Christos - Chatzidoukas 2004 PHD Thesis PDF

CONTROL AND DYNAMIC
OPTIMISATION OF
POLYMERIZATION REACTION
PROCESSES
CHRISTOS CHATZIDOUKAS
A thesis submitted for the degreeof Doctor of Philosophy of the University of London
and for the Diploma of Membership of the Imperial College
NIZ CENTRE FOR PROCESSSYSTEMSENGINEERING

711r. DEPARTMENTOF CHEMICAL ENGINEERING AND
CHEMICAL TECHNOLOGY
'IMPERIAL COLLEGE, LONDON
crM.
"Y"
Acknowledgments
I want to express my gratitude to my supervisors, Prof E.N. Pistikopoulos and Prof J.D. Perkins for
their invaluable guidance and advice during the course of this work.
I would also like to express my gratefulness to Prof C. Kiparissides for his priceless ethical and
scientific support that was determinant for the completion of this thesis.
Finally, I would like to thank the European Union for funding this work under the Growth Project
"PolyPROMS".
Abstract
The commercial technology development related to the olefin polymerization processesresults

from a respective commercial interest due to the wide range of application of polyolefins, and
polyethylene in particular, as well as from a considerable economic importance of this

commodity for the polymer industry. However, the rapid technological progressof polyethylene
processeskeeps step with the emergenceof a number of problems and questionsregarding their
operation. These problems originate from the complex physicochernical phenomena that
characterizethe catalytic olefin polymerization, from processstability issues,from the need for
product quality control, as well as from the process behaviour under transient conditions. A
comprehensiveunderstandingof all these issues that are experimentally observed is neededin
order to be effectively captured in the general frame of an integrated approach of the
polymerization processdesign,control and optimization interactive problems.
The operating profiles of polymerization processes are tightly related to frequent grade
transitions and the demanding problem of product quality control arises more urgently in the
transition periods. The optimal operation of the olefin polymerization processesis one of the
objectives of this thesis and is investigated in relation to a Ziegler-Natta catalytic gas-phase
ethylene-I -butene copolymerization fluidized bed reactor (FBR). A detailed theoretical
mathematical model of this polymerization unit has been developed in the gPROMS (Process
SystemsEnterprise Ltd., London) modeling environment, correspondingto the needsfor model-
based approach of this problem. The interaction of process control with the optimal operating
profile of the process during a grade transition have been investigated and an optimal control
structure has been found applying mixed integer dynamic optimization (MIDO) techniques.The
production planning of the process in a hypothetical grade transition campaign has been
examined in parallel with the optimal transient operation of the processin the framework of the
MIDO approach and an optimal sequenceof transitions has been found. Finally a generic
mechanistic module describing the steady state and dynamic behaviour of an industrial scale
multistage olefin copolymerization process has been developed in the gPROMS simulation
environment accounting for phaseequilibrium phenomenain the processunits. The capabilities
of the model have been testedcomparing the model predictions with experimentaldata.
Contents
List of Figures A
List of Tables xi
List of Symbols xiii
1. Polyolefin Market Status I
1.1 Introduction
...............................................................................
1.2 Polyolefin applications 2
..................................................................
1.3 Historical Overview-Statistics 4
.........................................................
1.4 Motivation-Research Justification 10
...................................................
1.5 Literature 13
.................................................................................
2. Polyolefin Technology Developments: Polymerization Processes&

Catalysts 14
2.1 Introduction 14
..............................................................................
2.2 Polyethylene Processing Characteristics 15
............................................
2.3 Polyethylene Processes 17
..................................................................
2.4 Gas-Phase Polyoleiin Processes 22
......................................................
2.4.1 Ile BASF Gas-PhasePolyolefin Technology 23
.................................
2.4.2 The AMOCO Gas-PhasePolyolefin Technology 24
.............................
2.4.3 The UNIPOL Gas-Phase
PolyolefinTechnology 26
.............................
2.4.4 The BP Gas-Phase Polyolefin Technology 28
.....................................
2.5 Catalytic Systems 30
.........................................................................
1
Contents
2.5.1 Catalyst for Gas-PhasePolymerization 30

.........................................
2.5.2 Polymer Particle Morphology Development 31
...................................
2.6 Summary .................................................................................. 34
2.7 Literature 35
.................................................................................
3. Catalytic Gas-Phase Olefin Polymerization Fluidized Bed Reactor

Model 40
3.1 Introduction 40
..............................................................................
3.2 Microseale Level 42
........................................................................
3.2.1 Polymerization Kinetic Mechanism............................................. 44
3.2.2 Kinetic Rate Expressions 48

.........................................................
3.2.3 Polymer Properties 53
.................................................................
3.3 Macroseale Level 54
........................................................................
3.3.1 The Fluidized-Bed Olefin Polymerization Reactor ........................... 58
3.3.2 Dynamic Mathematical Model 61

...................................................
3.4 Summary 64
.................................................................................
3.5 Literature 65
.................................................................................
4. Process Design and Control Optimisation 69
4.1 Problem Statement 69

.....................................................................
4.2 Control Synthesis Problem ..................... 0......................................
70
4.2.1 Five-StepProcessControl Synthesis 71

...........................................
4.2.2 ProcessControllability....................... 72
o....................................
4.3 Control Systemof the Ethylene Polymerization FBR........................... 75
4.3.1 ControlObjectives............................................ o....................

75
4.3.2 ControlandMeasureVariables................................. 76
o................
4.3.3 Degreesof Freedom-Manipulated
Variables 76
...................................
4.3.4 ControlStructureSelection....................................................... 77
ii
Contents
4.4 Dynamic Process Optimisation 80

.......................................................
4.4.1 Outline of the Grade Transition Problem 81
.......................................
4.4.2 ResearchOver Grade Transition Dynamic Optimisation 83
.....................
4.4.3 Existing Methods for the Time Optimal Control Problem 87
....................
4.4.4 Mathernatic Formulation of the Grade Transition Optimisation Problem.. 93
4.5 Conclusions 95
...............................................................................
4.6 Literature 96
.................................................................................
5. Optimal Control and Grade Transition Operation of a PE FBR 102
5.1 IntegratedSolutionof the GradeTransitionProblem-MIDO.................. 103
5.1.1 TbeMIDOProblemFormulation 103

................................................
for MIDO Problems
5.1.2 SolutionApproaches 104
.....................................
5.2 The CombinedOptimisationProblem.............................................. 107
5.3 MathematicalProblemFormulation......................... 0...................... 108
5.3.1 FixedControlStructure
Approach 110
...............................................
Approach
5.3.2 VariableControlStructure-MIDO 114
..................................
5.4 Post-OptimalityAnalysis............................................................... 122
5.5 ConcludingRemarks................................................................... 130
5.6 Literature................................................................................. 131
6. Optimal Production Campaign Scheduling in a PE FBR 133
6.1 Problem Statement-Motivation ...................................................... 134
6.2 Current Research Orientation ....................................................... 135
6.3 Construction of the Multilevel Problem ............................................ 137
6.3.1 Definitions .......................................................................... 138
6.3.2 Clarification Remarks 139

.............................................................
6.4 Illustrative Example .................................................................... 140
iii
Contents
6.5 Mathematical Model Formulation 141

...................................................
6.5.1 Steady State Constraints 146
..........................................................
6.5.2 Auxiliary Integer Variables 146
......................................................
6.5.3 Known Initial Operating Point 147

...................................................
6.5.4 Assignment of a Changeover Between Two Grades to One Transition Period
Only 147
..................................................................................
6.5.5 Sequential Transition Mode 147

......................................................
6.6 Solu tion Procedure 148

.....................................................................
6.7 Results 149

.....................................................................................
6.7.1 Optimal Transition Timing 149
.......................................................
6.7.2 Optimal Profiles 150
....................................................................
6.8 Problem Revision-Further Control Consideration............................... 154
6.9 Concluding Remarks................................................................... 156
6.10Literature 157
.................................................................................
7. Plant-Wide Issues 160
7.1 Introduction-The Borstaro Process.................................................. 160
7.1.1 Catalyst System - Pre-polymerization Section................................. 162
7.1.2 Plant Units - Model Consideration............................................... 163
7.2 Mathematical Model 164

....................................................................
7.2.1 Polymerization Kinetics 164

...........................................................
7.2.2 Reactor Model 166

......................................................................
7.2.3 Flash Separator Model 171

............................................................
7.2.4 Thermodynamic Model 173

...........................................................
7.2.5 Process Control Configuration 177

...................................................
7.3 Modelling Limitations .................................................................. 180
7.4 Model Input Parameters ............................................................... 183
iv
Contents
7.5 Simulation Results 185

.......................................................................
7.6 Optimal Plant Operation 192
...............................................................
7.7 Concluding Remarks 198
....................................................................
7.8 Literature ................................................................................. 199
8. Conclusions & Recommendations for Future Research 200
8.1 Thesis Contribution ..................................................................... 200
8.2 A Challenge for Future Research .................................................... 204
Related Publications Arising from this Work 206
Appendixes
A Pseudokinctic Rate Constants -Rate Functions for Olefin

Copolymerization 208
A. 1 Introduction 208
...............................................................................
A. 2 Kinetic Model 210
.............................................................................
A. 3 Literature ................................................................................. 216
B Physical Properties - Process Unit Design Parameters 217
C Detailed Analysis of the MIDO Algorithm 221
C. 1 Novel Solution Method of MIDO Problems ....................................... 221
C. 2 Algorithmic Procedure of the MIDO Method .................................... 224
C.3 Literature ................................................................................. 227
D The Sanchez-Lacombe EoS as a Tool for Thermodynamic

Calculations 228
V
List of Figures
1.1 Schematic of molecular structure for commercial PE 3

.....................................
1.2 Markets and applications of low-pressure polyethylene 3
..................................
1.3 Global demand of HP-LDPE resins 3
..........................................................
1.4 Production and capacity of polyolef ins, Western Europe, 1995-2001 6
..................
1.5 HDPE production, capacity and operating rate, Western Europe, 1995-2001 6
.........
1.6 LLDPE production, capacity and operating rate, Western Europe, 1995-2001 6
.......
1.7 IDPE production, capacity and operating rate, Western Europe, 1995-2001 7
.........
1.8 PP production, capacity and operating rate, Western Europe, 1995-2001 7
.............
1.9 W. European producer consolidation activity, 1995-2002 7

...............................
1.10 W. European producer consolidation activity, 1995-2002 8

..............................
1.11. World's largest polyolefin producers-2002 9

..............................................
1.12 Polyolefin producers in Western Europe-2002 9

...........................................
1.13 Pricing for polyolefin producers, 1990-2001 10

.............................................
1.14 Structure of the thesis based on the three thematic sections II

............................
2.1 Relationship between polymer properties and resin density.............................. 16
2.2 Relationship between polymer properties and resin molecular weight ................. 16
2.3 Production capabilities of low-pressure PE processes..................................... 18
2.4 Low-pressure polyethylene processes-technologies and overlapping in product

spccif ications......................................................................................... 20
.
2.5 Linear PE capacity by type and process..................................................... 22
2.6 BASF gas-phascethylene polymerization process 24

........................................
2.7 AMOCO gas-phascpolymerization process 25
................................................
2.8 Union carbide gas-phaseethylene polymerization proccss-UNIPOL 26
...................
2.9 BP chemicals two-stage gas-phaseethylene polymerization process 28
...................
2.10 The multigrain model of particle growth 33
..................................................
VI
List of Figures
2.11 Schematic polyethylene morphology development during gas-phase

polymerization ...................................................................................... 33
3.1 Modelling levels of polymerization reactor systems 41

......................................
3.2 Schematic representationof initiation-propagation chemical reaction 45
..................
3.3 Schematic representation of the fluidization profile in a catalytic gas-phase olefin
polymerization FBR ................................................................................. 56
3.4 Gas-phaseethylene polymerization FBR unit 59

..............................................
4.1 Grade changeoverscheme for ethylene polymerization 82
..................................
4.2 Embedded model approach to dynamic optimization under the sequential method 92
...
5.1 Calculated optimal density profiles for the transition from grade A to B and back to A for
a fixed control structure obtained via the RGA analysis...................................... 112
5.2 Calculated optimal MI profiles for the transition from grade A to B and back to A for a
fixed control structure obtained via the RGA analysis 113
........................................
5.3 Calculated amount of off-spec polymer production for the transition from grade A to B
and back to A under fixed control structure for the optimisation policies OPI &
OP2 113
....................................................................................................
5.4 Calculated optimal density profiles for the transition from grade A to B and back to A for
a variable control structure obtained by a MIDO algorithm .................................. 117
5.5 Calculated optimal MI profiles for the transition from grade A to B and back to A for a
variable control structure obtained by a MIDO algorithm .................................... 118
5.6 Amount of off-spec polymer produced under different optimisation policies using a
MIDO approach 118
.....................................................................................
5.7 Time-optimal control policies of the comonomer/monomer ratio and the hydrogen flow
rate for the transition from grade A to B and back to A ....................................... 119
5.8 Time-optimal control policies of the bleed and catalyst flow rates for the transition from
grade A to B and back to A ........................................................................ 119
5.9 Time-optimal set-point trajectory of the production rate feedback controller and time
variation of the respective controlled variable.................................................. 120
vii
List of Iligures
5.10 Time-optimal sct-point trajectory of the bed height feedback controller and time
variation of the respective controlled variable.................................................. 120
5.11 Amount of off-spcc polymer produced under a fixed (RGA) and a variable (MIDO)
control structure..................................................................................... 122
5.12 Impact of uncertainty of catalyst activity on the polymer density profile under a
predefined optimal operating policy ................................................... 124

.........
5.13 Impact of uncertainty of catalyst activity on the polymer MI profile under a predefined
optimal operating policy ......................................................................... 124
5.14 Impact of uncertainty of catalyst activity on the off-spec polymer production under a
predefined optimal operating policy ............................................................. 125
5.15 Impact of uncertainty of the fraction of the active sites of catalyst on the polymer
density profile under a predefined optimal operating policy 126
.................................
5.16 Impact of uncertainty of the fraction of the active sites of catalyst on the polymer MI
profile under a predefined optimal operating policy .......................................... 126
5.17 Impact of uncertainty of the fraction of the active sites of catalyst on the off-spec
polymer production under a predefined optimal operating policy .......................... 127
5.18 Temperature profile of the coolant in the heat exchanger 128

