: 1 From the Data Browser, click Components. 2 From the Components folder, click Specifications. 3 On the Selection sheet, click the Databanks tab to set the databanks to be searched for pure component properties. To define component names and types: 1 On the Selection sheet, in the Component ID field, specify an ID for each component. This ID is used to refer to the component in all subsequent input, and is also used to identify the component in the simulation report. 2 For polymers, oligomers, and segments, specify the component type in the Type field. By default, all components are assumed to be standard conventional components. For Aspen Polymers simulation you must correctly identify the component types: Use For Conventional Standard conventional components Polymer Homo and copolymers Oligomer Short chain polymer molecules Segment Polymer or oligomer repeat units 3 If component property data is being retrieved from databanks, you must also supply either the databank alias in the Alias field, or the databank name in the Component name field. Specifying Segments The Type of each polymer or oligomer segment must be specified on the Polymer Characterization Segments sheet. Segments can be repeat units, end groups or branch points attached to three or four branches. To access the segments definition input form: 1 From the Data Browser, click Components. 2 From the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. To define segments:  On the Segments sheet, assign a type to the segments from the Type field. Specifying Polymers For each polymer you must define the component attributes to be tracked. All components specified Polymer in the Components Specifications folder require component attributes. 3 Component Classification 29
  • 42. To access the polymer input specifications: 1 From the Data Browser, click Components. 2 From the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the Characterization form, click the Polymers tab. To specify component attributes for the polymers in your simulation: 1 In the Polymer ID field, select the polymer. 2 If you want to retrieve a predefined set of component attributes, in Built-in attribute group select a grouping. The attribute summary table is filled in. For a complete discussion of Aspen Polymers component attributes, see Polymer Structural Properties on page 33.  or  If you do not want to use a predefined set of attributes, or if you want to change the attribute selection for a given group, click the attribute table or click Edit to open the attribute list. 3 Click specific attributes to add or remove them from the list. Repeat these steps for each polymer. Specifying Oligomers For each oligomer you must specify an ID and a structure in terms of number and name of contained segments. To access the oligomers definition input form: 1 From the Data Browser, click Components. 2 From the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the Characterization form, click the Oligomers tab. To define oligomers: 1 In the Oligomer field, select the oligomer. 2 In the Segment field, enter the name of a segment contained in the oligomer. 3 Repeat these steps for each oligomer. You can define as many segments as needed for an oligomer. Specifying Site-Based Components Specify the structure and activity of site-based catalytic species such as Ziegler-Natta catalysts and ionic initiators. To access the site-based species definition form: 1 From the Data Browser, click Components. 2 From the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the Characterization form, click the Site-Based Species tab. 30 3 Component Classification
  • 43. To specify site-based species characteristics: 1 Select the component type: Ziegler-Natta catalyst, ionic initiator, etc. 2 In the Comp ID field, specify the component name. 3 Specify the number of site types in Number of sites for the component. For Ziegler-Natta catalysts, you must also specify the moles of sites per gram of catalyst. 4 Select the list of properties or component attributes to be tracked for that component. Click the attribute list table or Edit to open the attribute list. 5 Click specific attributes to add or remove them from the list for the component. References Bailey, J., & Ollis, D. F. (1986) Biochemical Engineering Fundamentals (2nd Ed.). New York: McGraw-Hill. Brandrup, J., & Immergut, E. H. (Eds.). (1989). Polymer Handbook (3rd Ed.). New York: John Wiley & Sons. Danner R. P., & High, M. S. (1992). Handbook of Polymer Solution Thermodynamics. New York: American Institute of Chemical Engineers. Kroschwitz, J. (Ed.). (1990). Concise Encyclopedia of Polymer Science and Engineering. New York: John Wiley and Sons. 3 Component Classification 31
  • 44. 32 3 Component Classification
  • 45. 4 Polymer Structural Properties This section discusses the use of component attributes for tracking polymer structural properties in a simulation model. Topics covered include:  Structural Properties as Component Attributes, 33  Component Attribute Classes, 34  Component Attribute Categories, 35  Component Attribute Initialization, 46  Component Attribute Scale Factors, 50  Specifying Component Attributes, 51 Structural Properties as Component Attributes Component attributes provide a convenient framework to associate structural characterization data to components in a flow stream. They are carried throughout the flowsheet along with state and composition information, and effectively extend the stream structure. Aspen Polymers (formerly known as Aspen Polymers Plus) uses component attributes as a vehicle for tracking important modeling information for polymers, ionic initiators and Ziegler-Natta catalysts (U.S. Patent No. 5,687,090). For example, there are component attributes to store:  Segment composition (segment fraction or segment flow)  Copolymer composition and average sequence length  Degree of polymerization (number, weight, and z-average)  Molecular weight (number, weight, and z-average)  Degree of branching (long and short)  Degree of cross-linking (cross-link density)  Molecular architecture (physical arrangement of segments within the polymer molecule) 4 Polymer Structural Properties 33
  • 46.  Live polymer properties  Aggregate polymer properties In the case of multi-site-type Ziegler-Natta catalyst polymerization, the attributes provide the structure to store the properties by site. Examples of catalyst attributes include the fraction of dead and potential sites. The catalyst attributes are used to track catalyst activity. There are also component attributes available to track user defined data. The complete list of available attributes is given in the Polymer Component Attributes, Site-Based Species Attributes, and User Attributes sections of this chapter (pages 35 through 45). Component Attribute Classes Component attributes are divided into classes to reflect the nature of various structural properties carried in process streams:  Class 0 component attributes are derived quantities from other attributes. They are therefore recalculated from these attributes after they are updated. For example, number average degree of polymerization is a Class 0 component attribute. It is computed from the zeroth and the first moments of chain length distribution.  Class 1 component attributes are structural properties per unit mass. They are not used for polymers.  Class 2 component attributes are structural properties per unit time. Examples are zeroth and first moments of chain length distribution The following table lists the differences between the Aspen Polymers component attribute classes: Class Conserved Quantity Convergence Treatment Unit of Measurement Examples 0 N/A Recalculated Varies Degree of polymerization 1 Attribute  component mass Direct substitution Attribute / component mass None for polymers 2 Attribute Accelerated convergence Attribute / time Segment flows, moments of chain length distribution For a typical polymer process simulation, Class 0 and Class 2 component attributes are used. Since Class 0 component attributes are calculated from Class 2 attributes, users have the option of entering either of the two types for simulation models where polymer is present in the process feed streams. For this reason, an attribute initialization scheme has been designed. For more information, see Component Attribute Initialization on page 46. 34 4 Polymer Structural Properties