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

High-Pressure
Reactor Technology
2) LDPE
 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 Product Properties Desired

Autoclave 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) Initiator(s)
Cw Cw Cw

Reaction Cooling Reaction

Ethylene
1 2 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-radicalÆ Ingredients: Initiator(s), Monomer(s), Modifier(s)

1) Initiator decomposition

Benzoyl 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 Æ Molecular Weight Control

i = 1,.., ∞

S S.
6) Chain Transfer to Polymer (Long-Chain Branching) Æ LDPE Unique Properties

i, j = 1,.., ∞

1 2
 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) Æ 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 Take 2

Multiply Multiply
2 through by through by

Sum both Sum both

sides over 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: ‰ Assumptions:
‰ Perfect mixing vs. compartment ‰ 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 Æ Lee-Kesler EOS
‰ Polymer Phase Properties Æ Complex Semi-Empirical Correlations

‰ Tubular Reactor Æ Rigorous Heat Transfer Model

‰ LDPE Properties Æ 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 Æ Time Consuming
‰ Laboratory Data vs. Plant Data

‰ Model On-line Implementation

‰ Reactor Variability Æ On-line Parameter Estimation
 Parameter Estimation
Parameter Estimation Problem

Model Reactor
1 2 NZ
Zone-by-Zone

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