..............................
5.19 Impact of uncertainty of the coolant temperature on the polymer density profile under a
5.20 Impact of uncertainty of the coolant temperature on the polymer MI profile under a
6.1 Comparison of two arbitrary production sequences in terms of the objective

function 142
...............................................................................................
6.2 Comparison of two arbitrary production sequences in terms of the off-spec
production ............................................................................................ 142
6.3 Optimal MI profile under the optimal production planning 151

..............................
6.4 Optimal density profile under the optimal production planning 151
.........................
6.5 Optimal PD profile under the optimal production planning 152
..............................
6.6 Comparison of the four campaigns in terms of the off-spec production.... -..;, 153
.......
viii
List of Figures
6.7 Grade transition campaignunder two alternative control schemes-Objectivefunction

comparison 155
...........................................................................................
6.8 Grade transition campaignunder two alternativecontrol schemes-Off-spec production
comparison 156
...........................................................................................
7.1 The catalyticethylene-l-butenecopolymerizationBorstarsprocess................... 161
7.2 Time profile of polymer density during the transition from grade A to B and
back to A .............................................................................................. 186
7.3 Time profile of polymer number average molecular weight during the transition from
grade A to B and back to A ........................................................................ 187
7.4 Time profile of the molar composition of the light phase in the FBR and the make-up
stream during the transition from grade A to B and back to A-Ethylene ................... 187
stream during the transition from grade A to B and back to A-Butene ..................... 188
stream during the transition from grade A to B and back to A-Hydrogen 188
..................
stream during the transition from grade A to B and back to A-Nitrogen 189
...................
stream during the transition from grade A to B and back to A-Propane 189
....................
7.9 Time profile of the bed level and the product removal from the FBR during the transition
from grade A to B and back to A ................................................................. 190
7.10 Time profile of the total bed mass and the product rate in the FBR during the transition
from grade A to B and back to A 191
.................................................................
7.11 Time profile of pressure and temperaturein the FBR during the transition from grade A
to B and back to A ................................................................................... 191
7.12 Time profile of pressure in the Flash unit and the previous process unit during the
transition from grade A to B and back to A ..................................................... 192
7.13 Comparison of the density profiles derived under feedback and optimal control during
the transition from grade A to B and back to A ................................................. 194
ix
List of Figures
7.14 Comparisonof the molecularweight profilesderivedunderfeedbackandoptimal

control during the transitionfrom gradeA to B andback to A .............................. 194
7.15 Comparisonof the butenefeedtrajectoriesderivedunderfeedbackandoptimalcontrol

during the transitionfrom gradeA to B and backto A 192
........................................
7.16 Comparisonof the hydrogenfeedtrajectoriesderivedunderfeedbackandoptimal
control during the transitionfrom gradeA to B and back toA............................... 195
7.17 Comparisonof the bed-levelprofiles derivedunderfeedbackandoptimalcontrolduring

the transitionfrom gradeA to B andback to A ....... ...... .................................. 195
7.18 Comparisonof theproductionrateprofiles derivedunderfeedbackandoptimalcontrol

during the transitionfrom gradeA to B and backto A 197
.......................................
7.19 Comparisonof the off-spec;polymeramountproducedunderfeedbackandoptimal
control during the transitionfrom gradeA to B andback to A 197
...............................
C.1 Algorithmic stepsof the MIDO problemssolutionmethod.............................. 226
List of Tables
1.1 World thermoplastic market 1

..................................................................
1.2 World polyolefin capacity & demand by regions 5
..........................................
2.1 Polymerization processesand reactor operating conditions 17
..............................
2.2 Comparison of high-pressure free-radical and low-pressure gas-phaseprocess 19
......
2.3 Low-pressure ethylene polymerization processes 21
..................... .....................
2.4 Typical operating conditions & production capabilities of gas-phase 29
processes......
3.1 General kinetic mechanism of catalyzed olefin copolymerization 46
.................. ....
3.2 Simplified kinetic mechanism of ethylene copolymerization over a Ziegler-Natta
catalyst................................................................................................ 61
4.1 RGA matrixc over the first operating opoint 79

...............................................
4.2 RGA matrixc over the secondoperating opoint 79
...........................................
4.3 Best pairings of manipulated and controlled variables based on static RGA
analysis................................................................................................ 80
4.4 Retrospectof the grade transition problem in polymerization reactors 88

..................
5.1 Operating conditions and product specifications for gradesA and B 109
...................
5.2 Constraints imposed on the bij binary variables 115
............................................
5.3 Calculated optimal control structure for the A to B grade transition 115
.....................
5.4 MIDO algorithm convergencecharacteristics for the transition form grade A to B 116
...
6.1 Polymer grade specifications 138
..................................................................
6.2 Optimal production sequence 150
.................................................................
6.3 Comparison between the proposed sequences 150
..............................................
6.4 On-spec periods during the transition campaigns 153
...........................................
7.1 List of controlled and manipulated variables of the FBR 178
..................................
7.2 Linking-parameters of the Flash Separatorwith previous units (Loop Reactor) 183
.......
7.3 Degreesof freedom and Initial conditions 184
...................................................
xi
List of Tables
7.4 Control schemeapplied for the optimal operation of the Borstaro plant ............... 193
A. 1 Basic reaction pseudokinetic rate constants 209

.................................................
A. 2 Numerical values of the kinetic rate constants of the ethylene-I -butene copolymerization
over Ziegler-Natta, catalyst of two active sites-FBR model .................................... 214
A. 3 Numerical values of the kinetic rate constants of the ethylene-I -butene co-
polymerization over Zicgler-Natta catalyst of two active sitcs-Borstare plant model...... 215
BA Processunit design and operational parameters-Borstaroplant model 217

..................
B2 Reactor and heat exchangerdesign parameters-FBRmodel 218
...............................
B.3 Components' physical property parameters 218
.................................................
DA Characteristic parameters of the Sanchez-Lacombe EoS for the components of the
polymerization mixture ............................................................................. 230
D. 2 Binary interaction parametersfor the mixing rule of the Sanchez-LacombeEoS..... 232
-t
xii
List of Symbols
A cross-sectional
area(m2)
[A] (Mol/M 3)
aluminum alkyl cocatalyst concentration
av volume fraction of amorphous polymer

(MOL/ 3)
Cd
concentrationof deactivatedcatalystsites M
Cd,,d mass of "dead" polymer in a processunit
Cý-. mass of polymer introduced in a processunit from a previous one
CPd mass of polymer produced in a reactor unit
CPman specific heat capacity of a mixture of components (cal/g/K)
Cp. specific heat capacity of water (caVg/K)
Dn
concentration of "dead" copolymer chains of length W (MOI/M3)
DP. number averagedegreeof polymerization of polymer
DP.,, weight averagedegreeof polymerization of polymer
(MOLI 3)
[E] electron donor concentration M
Fbiem bleed flow rate (kg/s)
F,
t catalyst feed rate (kg/s)
,.
Fffý, hydrogen feed rate (kg/s)
FM, feed rate of component Mi (kg/s)
Fn. 1,F.,, 2 monomer and comonomer make-up feed rates (kg/s)
FN, nitrogen feed rate (kg/s)
F,,.t total product removal rate (kg/s)
Fp polymer flow rate (kg/s)
F,..r recycle flow rate (kg/s)
xiii
List of Symbols
F,.co flow rateof the recyclestreamafterthe bleedstream(kgIs)
h bed level (m)
[H21 hydrogen concentration in the bed (Mol/m 3)
H&ccum accumulation enthalpy term (cat/K/M 3)
Hgas,
in gas input enthalpy rate (cal/s/m)
Hgas'Out gas output enthalpy rate 3)

(cal/s/m.
Hgenr polymerization heat rate (cal/s/m3)
Hprod, (cat/ 3)
out product output enthalpy rate S/M
k& (m3/mol/s)
kinetic rateconstantof the activationreactionby cocatalyst
k&E (m3/mol/s)
kinetic rateconstantof theactivationreactionby electron donor
k. kinetic rate constant of the activation reaction by hydrogen (m3/mol/s)

H
kam, kinetic rate constant of the activation reaction by monomer of type T (m3/mol/s)
k8sp kinetic rate constant of the spontaneousactivation reaction (s-1)
kdA kinetic rateconstantof the deactivationreactionby cocatalyst (m3/mol/s)
(m3/moVs)
kdE kinetic rateconstantof the deactivationreactionby electrondonor
(m3/mol/s)
kdz kinetic rateconstantof the deactivationreactionby impurities
kdll (m3/mol/s)
kinetic rateconstantof thedeactivationreactionby hydrogen
kdM, kinetic rate constant of the deactivation reaction by monomer of type T (m3/mol/s)
k dsp kinetic rateconstantof the spontaneous

deactivationreaction(s-1)
knstA kinetic rateconstantof the site transfonnationreactionwithout terminationby
cocatalyst (m'/mol/s)
xiv
List of Symbols
knstE kinetic rateconstantof the site transformationreactionwithout terminationby
3/mol/S)
electrondonor(m
knstZ kinetic rateconstantof the site transformationreactionwithout terminationby
impurities (M3/mot/ S)
knstH kinetic rate constant of the site transformation reaction without termination by
hydrogen (m'/mol/s)
knstm4 kinetic rateconstantof the site transformationreactionwithout terminationof a
in
polymer chain ending a monomer unit of type T with a monomer of type
(M3/mol/S)
k site transfonnationreactionwithout
kinetic rateconstantof the spontaneous
nstSp
termination(s-)
ko, kinetic rate constant of the initiation reaction with monomer of type T (m3/mol/s)
kP4 kinetic rate constant of the propagation reaction of a polymer chain ending in a
monomer unit of type T with a monomer of type J' (m'/mol/s)
kstA kinetic rateconstantof the site transformationreactionwith terminationby
(m3/mol/s)
cocatalyst
kstE kinetic rateconstantof the site transformationreactionwith terminationby
donor (m3/mol/s)
electron
kstz kinetic rate constant of the site transformation reaction with termination by
(m3/mol/s)
impurities
kstH kinetic rate constant of the site transformation reaction with termination by
(m3/mol/s)
hydrogen
-t
xv
List of Symbols
kstm, kinetic rateconstantof the site transformationreactionwithout terminationof a
polymer chain ending in a monomer unit of type T with a monomer of type
(MI/movs)
k kinetic rateconstantof the spontaneous

site transformationreactionwith
stsp
termination (s-1)
k,Aj kinetic rateconstantof the chaintransferreactionof a polymerchainendingin a
monomer unit of type T by (m 3/mol/s)

cocatalyst
k, Ej kinetic rateconstantof the chaintransferreactionof a polymerchainendingin a
(m3/mol/s)
monomerunit of type T by electrondonor
k, kinetic rate constant of the chain transfer reaction of a polymer chain ending in a
Hi
type T by hydrogen (m 3/Movs)

monomer unit of
k, kinetic rate constant of the chain transfer reaction of a polymer chain ending in a
m,
'j' (M 3/mol/s)
monomer unit of type T with a monomer of type
ktsp, kinetic rate constant of the spontaneouschain transfer reaction of a polyrner chain
endingin a unit
monomer of type T (s")
Maq
coolantmassin the heat (kg)
exchanger
Mgas
total massof gasesin the heatexchanger(kg)
Mi T
massof component in unit
a process (kg)
3)
IM, I monomerconcentration
(Mol/m
M,
numberaveragemolecularweightof polymer
MP total polymermassin the reactor(kg)

[MT1 (Mol/m 3)
total monomerconcentration
MW component molecular weight
M, weight averagemolecular weight of polymer
xvi
List of Symbols
[N21 concentrationof nitrogenin the bed (mol/m3)]
Ný numberof well-stirredzonesin theheatexchanger
N. total numberof monomers
No numberof catalystactivesites
P pressure in a processunit (bar)
PD polydispersity index of polymer

IPOI
concentration of vacant catalyst active sites (mol/m)
[P.,
ij concentration of "Iiveý' copolymer chains of length 'n' ending in an T monomer
3)
unit mo
[P.
total concentrationof activesites(vacant andoccupiedby polymerchain)
(Mol/ 1113)
Q heattransferrate(cal/s)
(m3/s)
QO volumetricproductremovalrate
3)
[SP concentrationof potentialcatalystactivesites
(Mol/m,
T temperature (K)
T. temperature of the recycle stream at the heat exchanger exit (K)
Tw,in inlet water temperatureto the heat exchanger (K)
TI, water temperaturein the heat exchanger(K)
U overall heat transfer coefficient (J/K/m2/s)
Ybed bed volume (m 3)
Vef (m 3)
effective volume where the polymerization takes place
Void void volume fraction in the fluidized bed
Xery, mass fraction of crystalline polymer
XIIj mass fraction of component T in the "heavy" phaseof a processunit
xvii
List of Symbols
XLj mass fraction of component T in the "light" phaseof a processunit
xMi massfraction of monomerT in thebed
XH, mass fraction of hydrogen in the bed
XN3 mass fraction of nitrogen in the bed
IZI concentration of poison or impurities (mol/m)
Greek IeUers
P. net reactionrateof activationreactions(s-1)
Pd net reactionrateof deactivationreactions(s")
P-t net reactionrateof site transformationreactionswithout termination(s-)
Nt net reactionrateof site transformationreactionswith termination(s-1)
Pt net reactionrateof chaintransferreactions(s-1)
Mmac heatof reaction(cal/g)
Cbed bedvoid fraction
Cef fractionof the effectivevolumein the fluidizedbed
X, "live" copolymermomentof I -order(moVm3)
(Mol/M3)
At "dead" copolymermomentof I -order
MI
melt index
4t totaV'buW' copolymer moment of i -order (mol/m)
P density (k g/M3)
9i instantaneouscopolymer composition with respectto the T monomer
(Di cumulative copolymer composition with respect to the T monomer
Subscripts and Superscripts

-
I ethylene property
xviii
List of Symbols
I -butene property
type of catalyst active site
polyiner property
rec: recycle stream value
sp set point
xix
CHAPTERI
Polyolerin Market Status
1.1 Introduction
Polymerindustryis classifiedwithin the mostcompetitiveandprofitable chemicalindustries

dominatingin the growing intermaterialsubstitutionpolicy of paper,aluminum,metal and
glass. Among the broad variety of polymeric materials, polyolefins are the leading
contestantsand they have receivedspecialattentionduring the last yearscapturinga large
portion of the future plastic markets.Theseolefin polymers include the isotactic poly-1-
butene, poly-4-methyl-l-pentene, ethylene-propylene-dienc (EPDM) copolymers,
copolymersof higherolefins, dienesand cyclic olefins, while homopolymersof ethyleneand
propylene(Low Density Polyethylene, LDPE, Linear Low Density Polyethylene,
LLDPE,
High Density Polyethylene,HDPE and Polypropylene,PP) exhibit the highestcommercial
growth dominatingin the world's thermoplasticmarket(Table 1.1;Zacca,1995).
Table 1.1: World thermoplasticmarket.

