Mathematical Modeling of High-Pressure Ethylene Polymerization Reactors

Victor M. Zavala

Department of Chemical Engineering Carnegie Mellon University Pittsburgh, PA PSE Seminar September, 2005

Outline

Motivation

Polymerization Processes Mathematical Modeling Polyethylene Processes High-Pressure Technology

Mathematical Model Development

Reactor Types

Kinetic Mechanism Material and Energy Balances Physical, Thermodynamic and Transport Properties

Parameter Estimation Reactor Model Implementation

Motivation Mathematical Modeling

$ Polymer Industry $

Changing and diversifying market New product development Tighter Product Quality Specifications Furious Cost Reduction Efficient process design and operation
Better process understanding

Polymerization Processes

Complex Kinetic Mechanism Highly Exothermic Special Phenomena

Analyze Physical Nature

First-Principles Models

Motivation Polyethylene

Polyethylene Most dominant polymer

28 million tons/yr (Ethylene) 15 million tons/yr (Polyethylene)

Polyethylene Classification Structure

Low-Density Polyethylene - Free-Radical

Extreme Operating Conditions 150-310 oC 2500-3000 atm 1) LLDPE & HDPE

2) LDPE

High-Pressure Reactor Technology

Outline

Motivation

Polymerization Processes Modeling Polyethylene Processes High-Pressure Technology

Mathematical Model Development

Reactor Types Kinetic Mechanism Material and Energy Balances Physical, Thermodynamic and Transport Properties

Parameter Estimation Reactor Model Implementation

Mathematical Model Development

LDPE Reactor types Autoclave Product Properties Desired Tubular

LDPE Autoclave Reactor

Ethylene

1. Large capacities small residence time 2. High degree of back mixing 3. Thick Walls - Inefficient heat removal

Low conversion (15-30%)

LDPE/Gas

Mathematical Model Development

LDPE Tubular Reactor
2 km long 8 in diameter
Initiator(s) Cw Cw Initiator(s) Cw

Reaction Ethylene

Cooling

Reaction

NZ
LDPE/Gas

Cw

Cw

Cw

1. Large capacities short residence times 2. Low degree of back mixing 3. Better heat removal

Higher Conversion (25-40%)

Mathematical Model Development

Typical LDPE Reactor Mathematical Model

Reactor Temperature Profiles Conversion LDPE Final Properties:

Average Molecular Weights Polymer Density

Mathematical Model Development

Free-Radical Kinetic Mechanism

Free-radical Ingredients: Initiator(s), Monomer(s), Modifier(s)

1) Initiator decomposition

Peroxide

2) Chain Initiation

Mathematical Model Development

Kinetic Mechanism

Live Polymer Chains

3) Chain Propagation

i = 1,..,

4) Chain Transfer to Monomer

Dead Polymer Chains

i = 1,..,

Mathematical Model Development

Kinetic Mechanism

5) Chain Transfer to Modifier Molecular Weight Control

i = 1,..,
S S.
LDPE Unique Properties

6) Chain Transfer to Polymer (Long-Chain Branching)

i, j = 1,..,
1

Mathematical Model Development

Kinetic Mechanism

7) Termination by Combination

i, j = 1,..,

8) Termination by Disproportionation

i, j = 1,..,

Mathematical Model Development

Kinetic Mechanism

9) Backbiting (Short-Chain Branching) Define Polymer Density

i = 1,..,

Polymer chain curls

Mathematical Model Development

Kinetic Mechanism

Reaction Rates

i, j = 1,..,
i = 1,.., i = 1,..,

i, j = 1,..,

i, j = 1,..,

i, j = 1,..,
i = 1,..,

Mathematical Model Development

Kinetic Mechanism

Reaction Rates

Live Chains

i, j = 1,..,
i = 1,.., i = 1,..,

i = 1,..,

i, j = 1,..,
Dead Chains

i, j = 1,..,

i, j = 1,..,
i = 1,..,

i = 1,..,

Mathematical Model Development

Molecular Weight Distribution

Define final-use properties Solve Infinite series of reaction rates vs. Number and Weight- Average Molecular Weights

Method of Moments

Number Chain-Length Distribution (NCLD)

NCLD Moments (kth order)

Live Dead

Mathematical Model Development

Method of Moments

NCLD Moments (kth order)

Live Dead
Number- and weight-average molecular weights

Reaction rates of 6 moments to capture MWD How do we get them ? From the Kinetic Mechanism

Mathematical Model Development

Polymer Chains Reaction Rates

Take

1
Multiply through by Sum both sides over

Take

2
Multiply through by Sum both sides over

Mathematical Model Development

Live Polymer Chains Moments k=0 k = 1,2

Dead Polymer Chains Moments k=0

k = 1,2

Mathematical Model Development

Initiators Monomer Solvent

Primary Radicals

Long-chain branching

Shot-chain branching

Mathematical Model Development

Material and Energy Balances Reaction Rates

Autoclave

Tubular

Assumptions: Perfect mixing vs. compartment

Assumptions: Plug flow

Single Supercritical Phase

Single Supercritical Phase

Large Number of Equations

Mathematical Model Development

Physical, Thermodynamic and Transport Properties

Extreme Pressures and Temperatures

Supercritical Conditions (Gas-Polymer Mixture) Gas Phase Density and Heat Capacity Lee-Kesler EOS Polymer Phase Properties Complex Semi-Empirical Correlations

Tubular Reactor Rigorous Heat Transfer Model

LDPE Properties From Moments

Outline

Motivation

Polymerization Processes Modeling Polyethylene Processes High-Pressure Technology

Mathematical Model Development

Kinetic Mechanism Reactor Types Material and Energy Balances Physical, Thermodynamic and Transport Properties

Parameter Estimation Reactor Model Implementation

Parameter Estimation

Polymerization Reactors

Kinetic Parameters (Arrhenius type) Critical Step in Development Time Consuming Laboratory Data vs. Plant Data Model On-line Implementation Reactor Variability On-line Parameter Estimation

Parameter Estimation
Parameter Estimation Problem Model Reactor Zone-by-Zone

NZ

submodel1

submodel2

submodelz

Reactor Model
370 Differential Equations Systematic Approaches 600 Algebraic Equations are NOT currently + used Model Nature - Nonlinearity High Parametric Sensitivity Kinetics masked by Transport Phenomena =

Large-Scale & Complex Parameter Estimation Problem

Outline

Motivation

Polymerization Processes Modeling Polyethylene Processes High-Pressure Technology

Mathematical Model Development

Kinetic Mechanism Reactor Types Material and Energy Balances Physical, Thermodynamic and Transport Properties

Parameter Estimation Reactor Model Implementation

Questions