Product Demand Market share
(Thousandof Tones) (%)
1983 1990 1995 2005 1990 2005
LDPE 11,322 13,999 14,367 15,873 19.4% 12.7%
LLDPE 1,460 4,739 7,760 15,251 6.6% 12.2%
HDPE 6,411 11,439 14,327 20,925 15.8% 16.7%
pp 8,422 12,587 17,066 27,710 17.5% 22.1%
Sub Total 25,615 42,764 53,520 79,959 59.3% 63.7%
Other 20,001 29,362 34,369 45,395 40.7% 36.3%
(PVC, PS, ABS)
Total 45,616 72,126 87,889 125,154 100% 100%
Chapter 1 Polyolerin Market Status
1.2 Polyolefin applications
The tremendous and continuous growth of interest for polyolefins stems from their highly
versatile physical and chemical properties in

resulting end-use properties and applications of
similar versatility. This polyolefin feature brings about several modifications and high
flexibility of the operating profiles in the polyolefin industry. One of the significant trends
observed in polyolefin producers has been the movement from the "traditional" polyolefin
commodities (i. e. LDPE, LLDPE, PP, etc.) toward specialty and value added polyolefins,
which are almost always associatedwith higher value to the end-usersas well as higher profit
margins for the polymer producers.
The polyolefin products are sold into the major end-use markets world widely, especially
extrusion coating, film and fiber, blow, injection and rotational moulding wire and cable, and
pipe and tubing. This broad range of applications is dependant on the molecular and
structural properties of polyolefins and polyethylene in particular; therefore, the American
Society for Testing and Materials (ASTM) has classified PE into four groups:
i.) (low density) at 0.910-0.925 g/CM3,
ii. ) (also low-density) at 0.926-0940 g/CM3,
iii. ) (high-density copolymers) at 0.941-0959 g/CM3and
iv. ) (high-density homopolymer) at 0.960g/cM3and above (Redman, 1991).
However, in the literature PE is broadly categorised in the following two general groups
based on its density: i. ) low-density (LDPE) at 0.910-0.930 g/CM3 and ii. ) high-density
(HDPE) at 0.931-0.970 gr/cM3, while the former is further classified as low-density (LDPE)
and linear low-density polyethylene (LLDPE) basedon the polymer chain microstructure and
the synthesis processes(Figure 1.1, Xie et al., 1994 ). Linear low-density polyethylene
(LLDPE) has many properties distinguished both from those of HDPE and conventional
LDPE. Particularly it is claimed to be useful for rubbish and millinery bags, stretch wrap,
heavy wall bags, frozen food bags, telephonejacketing, houseware and rotational moulding.
Hence, polyethylene applications are commonly referred with respect to the above
classification. Figure 1.2 (James, 1986) summarises schematically the market and
applications of HDPE and LLDPE produced in low-pressure polymerization processes,while

Figure 1.3 (Chemical Market resources, Inc., 2002) gives the global demand for high-
pressure LDPE (HP-LDPE) resins.
2
C I Poholefin Market Status
IIDIIE
0.93-0.97 g/ml
LLDPE
0.91-0.93 g/ml
LDPE
0.91-0.93 g/m
Figure I. I: Schematic of moleCUlar structurc foi- comnicrcial PE.
0.98
0.97
)N
0.95 HDPE BLOW HOPE

PIPE & G
40
MOLDING
SHEET
0.95
HOPE FILM
0
LU
ý
0.94
U) MOPEFILM
z LLDPE
ý PIPE &
0.93
SHEET
0.92
DEVELOPING
0.91 AREA -
,
0.90,
0.01 0.10 1.00 10.0 100
MELT INDEX, g/10 min
Figure 1.2: Markcts and applications ot'low-pressurc polycthylenc.
Others
6%
Other Extrus n
9% Food Packaginj
W- 19%
Extrusion
Coating
injection
Molding
7%
Slow
Molding Comnlercial &47%
Industrial
4%
Source Chemical Market Resources, Inc
Figure 1.3: Global demand off IP-IDPE resins.

Chapter 1 Polyolefin Market Status
1.3 Historical Overview-Statistics
The production of polyolefins in industrial scale goes back to 1934 when Imperial Chemical
Industries(ICI) first discoveredthe free-radicalhigh-pressure(over 3000 atm.) processfor

polyethylene production. This polymerization process was favourable mainly for low-density
(LDPE) density around 0.92 3
g/cm due to the free-radical mechanism,
polyethylene with
which results in a large degree of polymer chain branching. After this launch of polymer
industry in chemical industry, the commercialization of polyolefins was hampered mainly by
high manufacturing costs (due to the high operating pressure) and limited applications and it
needed almost two decades of intensive research for a breakthrough that radically changed
the polyolefin production. It was in the 1950s that Ziegler and Natta first demonstrated the
synthesis of linear high-density polyethylene and isotactic polypropylene over catalyst
systems based on titanium halides and aluminum alkyls (Hutchinson, 1990). Their discovery
led to the commercial production of polyolefins using TiC13"first generation" catalysts and
initiated a series of both catalyst and processdevelopments from the late 1960s till the middle
of the previous decadetargeting to the production of polyolef in commodities at low cost.
Within this period of time there have been developed several process and catalyst
technologies for polyolefin production, which have been patented by coliseum-companies of
industry taking advantage of the licences of these processes. Currently, only for
polyolefin
the production of linear polyethylene there are over 25 licensors offering technologies usually
combining both process and catalyst know-how. There are many factors associated with the
selection of an appropriate technology license including, but not limited to, capability of the
process to produce the desired resin grades, breadth of the process technology, ability to
importantly, cost. All these factors should
produce specialty grades,catalyst options and most
be given the appropriate importance by the licensees without focusing only on the cost
becauseoverlooking some of them may lead to technologies that are unable to expand with
the future needsof the licensee to satisfy the continuously growing market demand.
The following Table 1.2 (Chemical Market Resources, Inc., 2002) discretizes into several
the the polyolefin demand and capacity for the year 2002 of polyolefin
regions of world
industries applying different technologies. When the current state of polyolefin capacity and
demand is viewed in relation to the respective demandsand capacities over the last ten years,
then some useful conclusions for the status of polyolefin industry can be derived. The
Industry in Western Europe appearsto be as troubled as in North America. It is

polyolefin
4
Chapter I Polyolefin Market Status
Table 1.2: World polyolcfin capacity & dcmand by rcgions.
LDPE HDPE
World Capacity: 19,640thousand tn World Capacity: 28,894thousand tn
Asia/Pasific 4,354 thousandtn Asia/Pasific 9,026thousandtn
Europe 5,624 thousand tn Europe 3,492 thousandtn
North America 4,581 thousand tn North America 10,704 thousandtn
Rest of the World 3,991 thousand tn Rest of the World 5,669 thousandtn
World Demand: 14,560 thousand tn World Demand: 14,560 thousand tn
: 3,447 thousand tn Asia/Pasific 3,764 thousand tn
Europe : 5,171 thousand tn Europe 3,991 thousand tn
North America : 4,037 thousand tn North America 6,214 thousand tn
Rest of the World 1,905,thousand tn Rest of the World 2,041 thousand tn
:
'LLDPE PP
World Capacity: 22,362 thousand tn World Capacity: 44,044 thousand tn
Asia/Pasific 6,940 thousand tn Asia/Pasific 13,471 thousand tn
Europe 3,492 thousand tn Europe 9,480 thousand tn
North America 8,300 thousand tn North America 8,028 thousand tn
Rest of the World 3,628 thousand tn Rest of the World 4,898 thousand tn
World Demand: 11,521 thousand tn World Demand: 27,215 thousand tn
Asia/Pasific 3,401 thousand tn Asia/Pasific 9,797 thousand tn.
Europe 2,404 thousand tn Europe 7,937 thousand tn
North America 4,263 thousand tn North America 7,030 thousand tn
Rest of the World 1,451 thousand tn Rest of the World 2,449 thousand tn
facing the problem of high rates of capacity increasewithout equally increasingrates in

demandresultingin decreasingoperatingrates(Figure 1.4,ChemicalMarket Resources,Inc.,
2002). The variability in production and capacity is presented separately for each one of the
most commercial polyolefins for Western Europe in Figures 1.5-1.8. It is pointed out that the
capacity of LDPE remains almost constant the last seven years, while LLDPE exhibits the
higher capacity increase compared to the other polyolefins. These trends indicate a
continuously increasing interest for low-pressure catalytic polyolefin production technologies

(LLDPE, HDPE, PP) as well as reliance for the traditional technologies producing LDPE.
These trends should be considered taking into account the consolidation activities observed in
the last seven years between several polyolcfin producers in Western Europe (Figures 1.9,
1.10). This merger between polyolefin producers was influenced by various economic factors
affecting polyolefin industries, such as supply and demand economics, raw material cost,
targeting always to maintain profitability, to remain competitive and capture wider polyolefin
markets.
5
25,000 86
p- 20,000 84
x
2ý
,6 e-
82
15,000 Gi
19
80
0
10,000
.0
78
,t5,000 Capacity
76
Production
0 74 Utilization
1995 1996 1997 1998 1999 2000 2001
Source: Chemical Market Resources, Inc.
Figure 1.4: Production and capacity of polyolefins, Western Europe, 1995-2001.
5000 92
4500
90
4000
3500
3000 ýCapaclty
86
2500 IC=Production
84
2000
1500 82
1000
500
80
0 78
1995 1996 1997 1998 1999 2000 2001
Figure 1.5: HDPE production, capacity and operating rate, Western Europe, 1995-2001.
4000 80
35W 70
3000 60
2500 50
Capacity
2000 40 IM Production
S
0 Grati
1500 30
1000 20
sw 10
0 0
1995 1996 1997 1998 1999 2000 2001
Figure 1.6: LLDPF production, capacity and operating rate, Western Furope, 1995-2001.
()
Chanter I olefin Market Status
70DO 86
85
6000
84
5000 83
ci
0
82
4000 Capacity
CL
30DO
81 L?
80
'4= EM
--*--0
Production
ratin
co 20DO 79 0
78
1000 77
0 76
1995 19M 1997 1998 1999 2000 2001
Figure 1.7: LDPE production, capacity and operating rate, Western Furope, 1995-2001.
10000 92
9000 90
8000
88
CF 7000
6000
86
e p
5000 84
ý 1-0--oper-ati
4000 82 &
3000
80
2000
78
1000
0 76
1995 1996 1997 1998 1999 2000 2001
Figure 1.8: PP production, capacity and operating rate, Western Furope, 1995-2001,
montell E, d.. O. h.. MW-"

(5 (BP)
sichemlo
1
BP A.
Montefl 11
Elonec Targor
Shell (100%)
OP
Source: Borealis Presentation to financial conunuui(N, No-'ember 2002
Figure 1.9: W. Furopcan producer consolidation activity, 1995-2002.
7
lAppryl
jl"ýýA-pp,
yl
I ILD3MI1VtOIOUmI
L-*'(AtDchem) I
'Ir°
-T ri I DSM
(BP)
p'Y'
Source: Borealis Presentation to the financial community, November 2002
Figure 1.10: W. European producer consolidation activity, 1995-2002.
Figures 1.11 and 1.12 demonstrate the world's largest polyolefin producers and the most
dominant polyolefin producers in Western Europe, while Figure 1.13 presents the pricing of
polyolefins highly influenced by the supply-demand balance that is affected in turn by such
merging activities. Despite the research orientation towards low-pressure technologies for
LLDPE, HDPE and PP, LDPE produced by high-pressure polymerization processes, has
maintained a price premium over the other polyolefins in the last ten years, and considering
the constant production it seems that it cannot be replaced by the other types of polyethylene
in terms of its end-useproperties.
From the evaluation of all these financial indexes it is concluded that the macroeconomic
conditions around the globe as well as the Western European countries like UK, Germany
and France do not portray a strong recovery in near future. The industry has to continuously
focus on decreasing costs and improving operating efficiency. This motivates major
to
polyolefin producers reinforce Research & Development departments, which are receiving
serious consideration and seem to be the direction towards polyolefin industries turn to
awaiting reliable solutions to their problems.
8
Chat)ter I Polvolefin Market "Stattis
thousand tn
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Exxon Mobil Corp.

Dow
Basell
BP
SABIC
Borealis
TotalFinaElf
Equistar
Chevron Phillips
FPC
Source: Borealis Presentation to the financial community No %enrIf 2002

,
Figure 1.11: World's largest polyolefin prod Licers-2002.
thousandtn
0 1000 20(W 3000 5000 WWO
Basell
Borealis
BP
TotafFinaElf
DOW
Polimeri Europa
Exxon Mobil Corp.
RepsolSA
ypropylene
Polychim
Source: Borealis Presentation to the financial cojtununit. ý, November 2002
Figure 1.12: flolyolcfin producet-s in Western Europe-2002.
9
I Polyolefin Market Status
1000
900
800
700
600 LDPE
E/tn LLDPE
500
HDPE
400
-pp
300
200
100
0
1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001
Source: Chemical Market Resources,Inc.

Figure 1.13: Pricing for polyo1cfin prodUcers, 1990-200 1.
1.4 Motivation- Research Justification
From the preceding discussion over the status ofpolyolefin market there arc some key points
that one should keep in mind in order to outline the current state of the polymer industry and
to draw some conclusions that will indicate the directions where relative research work
should move towards. A crucial point is the economic potential ofpolyolefin industry, which
is one of the most active and evolutionary branches of chemical industry as a result of' the
continuously innovative applications of polyolefin commodities and the consequent growing

market interest and demand. However, the disproportional increase of product supply, on
behalf of polyolefin industry, together with the very severe and explicit specifications of
product quality are serious threats of the competitiveness and viability of' the polyolefin
industry. The period that the polymer manut'acturcrs were trying to improve the process
productivity in order to increase its profitability belongs to the past. Now, the polymer market
is much more qualitatively demanding and the competitive edge will come for the polyolcfin
industry from the technological developments that will account for an integrated
improvement of tile production performance and will excel in controlling the polymer
properties obeying simultaneously to the safety regulations throughout the processoperation.
On the basis of this establishment, this thesis is motivated by the chaotic nature of the
problem in the sense that economic, administrative, stratcg,ic manipu lations and engineering
10
issues are all involved with different impact on the problem formulation. Within this thesis,
the problem is approached from the process system enginecring perspective, "Ith evident
influences though from economic aspects. Precisely, an attempt to underline some of the
problem dimensions is made in order to demonstrate in a tangible way the importance of
utilising advanced techniques and mathematical tools to handle such mazy problems. Hence,
the remaining of this report is orgamsed based on the following schematic representation
(Figure 1.14), where three thematic sections are hierarchically discussed reflecting the
expanding nature of the problem:
Chapter 2: The problem is related to the catalytic olefin polymerization process.
Chapter 3: A mathematical model for a gas-phaseethylene copolymerization fluidized

bed reactor is developed for a model-based investigation of the problem.
Chapter 4: The process design, control and operation related elements of the problem are
highlighted and some mathematical tools for the solution of the problem are analysed.
Chapter 5: The optimal control and operation ofa polyolefin FBR is investigated as a case
study of this problem discussed so far, introducing the concept of an advanced mathematical
optimisation algorithm.
Chapter 6: A second case study related to the scheduling dimensions of the generic
problem is explored using the same mathematical algorithm.

Chapter 7: Development of a more detailed and comprehensive mathematical model of an
industrial polyolefin plant for the revision of the above problems on a plant-NAIdc base.
Chapter 8: Conclusions and suggestions for future research work are discussed.
" Understanding of the

Polymerization Chapter 2
Process Operation
" Development of a high Chapter 3
Fidelitv Mathematical
Model
e--
Introduction to Process
Lf Chaptcr 4 Chapter 7
lithe i,S,i,, rade
Transition Optimi sation
Chapter 5
L1,;
mphasisoil Cont1-4)[a
Ild
operationalissues Chapter 6
Figure 1.14: Structure ofthe thesis basedon three thernatic sections.

Within these chapters the main objectives that this thesis aims at is to identify and confront a
number of operational and design industrial scale problems that appear in the polyolefin
industry as a consequenceof the requirement of the polyolefin processesto follow a market
driven operating profile. The deliverables resulted from this work towards the above
direction are:
a great knowledge-theoretical know-how over the gas-phase olefin polymerization

reactor systems necessary for the dynamic simulation of such systems, the
understanding of several physicochemical phenomena and a model-based approach of
various problems related with them,
comprehensive dynamic models of a single catalytic gas-phaseolefin polymerization

Fluidized Bed Reactor (FBR) unit and an industrial scale polymerization plant,
study and solution approachesof the optimal control and optimal operation problem in
a gas-phaseolefin polymerization FBR with respect to the transient operation of this
reactor between different operating points as a multiproduct polymerization process.
12
Chapter 1 Polyolefin Market Status
1.5 Literature
Chemical Market Resources,Inc. (2002) New generation polyolcfins, Vol 8.
Hutchinson, R. A. (1990) Modelling of particle growth in heterogeneous catalyscd olcfin
polymerization. PhD Thesis, University of Wisconsin-Madison.
James, D. E. (1986) Encyclopaedia of Polymer Science and Engineering, Kroschwitz, J.I.,

Ed.; John Wiley & Sons: New York, Vol. 6, p. 429.
Redman, J. (1991) Polyethylene. Chem. Eng., 504, p. 26.
Xic, T.; McAuley, KB.; Hsu, J.C. C. H.; Bacon, D. W. (1994) Gas phase ethylene
polymerization: Production processes, polymer properties, and reactor modelling. Ind.
Eng. Chem. Res., 33, p. 449.
Zacca, J.J (1995) Distributed parameter modelling of the polymerization of olefins in
chemical reactors. PhD Thesis, University of Wisconsin-Madison.
13
CHAPTER 2
Polyolefin Technology Developments:

Polymerization Processes & Catalysts
2.1 Introduction
The production and the molecular properties of polyolefins are highly dependant upon the
type of polymerization process and the catalyst system that is employed for their synthesis.
Advancements of catalyst technology, in terms of catalyst efficiency and crystallinity of the
produced polymer, keep step with simultaneous polyolefin process technology

developments. However, researchin the area of catalyst technology seemsto be more active
and usually precede the developments in polyolefin processes.The technological progress in

terms of both the catalyst and polyolefin processeswill be studied in this report with respect
to polyethylene as a representative polyolefin, which attracts high industrial and research
interest.
Investigations over the catalyst technology were directed towards the polymerization process
requirements and the polymer property control. Improvement of catalyst productivity was
given first priority so that catalyst yield would be high enough allowing catalyst residues to
be left in the polymer without degrading polymer quality. Other catalyst features given great
attention was the catalyst morphology, with impact on the polymer particle morphology (via
the replica phenomenon during the particle growth), the copolymerization kinetic behaviour
and the catalyst activity with time, as well as the catalyst shape and size and the
incorporation of comonomer and chain transfer agents for the control of density, molecular
weight and molecular weight distribution (MWD). These important structural attributes of
polyolefins have great impact on the physical, mechanical, optical and rheological polymer
properties. These in turn, through their influence on the resin behaviour in various processing
operations, such as extrusion, injection moulding, blow moulding and rotational moulding,
14
Chapter 2 Polyolefin Technology Developments: Polymerization Processes & Catalysts
affect the end-usepolymer properties identifying the polyolefin markets. Therefore, there is a
chain-relationship between the polymer end-use properties from one side and the
polymerization process and the catalyst from the other side with a number of intermediate
stages in between them. Hence, it is important to understand the effect of the resin molecular
properties on the polymer processing characteristics at a first level, and the impact of the
polymerization processes and catalyst on the polyolefin molecular properties, at a second
level, in order to successfully correspond to the polymer market requirements.
2.2 Polyethylene Processing Characteristics
Different polyethylene processing operations have different resin requirements in terms of

their physical mechanical and rheological characteristics. Tensile properties, elongation
properties, stiffness and hardness as well as melting temperature and melt strength and
viscosity are some of the properties with great impact on polyethylene's processing
characteristics. On a polymer manufacturing level, all the above properties depend on the
polymer density, molecular weight and its distribution, which are commercially used for
polymer specification. Polyethylene density is an index of the degree of branching of the
polymer (in the case of LDPE) or in other words, the higher is the number of branches and the
branch chain length, the lower is PE's density. However, both the size of branches and the
branch frequency distribution significantly decreasespolymer's crystallinity, stiffness and
yield stress and increases the melt strength. Therefore, the different branch size and branch
frequency distribution between LDPE and LLDPE can result in radical differences in some
processing characteristics, although they might have similar densities. In Figures 2.1 and 2.2
(Xie ct al., 1994) the relationship between polymer mechanical properties and density and
molecular weight are schematically depicted. Analogous are the effects of MWD in the
processability of polyethylene. More specifically, at equivalent molecular weight, a
polyethylene with a narrow MWD is tougher than polyethylene with broader MWD. Broad
MWD results in enhanced melt shear thinning and consequently in easily flow resins with
high shear rates prevailing over other resins when extrusion is required. In general, the broad
molecular weight distribution is desired in PE since it attributes better processability to the

polymer and when it is combined with the appropriate density and/or molecular weight it
results in resins with suitable processing characteristics.
15
Chapter 2 Polyolefin Technology Developments: Polymerization Processes& Catalysts
-N
STI
ST
** r lFFNFSS
SILE
S X STRENGTII
T
-11EATRESISTANCE FLUIDrrY
:-HARDNESS DISTORTION RESISTANCE
PERMMEATION
.P,. RESISTANCE OPTICALS
. SI INU
-SHRINKAGE CA
.CPCREEPRESISTANCE w
rg - WEATlir-.RAB[LrrY
94.
-M4PACT STRENGTH
" STRESSCRACK RESISTANCE
TRANSPARENCY " ELONGATION
STRESSCRACK REMSTANCI " TENSILE STRrNGTII
FLEX113IL
QFNGTH " MELTSTRENGTH
IMPACT " ORIENTATION
" ELASTICITY
" PARL30N SAO RESISTANCE
0.90 0.91 0.92 0.93 0.94 0.95 0.96 0.97 0.1 1 10 100
MELTINDEX
DENSITY, g/nd
MOLECULAR WEIGHT
Figure 2.1: Relationship between polymer Figure 2.2: Relationship between polymer
properties and resin density. properties and resin molecular weight.
LDPE and LLDPE are two competing types of polyethylene with some distinctive differences
in their physical, mechanical and rheological properties, which are discussed here to
demonstrate the effect of these properties on the end-usepolymer characteristics. LDPE has a
very broad MWD. The lower MW fraction enhancesprocessability, while the higher MW
fraction enhancesmechanical properties. From the perspective of the degree of branching, the
long chain branching characteristics of LDPE attribute tremendous melt strength, low
crystallinity, soft and smooth feel with excellent optical characteristics but moderate tear and
tensile strength, which is easily processing particularly in blown film and extrusion coating.
The narrow MWD of the LLDPE on the other hand, its high shear viscosity and the absence
of long chain branching render it inappropriate for extrusion, but its higher crystallinity
attributes higher resistance,tensile and tear strength and therefore it dominates over the LDPE
for the production of very thin films. It is apparent that a PE combining some molecular
properties of LDPE and LLDPE would be desired. A common approach applied in the
polymer processing industry is to blend the right proportion of LDPE and LLDPE in order to
improve the overall processability and to exploit the beneficial mechanical properties of
LLDPE in parallel. This has always been a practice in the film industry, while an alternative
approach, emerged the last years, is the production of LLDPE with bimodal MWD. This
approach is the result of both polyolefin process and catalyst technology developments and
raises the second level of the chain-rclationship between the polymer cnd-use properties from
one side, and the polymerization processes and catalysts from the other side, through the
impact of the latter on the polymer molecular properties.
16
2.3 Polyethylene Processes
Commercially, polyethylene is exclusively produced by continuous processes.Within the last

50 years the developments over process and catalyst technologies were tremendous with their
major impact located mainly on the polymerization mechanism and the operating conditions.
It is indicative that while PE was conventionally produced under high-pressure
homopolymerization processes,with this technological progress in polyolefin industry it has
been achieved to be successfully produced by low-pressure processes as well. Currently,
polyethylene production processescan be sorted into at least five process categories as shown
in Tables 2.1 (Xie et al., 1994). It is well distinctive how polyethylene molecular properties
are influenced by the process applied for its production. This effect is more evident when the
differences in polymer properties are studied from the perspective of low- and high-pressure
processes where the different polymerization mechanisms affect the linearity of the main
polymer chain, the type of chain branching and consequently the molecular weight
distribution. More specifically, in the high-pressure processes,the polymer density and the
branching degree are regulated by the reaction pressure; the higher the reaction pressure, the
lower the branching degree and the higher the polymer density. On the other hand, in the low-
pressure processes,polymer density is commonly regulated by the comonomer incorporation

(usually higher a-olefins such as butcne-I or hexene-I) in the polymer chain. However, even
within the low-pressure polyethylene processes,each type of process has limitations on the
breadth of resins it can produce. Figure 2.3 (Chemical Market Resources, Inc., 2002)
Table 2.1: Polymerization processesand reactor operating conditions.

Conventional High-pressure Solution Slurry Gas-phase
high-pressure bulk process polymerization polymerization polymerization

process
tubular or flUidizedor
Reactor type autoclave CSTR Loop or CSTR
autoclave stirred bed
Reactor pressure, 1200-3000 600-800 30-35 20-35
bar -100
Temperature, *C 130-350 200-300 140-200 85-110 80-100

Polymerization
free radical coordination coordination coordination coordination
mechanism
Loci of Solid
monomer phase monomer phase solvent solid
polymerization
Density, g/cm 3 0.910-0.930 0.910-0.955 0,910-0.970 0.930-0.970 0.910-0.970
Melt Index, 0.80-100 0.50-105
0.10-100 <0.01-80 <0.01-200
g/10 min
17
Chapter 2 PolvolefinTechnology Developments: Polymerization Processes& Catalysts
illustrates the capabilities of different processes as it pertains to density and melt index.
Slurry-based processesproduce PE covering a broad range of melt index but limited range of
3
densities is feasible. At a density below of 0.937s,,
/cm polymer dissolution occurs and
significant fouling of the reactor is caused. Hence slurry processesare not suitable for LLDPE
production. Solution processeshave a broader operating range in terms of densities and melt
indexes. However, as molecular weight increases above a certain point, solution viscosity
increases consequently and limiting the reactor operability and productivity rendering the
process inappropriate for high molecular weight IIE. Gas-phascprocessesdominate over the
others because they have the widest operating window but encounter some difficulties in
producing resins with very low densities due to stickiness and particle agglomeration.
Comparing the low-pressure processes,from an operating point of view, ignoring their impact
on the processing characteristic of the produced polymer, one can notice that an attractive
feature of the slurry polymerization process over the others is the excellent temperature
control. However, when polyethylene is produced by copolymerizing ethylene with a-olcfin

comonomers, polymer swelling occurs, polymer density decreasesand the resin solubility in
the dilute increases, which is a major problem for the slurry processes. The solution
polymerization process overcomes this problem and moreover ensures better molecular
weight distribution control and process variables control becausepolymerization occurs in a
0.967
0.939
C.)
0.920
d)
0.914
0.900
0.01 0.1 1.0 10 100
Melt Index (q/10 min)
Figure 2.3: Pi-oduction capabilities oflo\k-lm-essure PE processes.
18
homogeneousphase. However, as it was statedbefore, very high molecular weights cannot be
produced easily at the high temperaturesof the solution processes,and since the solids content
is relatively low compared with the slurry process, greater diluent recovery is required.
Polymer separation, diluent recovery, and polymer drying steps may be eliminated in gas-
phase polymerization processes,but the gas-phaseprocessessuffer from difficulties in reactor

temperature control. Reactor operating temperature is limited to the resin softening point and
the poor heat-transfer efficiency of the gas phase is restrictive for high production rates.
Therefore, an inert heat transfer agent is required to maintain stable reactor operating
conditions. However, there is still a danger of local hot spots formation when a high-activity
is
catalyst used, bringing about undesirable polymer particle agglomeration. Hence, a catalyst
preparation stage usually referred as "prepolymerization" stage, where polymerization takes
place under well-controlled conditions, is necessaryfor high-activity catalysts.
A comparisonof the polyethyleneprocessesis presentedin the following Tables2.2 and 2.3

betweenthe high- and low-pressureprocessesat a first level and betweenthe various low-
pressureprocessesat a second level. Precisely, the high-pressure polyethyleneprocess is
compared in Table 2.2 (Imhausen et al., 1981; Karol, 1983) with the gas-phaseprocessas
and
representative most competitivecase of the low-pressurepolyethylene processes,in terms
Table 2.2: Comparison of high-pressure free-radical and low-pressure gas-phaseprocess.

High-Pressure Process Low Pressure Gas-phase Process
tubularor autoclavereactor fluidized bedor stirredbed reactor

high operation pressure,-3400 atm Low operating pressure,-20 atm.
high reaction temperature -300 OC low reaction temperature 80-100 OC
high energy requirement low energy requirement
high capital cost Low capital cost

limited to low-density PE can produce both high- and low-density PE
no comonomer required (homopolymer) for
up to 10-15%comonomer required (copolyincr)
LDPE production
catalyst is less sensitive to feedstock impurities is

catalyst very sensitiveto impurities
feedstock
low raw material cost high raw materialcost
canproduceethylene and vinyl acetate

copolymer currently a limited rangeof comonomers
mostly linearpolymerchainswith short-chain
polymerwith long-chainbranching branching
19
Chapter 2 PolyolefinTechnology Developments: PoI.Nmerization Processes& Ca(ahsts
of both operating characteristics as well as polymer properties. In Table 2.3 (Chol and Ray,
1985a) the basic features of the three low-pressure polyethylene process categories are
highlighted while some of the most commercial technologies applied in each one of the
polymerization processesare also reported.
There is a significant overlapping between the low-pressure processes with respect to the
LLDPE and HDPE production (see Figure 2.4), however the dominance of each one of these
processes over the others in the production of one or the other type of linear PE is very
distinguishable. In Figure 2.5 (Chemical Market Resources, Inc., 2002) it is shown that
currently the global capacity of linear polyethylene processes is in excess of 43,5 million
tones with 63% of linear PlEs being VIDPF and the 37%, I. I. DPF. Note that sixty five percent
of HDPE is produced via slurry processeswith the gas-phaseprocessescontribute only to the

25% of HDPE production. Compared to HDPE though, only 4'YOof LLDPE resins are
produced via slurry processes and 75% applying gas-phase processes. In the total linear
polyethylene market, gas and slurry processes hold an equal share (of 43(yo and 42%
respectively) accounting for 85% of total capacity and the remainder being solution processes.
Slurry Solution
LLDPE
Hostalen Unimadfilfama CwTIPACI
Mitsui Unipol, Irrovene Dowlex
Nissan! Equ istar/Marwerl Sclairlech
Nisseki mn'l Solution
Phillips Compact, Dowlex-Scairtech
Phillips
Solvay
Solvay
USI
US
Birnodol Sluii BkncW&l Gms
Borslar
Hoslah, Urýpol 11,Spherilcý
Mitsu:,
Nissa
Fluid Bed
EVOIU6
LupolechG
Innovene
Spherilene
Unipol
Unipol11
Figure 2A Low-pressure polyethylene processes-tcchnologics and overlapping in product

specifications.
20
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Chapter 2 PolyolefinTechnology DeNelopments: Polymerization Processes& Catalvsts
LIAM, 37%
16,363 ktn
fur
Ga
.
4%
dj
Wq
21%
Figure 2.5: Linear PE capacity by type and pi-ocess.
Gas-phase processes in particular, has experienced a healthy growth rate over the last ten
years with an average growing rate of 6. PYO.In I linear polyethylene capacity expansion of
5.5 million tones anticipated to come on stream by 2007, approximately 50(yoof the capacity
addition is expected to be based on gas-phasetechnologies. This world\k idc popularity of the

gas-phaseprocesses,within the resin producers due to their features In producing commodity
grade resins, motivates an extensive survey over the most commercial gas-phaseprocesses,
since one of these processeswill provide the base for this work upon which further research
activities related to advancedoptimization and processcontrol will be applied.
2.4 Gas-Phase Polyolefin Processes
The gas-phase polymerization process is the most recently developed as well as the most
versatile. Due to its economic and technical advantages it gains ground particularly In tile
production of LLDPE over the other processes. There are sig,nit'icant research and product
development efforts undemay exploiting (i) catalyst-process advancements and cornonomer
combination and/or (]I') multiple reactors in series to Manufacture, through gas-phase
processes, ethylene-based copolymers that have the processability of LDPF and tile improved
physical, mechanical and optical properties of linear ethylene-based copolymers. Tile
economic benefits expected from these features prompted many polyethylene manufacturers
to apply gas-phase ethylene polymerization technologies utilizing relatively "ell-proven
silica supported chromium oxide catalysts or high activity Ziegler-Natta catalysts (Choi and
Ray 1985b).
22
Gas-phase processes provide an attractive environment for olefin polymerization with no

liquid inventory. This is the distinguishing characteristic of these processes,that the system
does not involve any liquid phase in the polymerization zone and therefore, diluent recovery
and polymer drying steps are redundant. A survey over the development of the gas phase
polymerization process reveals that the first gas phase process goes back to the 1950s. Dye
(1962), whose patent was filed in 1957, was perhaps the first to adopt a fluidized bed reactor
for gas phase olefin polymerization. The ethylene polymerization reactor was operated at a
30 temperature 100 OC. Some improvements
pressure of atm. and a of and changes were
performed by Goins (1960) who carried out ethylene copolymerization in a countercurrent
fluidized bed reactor in the presenceof inert diluent gas. Both patents (Dye, 1962 and Goins,
1960) were assignedto Phillips Petroleum Company.
2.4.1 The BASF Gas-Phase Polyolerin Technology

Few years later, Schmid et al. (1967) carried out ethylene polymerization in a stirred
fluidized bed reactor. Their patent was assigned to BASF which was the first company who
developed a gas-phase ethylene polymerization process using Phillips catalysts in 1964
(Wisseroth, 1969; Sailors and Hogan, 1981), but it took them more than 10 years to built a
commercial gas-phaseplant in Germany in 1976. BASF uses a continuous stirred-bed reactor

shown in Figure 2.6 (Trieschmann et al., 1977; Choi and Ray, 1985a), which is equipped
with an anchor agitator used for the mixing in the polymer bed by agitation rather than
fluidization. The reactor operates at 35 atm and 100-110 OC.Fresh monomer, catalyst and
hydrogen, for MW control, are fed through the bottom of the reactor. Polymer is discharged
through a cyclone, with the polymer particles moving to the direction of monomer flow by
stirring, while unreacted monomer and the heat transfer agent are removed though the top of
the reactor, liquefied by a condenserand recycled back to the reactor. Temperature control in
the polymerization zone is achieved by cooling the reactor walls and by controlling the feed
rate of the liquefied recycle stream. Pressure control, on the other hand, is attained by
manipulating the fresh monomer feed rate. Both the temperature and pressure operating
conditions have been selected and maintained at levels such that the vaporized monomer and
heat transfer agent remain in the gaseous state. In parallel with the process development,
BASF induced some modifications on the Philips catalyst. Two catalyst systems are used, a
magnesium-supportedtitanium halide catalyst with aluminum alkyl compounds as cocatalyst

and a silica supported modified chromium oxide catalyst, with the overall catalyst yield
23
Chapter 2 Polyolefln Technology Developments: Polymerization Processes & Catalysts
reaching the 14 million g/g Cr and mainly differing from the conventional Philips catalyst on
the lower chromium content.
2.4.2 The AMOCO Gas-Phase Polyolefin Technology

The next novel technology for gas phase polymerization was developed by Amoco (Standard
Oil Company) in the mid-1970s. Amoco entered into a technical exchange agreement with
Chisso Petrochemical Company, and the match of Amoco's expertise in the production of
homopolymer with Chisso's expertise in copolymer technology gave birth to the new
horizontal gas-phasetechnology (see Figure 2.7) with three major process section areas: (1)
the catalyst feed area, (2) the reactor polymerization area and (3) the post reactor polymer
processing area (Peters et al., 1976; Shepardet al, 1976; Jezl and Peters 1978a,b).
Amoco owns a proprietary catalyst technology for the gas-phase process capable of
producing a wide range of polymer grades for injection moulding, blow moulding, fibers and
films. This is a titanium supported MgC03 catalyst with high yield and activity and
controlled morphology, which achieves the desired polymer grades and production rate
through its feed rate and composition control. The reactor polymerization area consists of a
compartmented horizontal stirred bed reactor divided by weirs into four individually
controllable polymerization sections. Make-up and recycle monomer and hydrogen are fed
into eachreactionzonealongthe bottom of the reactor.Catalystis fed into the reactorwith a
0:
ui
CYCLONE
48
z
8
PF
CATALYST
HYDROGEN
MONOMER
RECYCLE
Figure 2.6: BASF gas-phaseethylene polymerization process.
24
quench liquid, usually isobutene or isopentane. The latter, as it is introduced into each
polymerization zone through spray nozzles, located at the top of the reactor, is used for
temperature control of the exothermic polymerization reaction in each reactor compartment
by evaporative cooling. Unreacted monomer, hydrogen and quench vapour are removed from
the top of the reactor partially condensed and recycled back. The polymer powder as it is
produced into a low-pressure environment gradually exceeds the decreasing-height weirs
from the first to the last compartment and falls into the adjacent reaction zone in the direction
of the polymer discharge and withdrawn to the post reactor processing area. There, after a
gas/powder separation system, the polymer powder, which have been stripped from absorbed
monomer, together with suitable additives and external heat are continuously fed into a
mixer, where vigorously blended, melted and finally converted into uniform pellets.
The multicompartment character of the reaction zone is the distinguishing feature of the
Amoco process, which provides significant benefits since the reactor operates like a set of
CSTRs in series. This near plug flow reactor operation brings about high production rate per
reactor volume, feasible polymer molecular property (particularly MWD) control permitting
production of ethylene-propylene copolymers with high impact strength and good stiffness
while the narrow solids residence time distribution results in quick startups and shutdowns,
and rapid grade transitions (Brockmeier, 1991).
RECYCLEMONOMER-HYDROGEN-OUENCH
VAPOR
ý;
ýTALYST
SPRAY NOZZLES
; Tl-ý 44-. 4 4z
OI
5
0
16Q6Q66.. 91 -
LU
MONOMERAND HYDROGENINLETS
POLYMER
DISCHARGE
Figure 2.7: AMOCO gas-phasepolymerization process.
25
2.4.3 The UNIPOL Gas-Phase Polyolefin Technology

The first commercial gas-phase polymerization plant using fluidized bed reactor was
constructed by Union Carbide in 1968 (Rasmussen, 1972; Batleman, 1975) launching an

homonymous gas-phase process, broadly known as Unipol. The Unipol is a process
technology developed initially for HDPE and after a successful and profitable course it was
extended to produce LLDPE (1975) and subsequently PP (1983) as well. Following a
strategic policy Union Carbide decided to license its technology demonstrating first the
success of two new plants in US, and since then more than 45 licenses for PE have been
granted around the world and 70 reactors operate with a total capacity exceeding the 7.25
million tones (Chemical Market Resources, Inc., 1996). This strategic movement of Union
Carbine has made LIDPE widely available and initiated the successful LLDPE penetration
into LDPE markets, and prompted the Unipol technology to be the most widely chosen
process for manufacturing PE reflecting both the efficiency of the technology and the
licensing organization.
In the Unipol. PE process purified gaseousethylene, a-olef in comonomer (usually 1- butene
or I-hexene) and hydrogen are continuously fed to a fluidized bed consisted of a reaction
zone and a disengagementzone (Figure 2.8). The first has a height to diameter Mtion of about
6-7.5, while the second a respective ratio of about 1-2 (Xie et al., 1994). In the reaction zone
polymerization occurs over organochromium titanium supported or Ziegler-Natta catalyst.
GAS RECYCLE
CYCLONE
GAS
ANALYZER
CATALYST 7
P 2
2
'r;...
A -iflMER
PRODUCT
GASFEED
COMPRESSOR HEAT
EXCHANGER
Figure 2.8: Union carbide gas-phaseethylene polymerization process-UNIPOL.
26
The catalyst is stored in a catalyst feeder under a nitrogen blanket and is continuously
injected with inert nitrogen in the reactor at a rate equal to its consumption rate. The
unreacted gasesas well as the inert gas are withdrawn from the top of the reactor, through the
enlarged disengagement zone, where entrained particles drop back into the bed. Then the
gases are compressed,cooled in a heat exchanger and recycled back to the reactor, entering
the reaction zone through a distribution plate, along with sufficient amount of monomer to
make-up the monomer consumed for the polymerization. This recycle stream serves the dual
purpose of keeping the bed in a fluidized state as well as removing the heat of the exothermic
polymerization reaction from the reactor. The polymer particles are withdrawn either
intermittently or continuously near the distributor plate into discharge tanks, where the
is
ethylene gas separatedand recycled. This product removal stream is responsible to adjust
the bed volume. The selection of the reactor operating conditions (bed height, temperature
and pressure) has great impact on the smooth operation of the reactor and the polymer
molecular properties and morphology. The reactor pressure is controlled by the inert gas feed
stream introduced with the catalyst stream and ranges from 20-30 bars. A well-controlled bed
height reflects normal fluidization conditions in the bed. This means that the recycle stream
ensuresadequate mixing in the bed and removes also the heat of polymerization retaining the
temperature in the bed between 90-110 'C for IIDPE and 75-100 'C for LLDPE due to its
lower melting point (Levine and Karol, 1977). The demanding temperature control in the bed
is a limiting factor for the production rate of polymer; since the temperature in the bed should
remain below the polymer melt point. Therefore, the higher the amount of heat removed by
the recycle stream, the higher the production rate can be. However, this amount of heat
removed by the recycle stream is determined by the temperature of the recycle stream.
Conventionally, the recycle gas temperature was always kept 3-10 'C above its dew point
it
since was believed that the presenceof any liquid condensatein the recycle stream would
disrupt the bed. That was where the technology stood until Union Carbide introduced an
innovation in the Unipol fluidized bed reactor operation. Union Carbide demonstrated that
the recycle stream could be partially cooled below the dew point resulting in a two-phase
(gas and liquid) recycle stream. This is known as the "condensed mode" operation and its
advantage compared to the conventional operating mode is that it essentially facilitates
greater heat removal and therefore higher production rate. The benefits from this operating
profile become more valuable for ethylene copolymerization with comonomers like I-hexene
or heavier a-olefins, which have high dew point restricting even more the temperature that
the recycle stream could be cooled.
27
The deficiency of the Unipol process to satisfy the requirements of the polymer processing
industry, based on its current equipment for the polymer processing operations, drove the
Union Carbide to the development of Unipol 11,which is the evolution of the conventional
Unipol technology. The Unipol 11 process is the second-generation gas-phase PE
manufacturing technology, targeting to a more precise design and control of the molecular
weight, molecular weight distribution, branching and comonomer incorporation. Innovations
in the catalytic system, comprising the conventional Ziegler systems as well as super high
activity Ziegler catalysts developed by Union Carbide, significantly contribute to the targets
above. Furthermore, the process was designed to take advantage of metallocene catalysts as
well, while the two-reactor process configuration additionally enforces the broadening of the
molecularweight distribution.
2.4.4 The BP Gas-Phase Polyolefin Technology

The other major fluidized-bed production technology for polyethylene is BP's Innovene
process developed by Naphtachimie, soon after the Union Carbide process was introduced,
and was later transferred to BP Chemicals (Delgrance, 1987; Brockmeier, 1987). This
is
process a continuous two-stage polymerization process, combining a stirred tank reactor
and a fluidized bed reactor in series, as shown in Figure 2.9 (Chinh and Dumain, 1990;
Redman, 1991; Martens and Morterol, 1992; Havas and Lalanne-Magne, 1992), with the
fluidized bed reactor being the main polymerization reactor with most of the conversion
MONOMER RECYCLE
HYDROGEN
POLYMER
DIS9ZIE
PREPOLYMER
FEEDER A
MONOMER AND GAS FEED PRODUCT

COMPRESSOR
Figure 2.9: BP chemicals two-stage gas-phascethylene polymerization process.
28
taking place in it. The distinguishing difference of the BP Chemicals process from the Unipol
process is that prepolymer particles rather than catalyst particles are fed into the fluidized bed
reactor. In other words, the stirred tank reactor serves as a "prepolymerization" reactor where
fresh catalystis introducedin the form of dry powder. The prepolymerizationstep of the
processenablesefficient control of catalystactivity in the fluidized bed reactorsinceall the
abrupt phenomena at the beginning of the polymerization(e.
g., the catalyst fragmentation
into fine particles increasing the risk for hot spot formation) take place in the
prepolymerizationreactorunder well-controlledconditionsand reactortemperaturesof 40-
115 T. Besidesthis, prepolymerizationoffers also advantagesin polymer particle size and
MWD control. Towardsthis direction BP processusesboth Ziegler and chromiumcatalysts
and henceis capableof makinga broadspectrumof Finally
products. it is pointedout that BP
following the stepsof Union Carbide,adoptedthe "high productivity technology"which is
analogous of the "condensedmode operation" of the Unipol process,utilizing a partially
liquefied recyclestreamin the fluidized bed reactor.The liquid fraction of the recyclestream
is separatedfrom the gas fraction and is pumpedinto the fluidized bed through specially
designednozzlesand it is vaporizedattaining additionalheat removalbecauseof the latent
heatof vaporizationandhenceincreaseof polymerproductionrate.
Table 2.4 (Xie et al., 1994) summarizestypical operating conditions and production
capabilitiesof the gas-phase discussedabove.
processes
Table 2.4: Typical operating conditions & production capabilities of gas-phaseprocesses.

BASF AMOCO Union Carbide BP Chemicals
Reactor type stirred reactors and
stirred bed horizontal stirred bed fluidize bed
fluidize bed
Catalyst supported CrC03 supported Ti and supported Ti, V supported Ti and
catalyst CrC03 catalyst and CrC03 catalyst CrC03 catalyst
Catalyst size, 30-250 -5 0 for prepolymn
PM
Pressure, atm 2040 20-30 15-25
-35
Temperature*C 100-110 70-110 75-110 70-115
Propyleneor I-buteneor I -buteneor
Comonomer I -butene
I -butene I-hexene I-hexene
112and temperature 112 112
MW control H2
MWD, M, /M, narrow to broad 5-17 4-30 6-20

Density g/cm 3 0.95-0.98 0.91-0.97 0.91-0.96
Polymer particle 500-1300 300-1200
size, pm
Trieschmarm et al. Bailly & Speekman
References Shepard et al. (1976); Rasmussen(1972);
(1977); Choi & 0 986); Speekman
Jezl & Peters (I 978ab) Nicoletti et al. (1988)
Ray(1985a) (1991)-,
29
2.5 Catalytic Systems
Most of the major improvements currently obtained in the production and utilization of
polyolefinic materials as commercial products are strongly related to the technological

development of the catalytic systems. It is apparent from the previous section that different
polymerization processesuse different types of catalyst and it was a common practice for
companies developed polymerization processes to exhibit analogous activities towards the
catalyst technology for the construction of tailor-made catalyst for their process indicating the
dependenceof the polymerization process from the catalyst and vice versa.
2.5.1 Catalyst for Gas-Phase Polymerization

The complexity and depth of the researchfield over the catalyst technology from one point of
view and the extensive commercial applications in this area from the other, combined with
the need for highly active and selective catalysts, concentrate major research activities over
the area of catalysis in ethylene polymerization with both industrial and academic
laboratories participation. The degree of complexity additionally enlarges in the case of gas-
phase polymer processes,where polymerization takes place under heterogeneouscatalysis.

There are two major transition metal catalyst families broadly used in commercial
polyethylene production: titanium/vanadium based catalysts, known as Ziegler-Natta
catalysts, and chromium oxide based catalysts, known as Phillips catalysts. These catalysts
are complex mixtures of TiC14 and Cr03 respectively with an organo-metallic compound
(usually aluminum alkyl, AlEt3) and various other additives used to enhance the catalyst
activity or to improve the catalyst capability in controlling polymer properties (Taylor et al.,
1983; Karol, 1984; Choi and Ray, 1985a,c; Zacca, 1995). Kinetic studies of ethylene
polymerization were carried out firstly by Edgecombe (1963) and Lipman and Norrish (1963)
using conventional Ziegler-Natta catalysts, while Wisseroth (1969) reported on gas-phase

polymerization of ethylene using Phillips catalysts. The technology behind these catalysts is
very advanced and several evolutionary generations of these catalyst families emerged in the
last five decadesas a result of these technological developments. From one generation to the
other the effectiveness of these catalysts was tremendously increased by chemical treatment
and by deposition of the active metal modifier onto appropriate support materials. Porous
silica and magnesium halide are common supports. The significant difference between Ti-
and Cr- based catalysts is that the molecular weight distribution (MWD) of polymers made
30
using Ti catalysts is narrower than that using Cr-based catalysts. However, broader molecular
weight distribution is observed in olefin copolymerization with both Ziegler-Natta and
Phillips catalysts, compared with the MWD of polyolefins when the olefin copolymerization
is carried out using a new generation of catalysts, the metallocene-basedcatalysts known as
homogenous Ziegler-Natta catalysts (Huang and Rempel, 1995; Hamielec and Soares, 1996;
Kaminsky, 1996). This phenomenon despite the extensive research activities remains poorly
understood and a matter of controversy between two main theories attempted to explain it.
The first theory claimed that the former two catalysts and particularly the Ziegler-Natta
catalysts comprise multiple active sites of different activities (Floyd et al., 1988), while the
second theory attributes this phenomenon to the existence of concentration gradients within
polymer particles causedby diffusion effects limiting the transport of reactants(Nagel et al.,
1980).
According to the first point of view, different catalyst sites, each with its own characteristic
kinetic rate constants for propagation, copolymerization and transfer reactions account for
broad molecular weight distribution and copolymer composition inhomogeneity. As for the
second hypothesis two consequences should occur: (i) the efficiency of the catalyst will drop
as catalyst particles become more and more encapsulated (Carvalho de et al., 1989), and (ii)
catalyst sites at different radial position in a growing polymer particle are subject to different
reactant concentrations which account for broad molecular weight and composition
distribution (Galvan, 1986).
2.5.2 Polymer Particle Morphology Development

in the heterogeneous catalytic gas-phase polymerization systems it is apparent that
complicated physicochernical phenomena are taking place during the transition from gaseous
monomer to solid polymer particles formed upon a solid catalytic substrate. A number of
microscopic phenomena occur consisting the polymer particle growing mechanism. Various
models have been developed for a reasonable representation of the growth mechanism
targeting to a comprehensive understanding of the relevance of catalyst morphology and the
polymer particle morphology for an improved catalyst design. Yiagopoulos (2001) presented
an analytic description of these mechanistic models of polymer particle development, but it is
out of the scope of this study to elaborate on all these mechanisms. However, the basic
principles of the Multigrain Model (MGM) of particle growth as the most popular and
extensively studied model (Floyd et al., 1986; Ferrero and Chiovetta, 1987a,b; Hutchinson et
31
Chapter 2 Polyolefin Technology Developments: Polym! rization Processes & Catalysts
al., 1992; Debling and Ray, 1995) are briefly presented here to demonstrate the catalyst-
polymer particle interaction.
According to this model, a typical solid catalyst used for olefin polymerization consists of
porous particles of mean diameter 5-100 gm ("macroparticles'). Each catalyst macroparticle

is an agglomeration of smaller fragments ("microparticles" or "primary particles') of
dimension 0.001-0.5 jim. These fragments are held together with Van der Waals forces and
there are interstices or pores between them providing a large surface area of the
macroparticle. From the formulation of the catalyst macroparticle to the formulation of the
final polymer particle there are four stagesinterposing:
Monomer diffuses through the interstices onto the surface of catalyst fragments where
the active sites are located and hence the polymerization reaction occurs.
During the reaction monomer is converted to polymer and the large pores in the
catalyst macroparticles quickly fill up with solid polymer and due to hydraulic
pressure and stresses between the catalyst fragments, the catalyst macroparticle
undergoes breakup. Despite the spreading apart of the catalyst fragments and the
increase of the distance between them with the increase of polymer yield, polymer
cements the catalyst primary particles that remain loosely associated to one another
within the growing macroparticle.
The polymer around the catalyst fragments is swollen with monomers (either ethylene
or a-olefin). Since olefin polymerization is highly exothermic, the temperature may

exceedthe softening or melting point of the resin (Karol et al., 1987). Due to the rapid
growth of catalyst primary particles, the polymer chains between them fuse together
to form polymer primary particle aggregatesof diameters in the range of 0.5-1.0 pm.
The final polymer particles are composed of aggregatesof primary polymer particles
with averagediameter in the range of 200-1000 gm. (Galli et al., 1981,1984; Bohm et
al., 1988; Kakugo, 1988).
A schematic representation of transport phenomena within the polymer particle is shown in

Figure 2.10 (Hutchinson et al., 1992) while the four stage mechanism of the polymer particle
formulation described above is expressedschematically in Figure 2.11 (Xie et al., 1994).
32
Polymer Macroparticle
Dt
IMI
tr, t) I
R, (t
Growing
Microparticles
External Film Catalyst Fragment (rcrys)

&T, AM
Bulk Fluid t), CMISQ, 0
TS
(Nljb' Tb
R, (t)
Imph
Polymer
Microparticle
Figure 2.10: The multigrain model of particle growth.
0 10-30 micron in diameter

CATALYST
(30-100 micron for silica supported catalyst)
CIH4 Composed of crystal domains, 20-200 A* in diameter
LOW Formation of polymer primary particles,

POLYMER -0.2 micron in diameter
YIELD Separation of catalyst domain
C2H4
MEDIATE Growth of primary particles

POLYMER Ole
Formation of primary particle ag6ncgations,
YIELD
-1 micron in diameter
C2H4
HIGH Final polymcr partic1c,

POLYMER 200-1000 micron indiamctcr
YIELD Ti or Cr Icss than 10 ppm
Figure 2.11: Schematic polyethylene morphology development during gas-phase
polymerization.
33
2.6 Summary
This chapter provides a quick review over various polyolefin processesfocusing in

particularly on the gas-phaseprocesses.The operating characteristicsand the production
capabilities(in terms of the product molecularproperties)of theseprocesseswere presented
to let the readerunderstandhow the problemsthat will be studiedin the following chapters
are relatedto all of theseprocessesand to link the economicnatureof theseproblemswith
engineering-likeaspectsof the processes.Finally a brief descriptionof the polymer particle
developmentover catalytic systemswas also presentedto provide theoreticalbackground
information necessaryfor the mathematicalmodel developmentof a polymerizationreactor
that follows in the next chapter.
34
Chapter 2 Polyolefln Technology Developments: Polymerization Processes& Catalysts
2.7 Literature
Bailly, J.C.; Speckman, J.G. (1986) Process for the polymerization of ethylene or the
copolymerizationof ethylene and a-olefins in a fluidized bed in the presenceof a

chromiumbasedcatalyst.Eur. PatentAppL EPI 75532A 1, March 26.
Batleman, H. L (1975) Gas-phasepolymerization-a new route to IjDPE. Plast. Eng., April, p.
73.
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Catalysts for Olefin Polymerization. Kaminsky, W., Sinn, H., Eds.; Springer-Verlag:
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Brockmeier, N. F. (1987) Encyclopaedia of Polymer Science and Engineering, Kroschwitz
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Carvalho de, A. B.; Gloor, P.E.; Hamielec, A. E. (1989) A kinetic mathematical model for
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Choi, KY.; Ray, W. H. (1985a) Recent developments in transition metal catalysed olefin
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Choi, KY.; Ray, W. H. (1985b) Recent developments in transition metal catalysed olerin
polymerization-A survey. 11. Propylene polymerization. Jms-Rev. MacromoL Chem.

Phys., C25, p. 57.
Choi, K. Y.; Ray, W. H. (1985c) The dynamic behaviour of fluidized bed reactors for solid
catalysed gas phase olefin polymerization. Chem. Eng Sci., 40, p. 226 1.
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35
Chapter 2 Polyolefin Technology Developments: Polymerization Processes& Catalysts,
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organotitaniurn catalytic surface. Can. J. Chem.,41, p. 1265.
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polymerization: Part 1. The effects of grain size and structure. Polym. Eng. Sci., 27, p.
1436.
Ferrero, M. A.; Chiovetta, M. G. (1987b) Catalyst fragmentation during propylene
polymerization: Part 11.Microparticle diffusion reaction effects. Polym. Eng. Sci., 27, p.
1448.
Floyd, S.; Choi, KY.; Taylor, T. W.; Ray, W. 11. (1986) Polymerization of olefins through
heterogeneouscatalysis: 111.Polymer particle modelling with an analysis of intraparticle
heat and mass transfer effects. J AppL Polym. Sci., 32, p. 2935.
Floyd, S.; Heiskanen, T.; Ray, W. H. (1988) Solid catalyzed olefin polymerization. Chem.
Eng. Prog., 84, p. 56.
Galli, P.; Barbe, P.C.; Noristi, L. (1984) High yield catalysts in olefin polymerization.
Angew. Makromol. Chem., 120, p. 73.
Galli, P.; Luciani, L.; Cechin, G. (1981) Advances in the polymerization of polyolefins with
coordination catalysts.Angew. Makromol. Chem., 94, p. 63.
Galvan, R. (1986) Modelling of heterogeneousZiegler-Natta copolymerization of a-olefins.

PhD Thesis,University of Minnesota.
Goins, R.R. (1960) Olefin polymerization. U.S. Patent 2936303, May 10.
Hamielec, A. E.; Soares, J.B. P. (1996) Polymerization reaction engineering-metallocene
catalysts. Prog. Polym. ScL, 2 1, p. 65 1.
Havas, L.; Lalanne-Magne, C. (1992) Gas phase polymerization process. Eur. Patent Appl.
EP4 75603 A 1, March 18.
Huang, J.; Rempel, G.L. (1995) Ziegler-Natta catalysts for olefin polymerization:
Mechanistic insights from metallocene systems.Prog. Polym. Sci., 20, p. 459.
36
Hutchinson, R.A.; Chen, C.M.; Ray, W. H. (1992) Polymerization of olefins through

heterogeneouscatalysis X: Modelling of particle growth and morphology. J. AppL Polym.
Sci., 44, p. 1389.
Imhausen, H.C.ICH.; Hippenstiel-Im-Hausen, J.; Newman, P.; Berndt, R.; Schoffel, F.; Zink,
J. (1981) A comparison of a modem high pressure tubular low-density polyethylene
process with gas phase linear low density polyethylene technology. J AppL Polym. Sci.
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Jezl, J.L.; Peters, E.F. (1978a) Horizontal reactor for the gas phase polymerization of
monomers. US. Patent 4101289, July 18.
Jezl, J.L.; Peters, E.F. (1978b) Horizontal reactor for the gas phase polymerization of
monomers. U.S. Patent 4129701, December 12.
Kakugo, M.; Sadatoshi, H.; Yokoyama, M.; Kojima, K. (1988) Transition Metals and
Organometallics as Catalystsfor Olefin Polymerization. Kaminsky, W., Sinn, H., Eds.;
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37
Chapter 2 Polyolerin Technology Developments: Polymerization Processes & Catalysts
Nicoletti, J.W.; Cann, K. J.; Karol, F.J. (1988) Process for the production of polyethylene
having an intermediate molecular weight distribution. Eur. Patent AppL EP286001 Al,
Oct 12.
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3971768, July 27.
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1377.
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(1967) Process and apparatus for the polymerization of monoolefins. U.S. Patent
3300457, Jan 24.
Shepard J.W.; Jezl, J.L.; Peters, E.F.; Hall, R.D. (1976) Divided horizontal reactor for the
vapor phase polymerization of monomers at different hydrogen levels. U.S. Patent

3957448, May 18.
Speekman,J.G. (1991) Processfor the gas phase(co)polymerization of ethylene. Eur. Patent

Appl, EP435515 A], July 3.
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Phase Propylene Polymerization. MMI Symp. Ser., Harwood Academic, New York Ed.,
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41.
Xie, T.; McAuley, K. B.; Hsu, J.C.C.H.; Bacon, D. W. (1994) Gas phase ethylene
polymerization: Production processes, polymer properties, and reactor modelling. Ind.
Eng. Chem. Res., 33, p. 449.
38
Yiagopoulos, A. (2001) Micro- meso- and macroscale dynamic simulation of polyolefin

fluidized bed reactors.PhD Thesis,Aristotle University of Thessaloniki (in Greek).
Zacca, JJ (1995) Distributed parameter modelling of the polymerization of olefins in
chemical reactors. PhD Thesis,University of Wisconsin-Madison.
39
CHAPTER3
Catalytic Gas-Phase Olefin Polymerization

Fluidized Bed Reactor Model
3.1 Introduction
The modelling of gas-phasepolyethyleneproductionprocessesin fluidized-bedreactorsis a

composite task with widely recognized importance in both the industrial and academic
research community, which has received attention
considerable in recent years.The major
target of these models is to provide a means for a comprehensiveunderstandingand
interpretation of complex and interacted phenomenaoccurring at different levels of
polymerizationsystems,and subsequentlyto simulate,predict and optimisethe operationof
the polymerization processes.Prerequisitefor a model to successfullycorrespondto the
above target is to adequately describe the polymerization reactor systems in terms of
different modelling perspectivelevels.Ray (1991) was the first to define a hierarchyfor the
modelling levels of polymerizationsystemswhile various others investigators(Xie et al.,
1994;Zacca, 1995;Hatzantonis,1999)adoptedand evolved this hierarchyschemein their
effort to develop a well-organised model. According to this hierarchical structure,
polymerization phenomena have beenclassifiedinto four modelling levels (seeFigure 3.1)
basedon their relativescaleand time dimension(microscale,mesoscale,macro-mixingscale
andmacroscale).
The first modellinglevel coversthe fast microscalephenomenarelatedto the polymerization

kinetic mechanismover variouscatalystsites. At this level a thoroughmodel accountsfor
different reactionsteps,the polymerizationrate development,polymer molecularproperties
and their distributionsincluding chain branchingand copolymercompositiondistribution,as
well as the impact of various reactantson theseproperties.Catalyst site multiplicity and
catalyst site deactivation adds to model's complexity.
40
Chapter 3 Catalytic Gas-PhaseOlefin Polymerization Fluidized Bed Reactor Model
Although an accurate description of the microscale phenomena is the base and precursor for
the efficient development of the other modelling levels, the boundaries between these levels
are not well distinguishable in the sense that they are interacted and there is a two-way
transfer of information between them. The polymer particle growth in heterogeneous
systems, such as gas-phase processes, is the modelling field of the mesoscale level. The
interaction of this level with the previous one is apparent.The polymer production rate in the
polymer chains (microscale level) clearly affects the particle morphology development from
one side, and from the other side the component solubilities in the polymer particle and the
heat and mass transfer phenomena(mesoscalelevel); defining the temperature and reactants'
concentrations near the catalyst active centre, clearly influence the polymerization rate.
The interacted relationship between the modelling levels retains in the next level
(macromixingscale)as well. At this level, the modellingstudiesareextendedfrom the single
particle to the behaviourof the entire polymer particle population in the continuous-flow
reactorin termsof the particlesizedistribution.The impactof the residencetime distribution
and the mixing pattern in the reactor on this macromixing scale phenomenais evident.
However,both the residencetime distribution and the mixing profile of different phasesin
the reactor,togetherwith the overall material and energy balances,reactor dynamicsand
control are on
elaborated the last modelling level.
macroscale
Mesoscale
Particlegrowth
I's
hficroscale
Polymerizadonmechan6im
k
P., Nii ', ) p.".IJ
',
IV
-ý, V,
., 41- -'.
.........................
Macromixing Scale
Afacroscale Population balances
Reactormodels
Figure 3.1: Modelling levels of polymerization reactor systems.
41
Chapter 3 Catalytic Gas-PhaseOlerin Polymerization Fluidized Bed Reactor Model
An integrated dynamic model of a polymerization reactor should efficiently deal with all the
above modelling fields. To the knowledge of the author however, no publication has
appeared combining research activities in all these modelling levels. It is common practice
among several investigators who try to selectively study different topics of the multilevel
behaviour of polymerization systems based on mathematical models, to apply some
simplification assumptions in order to ignore some modelling levels (despite their

interdependence)without affecting model's autonomy. In this thesis a model-based study of
the behaviour of a catalytic gas-phase ethylene-I -butene copolymerization fluidized bed
reactor is attempted with great emphasis being given on the macroscale level. However, a
theoretical substrate for the microscale level phenomena,necessaryfor an accurate model, is
also built together with combined simplification assumptions and thermodynamic equations,
accounting for phaseequilibrium calculations and component solubilities, approximating the
mesoscale modelling level, ignoring though phenomena related to the macroscale mixing
level.
3.2 Microscale Level
The accuratemodeling of the microscalephenomenain catalytic polymerizationreaction

systemsprovides the basefor the development
of modelscapable of efficiently describing
meso-and macroscale phenomena. Therefore,specialeffort was given over many yearsby
variousinvestigatorson defining the key elementaryreactionsconstitutinga comprehensive

polymerization kinetic mechanism based on information about polymerization rate
development, polymer molecular properties and their distributions and active site
Apart
concentrations. from the group of reactionsinvolved in the polymerizationmechanism
the disagreementand controversy matter between the researcherswas the catalyst site
multiplicity (Floyd et al., 1988) and the reactantconcentrationgradientswithin polymer
particles,caused by diffusion limitations (Nagelet al., 1980),as a meansfor predictionof the
broadmolecularweight distribution(MWD) of polymerchains.
In the late seventy'sBohm (1978)proposeda kinetic mechanismfor ethylenepolymerization

involving perhapsthe most comprehensiveelementarychemical reactions.Various others
investigatorshave subsequentlyadopted Bohm's mechanismand they extendedand/or
modified it to accountfor ethylenecopolymerizationwith a-olefinsas well, for a thorough
of
representation polymer molecular properties.Authors of recent literature reviews on
42
modeling studies (Boehm et al., 1986; Galvan and Tirrell, 1986; Carvalho de et al., 1989)
positively claimed that broad molecular weight distributions produced by heterogeneous
Ziegler-Natta catalysts are most likely the result of multiple active sites. The kinetic
mechanism employed by the above authors that forced them to come up with this conclusion
involves activation, initiation, propagation, chain transfer and deactivation reactions in the
copolymerization scheme. Carvalho de et al. (1989) based on this kinetic scheme developed
a model capable of predicting polymerization rate, copolymer composition and chain length
distribution applying the stationary state hypothesis (SSH) to make simpler the derivation of
the mass balances of the various length polymer chains for the calculation of chain length
distribution. McAuley et al. (1990) using the same kinetic mechanism they developed a
dynamic multiple active site model for the ethylene copolymerization with a-olefins in a gas-
phase FBR over Ziegler-Natta titanium based catalyst. They introduced the pseudokinetic
rate constants for uniform kinetic rate expressions while they applied the SSH in order to
reduce the differential equation system for the calculation of polymer molecular properties
and their distributions as well as the density and melt index, defining heuristic correlations
with molecular weight and copolymer composition. A similar model limited though to the
microscale level without accounting for the reactor level, was developed by Lorenzini et al.
(1991) to fit molecular weight averages and distribution data over a range of experimental
condition where experimental data were available, by tuning the kinetic parameters.In spite
of the consideration of catalyst site multiplicity by the model, the effects of monomer type on
the reactivity of active sites was neglected in the parameter estimation. Significant was the
contribution of Hutchinson et al. (1992) toward a deeper understanding of the microscale
phenomena in heterogeneousolefin copolymerization, through the study of particle growth.
A detailed kinetic scheme consisting of groups of activation, deactivation, transformation,
chain transfer and propagation reactions over a multisite catalyst was employed in order to
portray the polymer particle development. Diffusion and sorption phenomena in the polymer
particle were considered accounting for the reactant concentrations in the particle for the
prediction of particle morphology and average polymer molecular properties. Finally, Xie et
al. (1995) studied systematically the molecular weight developments of ethylene and a-olefin
copolymerization using a very general kinetic scheme over a multisite heterogeneous
transition metal catalyst in a gas-phaseprocess.Extensive analysis of the influence on MWD
of a number of factors such as the type of active centres, the concentration level of each type
of active centers and the elementary chemical reaction, was presented.The SSH was applied
to simplify the mathematical calculations, while some calculations on the mesoscale
43
modelling level were also incorporated in the model, for the prediction of the reactant
concentrations in the polymer particles neglecting though the effect of polymer crystallinity.
A complete kinetic representation of heterogeneous catalysed olcfin polymerization for a
multiple monomer, multiple site catalytic system is presented next. Gcneraliscd kinetic rate
expressions and the polymer properties expressions are derived based on this kinetic scheme
composing the microscale model, which interacts with the respective macroscale model
developed in the following section.
3.2.1 Polymerization Kinetic Mechanism

There is a set of key elementary reactions, which include formation of active centres,
insertion of monomer into the growing polymer chains, chain transfer reactions and catalyst
deactivation, that have been accepted by the majority of the researchers.Since commercial
production of LLDPE and HDPE consists of a copolymerization process, it is obvious that a

copolymerization kinetic mechanism is required in order to effectively describe and
understand the kinetic behaviour and polymer properties. This remark led to the postulation
of a kinetic mechanism composed of several reaction steps. A complete representationof the
kinetic schemeof multiple monomer heterogeneouscatalyzed olefin copolymerization over a
multiple active site catalyst based on the ideas developed by Hutchinson et al. (1992), Chen
(1993). Zacca (1995 ), and Shaffer and Ray (1997) is presentedbelow. A brief description of
each group of reactions is given here.
Activation of Catalyst Potential Sites Activation is the reaction through which a potential
catalyst site (SI) is converted into a reactive vacant site mainly with the alkylation reaction
P
of the catalyst active metal with a cocatalyst, usually aluminum alkyl. This reaction is very
fast and the rate of catalyst activation depends on the ratio AIM in the catalytic system.
Recent studies showed that the effect of monomer is very important for the activation of the
catalytic sites, while according to remarks of Hutchinson et al., (1992) and Chen (1993) the
kinetic scheme additionally includes activation reactions with hydrogen and electron donor,
as well as spontaneousactivation (Yiagopoulos, 2001).
Chain Initiation and Propagation. Chain initiation is the first reaction of a vacant catalyst
site (POI)with a monomermolecule(M) producingan occupiedreactive site of length I

(Pill ). From this time on the propagationreactionstartsthroughwhich the growth of polymer
44
chains takes place. Each new monomer molecule is interposed first between the bond of
carbon and catalyst metal and then is added in the polymer chain (see Figure 3.2)
Deactivation of Catalyst Sites.Deactivationreactionshavebeenadoptedmainly to describe

the loss of catalystactivity. Reductionof catalyst activity results from severalphenomena
such as: (i) limiting effects on the transportof reactantsto catalystactive sites,(ii) thermal
deactivationof catalyst sites due to extremely high temperature(heterogeneous catalytic
systems),(iii) chemicalabsorptionof impuritiesand other species.The latter phenomenonis
the most dominant. It is pointed out that the mechanismpresentedhere assumesvarious
types of deactivation (spontaneous,by impurities, by cocatalyst, by electron donor, by
hydrogenandmonomer)of both occupiedandvacantactivesites.
Chain Transfer Reactions. Chain transfer reactions terminate a "live" polymer chain (P.k.,)
producing "dead" polymer (D, ', ). However, polymerization carries on since a vacant active
is
site produced in parallel with the "dead" polymer chain. Generally a chain transfer agent
remains attached to the active site cutting off the live polymer chain. In Ziegler-Natta olefin
polymerization the main chain transfer agent is hydrogen while chain transfer to monomer
has been observed as well (Carvalho de et al., 1989). The present kinetic schemeadditionally
considers spontaneous chain transfer, chain transfer to cocatalyst and electron donor
reactions (Yiagopoulos, 2001).
ýS
CH3CH'ýa2 CHH CHCH3

2,,,.. &P2
'j 5+
Al "-,
-Tlý, , --
R .,
R
TI
/
AI
Figure 3.2: Schematic representationof initiation-propagation chemical reaction.
45
Chapter 3 Catal) tic Gas-I'llast, 010-111Pol) 111crizatioll 1,Illidized Bcd Reactor Model
CataIN'st Site Traitisl'ormation. Considering that inl'ormation about polymerization rate and
11101CCUL11- IS tile (Undcline [or the formulation

1)1-01)Cl't)CS of' the polymerization median i sill,
site transformation reactions have been Introduced in the general kinetic inechan Isill by sonle
rcscýirclicrs (Clicn, 1993-, Shaffer and Ray, 1997). In this reaction step, which applies only to
Illultisite catakst.. ", a type ()I' [Cti\'C Site is COII\Cl*tC(I10 ifflOtlIff One Mid in CLIttin-
I-CSLI11
01T of' tile polymer chain [1-0111

the active sitc ploducill", Alcad" polymer chain (death
or It Illay he carried out with the live polymer chain preserved (no-death
11'(111.401-111(111,011),
11"allslormalion). Site t ranst,orniat i oils hy hydrolgen, cocatalyst, electron donor, poison,
monomer and by spontaneous mcclianism are considered in tile present kinetic scheme.
Aftcr the pl-ccedifig CIC. thill illl Of UIC lCtiVC Celltl-CSI)CI-I'01-111

Scl-IPtlOll, 11,SLI111illl-l the same
hut the
reaction
Illechall rsills \Vltll different ivactioll rates, set ()I the clellicill. 11-Nreactloll
ýI(loj)led fol' O SILILlICS

IIIOCICIIIII, III
IS SLIIIIIIIiII-I/,CCl I ZINC3.1
-
Table 3.1: (; cncjd kmclic mcch, 1111sill

()I catalvic(l o1clill
REACTION DESCRIPTION
Adhalioll
k
acllVMl()ll
spolliallemis
sp
1) C(wa IaI ys I
JA I-'
Sk+ (ZiI Llill MUM al kyl ) (A)
activa(ioll hy electron dollor (F)

Sil
activation by Ilycli-ogell (112)
acmatioll
Vo
I nifial ion- Propagat ioil
(I Mt Kit[Oll )
fil sl Inom )II)CI Ullit
+ pk
Ij
k,
Im, ); add II ii ma I till it-, ( Propagation
C7
Pk + pk
'i'J''
Deactivation
k
Isp 1,1)()111MICý RIS (ICýIC IIý ýtIIýM
Cd ,
IIt, at It )II h) C()k:

il I it I Y.
St it ILI
I I) III it III ;II ký I (A)
C",
+(1)ý') LICiIC
(I)
Cd + deacmation by inipwitics oi porsoil (Z)
46
Chapter Catalytic (Mefin Polymerization Flifidized Bed Reactor Modul
.;
++ deactivation by clection (hmoi (F.)
&ýW II VA I It) Hb llý'LJI-OgC IIý, )

+ I I(
k,L%" (DK) deactivation by monomer (M, )

13k Ck +
ChainTransfer
k
Isp, kk spolliallcous chaill 11-all"Icl.
I)k Po + Di,
k
k+ lA, k+k tlMllICI VSI ALIMIJIL1111ýIlk)'l (A)
to CoCMý11.
k
11:1 diain tiajistci to clection donor (E)
++ pk
kk111.1 k Chain 11*all'slcl* lo IIY(11.o"cll

tý
(I l')
+ PO + Dn -
k
k=L--> clizim (ransfer to niononler (M, )
pI kj +Im, I)k + I)k
1.1 11
.,
,h-allsforillation ýsilh termination
P, ý + S Pt) II I'l i IC() u.."
[-)yCOC,
'Itlly. Sl ýIlkllllillfflll alkyl (A)
+
l3k (Di'j hV 1111pill

[ties or poisoll (Z)
+IZI +
(1)
+ hN,election doilt)l (F)
1kI
1) hydroucil (I I')
111(monler(M, )
,rransforma(ion without termination
kIkII
'I"l, SI)MILHICOLIS
kI
1)),cocaialyst altuninum alkyl (A)
+
k,k,I" h) illll)Lll'itiC', M- 1)01,011 (Z)

+
pi 1)),clectron donor ( F)
ki
III I)III'l hy hydrogen (If, )
I)Ik1.1,
,
k kl
Im I)II1.1 I) tft)tl(H1Cl ( ri,
pi,
ii Iý I
47
3.2.2 Kinetic Rate Expressions

The polymerization rate functions can be derived according to the kinetic mechanism
reported in Table 3.1, accounting for all the reaction groups, however, it is worthwhile to
explain before some of the terms appeared in this mechanism. Since it is a multicomponent
polymerization mechanism, and considering that the polymer molecular properties are highly
influenced by the fraction of comonomer in the polymer chains, the "live" polymer chains
are differentiated with respect to the ending monomer unit, accounting for the amount of
comonomer introduced in the polymer chains with the progress of polymerization. The terms
pk and D. k stand for the concentrations of "live" polymer chains of length W ending in
n,
monomer unit of type I' and of "dead" polymer chains of length W, respectively. Both these
polymer chains are connected to a catalyst active site of type W. Pk denotes the
0
concentration of vacant active sites of type V derived from the activation reaction of
catalyst, the chain transfer and transformation reactions. The symbol P.k is used for the total
concentration of active centres either vacant active sites or "live" polymer chains whatever is
their chain length or their ending monomer unit. Finally, Sk and Ck are the concentrations
pd
of potential catalyst sites and deactivated polymer chains formed at a catalyst site of type V.
It is pointed out that all the other symbols represent the actual-local concentrations of the
reactant speciesat the area of the active catalytic sites.
Accordingly, adopting the analysis of Hutchinson et al., (1992) and Chen,(1993) for the set
of multiple reactions for each polymerization step, the grouping rate functions for catalyst
site activation, deactivation, chain transfer reactions and transformation of active sites and
"live" chains as well are defined, for a uniform and structural development of the net reaction
rates of the various polymerization species.
Activation:
Nin
[A]+ [MI 1
P. k kkkkk+k. kaH[H21+kuE[E3+Zk (3.1)
=kasp A am,
1-1
Deactivation:
Nm
[H2 ]+ k kE [E]+kkdZ [Z]+Ekkm [Mi]
Ok kk kk
dSp + dA
[A]+ kk (3.2)
d = dH d. d
i=l
48
Chain Transfer-
Nm
pk [Al+kk [E]+kk [H ]+ k k Imi I
ti =kktspi +kktAl tEi tHj 2 Y,
j=l
tmij
(3.3)
Transformation with tennination:

Nm
ßkl=kkl [AI+k kl [E]+k ki [Z]+ kkl [H2 l+ Zk ki X1
+kkl (3.4)
st sLsp stA stE stz SIH stmi
i=I
while the total transformation rate, with termination, of active centres of type T to active
centres of type T is given by:
N, N,
Eplkpi Epklpk
Gk= st - st
(3.5)
I=Isk I=Isk
Transfonnation without tennination:

Nm
[A]+ [EI+ kkitz [Z]+ kkl [H2 IMJ1
ßkiti = kk,
ns nstspi
+ kkItA
ns i
kkl
nstEi ns i nstHi +Z kkns1tm (3.6)
and similarly the total transformationrate, without termination,of active centresof type T
to activecentresof type T with endingmonomerunit of type T is given by:
NN
2P
k=k P."i Pkl P,ýi
(3.7)
nist -2 nsti
nsti
1=1*k 1=1;
tk
Based on the above expressions and the generalized kinetic scheme of Table 3.1 the
following functions for the formation rates of "live" and "dead" copolymer chains and
potential and vacant active centres are derived.
Net fonnation rate of "live" copolymer chains of length 'it' with tenninal monomer unit of
type Tformed at the T active site:
N
k k'pnk
ýk kkk jpj
R =_pkpak
d -pkpik. n1
+rnk +Ij0 8(n)ý [pk]
+ 8(n)ko, IM, I
p.,, sti
tm,n-I
.12kC,
I-Isk 5 J-1
N
(3.8)
ý ýMj]_ýýk
12
11
+ - 8(n)
k pk_ pki[Mj]l
Pý n I,j po n,
j-1 J-1
for n=I... -
a
49
I for n =1
where8(n) is the Kronecker'sdeltafunction, 8(n)=
0 forn: A I
Netfonnation rate of "dead" copolymerchainsof length V at the T activesite:
ipst Nm Nm
Rk" kl + jpk + pk)E Pnýi (3.9)
D ti d
1=1*k i=l
Reaction rate ofpotential catalyst sites of type T
Rkkk P. ISP1 (3.10)

s,,
Reaction rate of vacant catalyst sites of type T

Nm NN
Rkp, = fkok, ý. kl k
[Pok][MI] [pol [p.
o -Pdk[Pokl-l: 1-1*k
I-Isk
Nm Nm
)ý
p. k li I.,
Pn
-R' SP+F, +k4jA]+kV[lj +Ylýýk, [H 2
i-I n-I 1-1 1-1 jkj, n-I
According to the preceding kinetic rate expressions, for the description of the polymer
molecular weight development in a catalytic reactor the application of conservation

principles for all the polymer speciesof any length from I to n is necessary.Hence, since it is
impractical to formulate an infinite system of differential equations and the solution of such a
system is extremely computationally expensive, the statistical method of moments is used to

reduce the system of macromolecular differential balance equations into a lower-order
system, which can now easily be solved. Therefore, a statistical description of molecular
properties of polymer (such as M,,, Mj is achieved in terms of the first three leading
moments (zero, first and second order) of the total number chain length distributions
(TNCLDs) of "live" and "dead" copolymer chains for each catalyst site of type V (Achilias
and Kiparissides, 1992). The first three moments, of zero, first and second order, are defined
below:
NN
lk 22 2EntP, ý,
t = A = i ,2 =0,1,2 (3.12)
i-1 i=I n-1
En'Dk,
n 1=0,1,2 (3.13)
n=2
50
Additionally, a total-"bulk" moment that includes the moments of "live" and "dead"
copolymerchainsis alsodefined:
Nm
4k =Z%k +gk,
ti t1 =0,1,2
Furthermore, due to the complexity of the kinetic expressions as a result of the
multicomponent polymerization, "pseudokinetic" rate constants are introduced (Carvalho de

et al., 1989; McAuley et al., 1990; Hutchinson et al., 1992; Hatzantonis et al., 1999;
Yiannoulakis et al., 2001) substituting the different monomers in the polymerization
reactions by a "pseudocomponent" for the sake of a compact representation of the kinetic
rate expressions.The derivation of the "pseudokinetic"rate constantsand the modified

grouping rate functions are analytically stated in Appendix A. Consequently,the rate
functionsfor the momentsof theTNCLDs of "live" and"dead" copolymerchainsderivedby
multiplying each term of Eqns (3.8) and (3.9) by n' and summing up the resulting
expressionsover the total in
variation of n are presented a concrete form below:
"Live " polymer nionzents:
N
ki
PStT
JPnsIT
kl
ktT
Ik ko 'I
Rkk Pd Xk +
-pk
1, 1-1*k tT I-Isk
02 1-1*k
(3.15)
k [MT1 k [pk] [MT1
+ ktmrr + kor o
ýp ) N
ktTlk I
kk Pd kl
PStT kl Xk + %,,
-pk tT - nst., 12
I I*k W*k 1-1*k (3.16)
k+k [MTI+ k [pok] [MT1
kpIT )Xk
+ (ktmTT 0
kOT
jP N
ýnStT
lk X12J+
Rkk kl
PstT kl Xk [MT1
Pd -pk tT Xk +
22 ktmTT 0
13 1-1*k 1-1*k
nstT
I-Isk
(3.17)
k (Xk + Xk [MT1 k [pk] LMTI
+ kPrr + kOT
01) 0
51
"Dead" polymer moments:
N,
Rk pkl
StT +pk d)0 Xk
tT +pk
A0Z I=Isk
N,
Rk =( pkl
StT +pktT +pkd1 Xk (3.19)
1=1*k
RkA2 pkl
StT +pktT +pkd2
Xk (3.20)
=I*k
Using the definition terms of the "live" polymer moments, the monomer incorporation into
the polymer chains formed at active site of type T is expressedas:

(kk k1l )Xk ][Mi
Rk [kk [pk + (3.21)
M. oi 0 +kp0
tm.,,
.=
Obviously, the total incorporation rate of monomer T into the polymer chains for all the
active site N, and the overall polymer production rate will be given by:
N, )Xk )[Mi
k, [pok +kk(k
Rm, =Z(ko +k pTi 0 (3.22)
k-I
tm,,
(kk klT )Xk IM

IRm, kk0, [p k]+
(3.23)
Rp = 0, +k T
i-i k-id
tm p0
It is pointed out that in Eqns (3.21) and (3.22) the terms for deactivation and transformation
(with or without termination) by monomer have been omitted since in these reactions no
monomer unit is added to the polymer chain. Hence the total monomer consumption rate
over all the catalystsitesis given by:
ýk )Xk
k0oi[pk + ýjýkstm,lk kl k
01+(ktm +kkpT10
lrxn Wsk IM, 1
R (3.24)
m, k-i
+
k Xk
kdMi +N ýkki xk
0 nstmil 0
1-lok
52
__
3.2.3 Polymer Properties

The descriptionof the chain lengthdistribution by meansof live and bulk polymermoments
allows the estimation of polymer architecture properties, important in terms of the
characterization and prediction of end use performance of the produced material
(Hatzantoniset al., 2000).
Copolymer composition
The "instantaneous" copolymer composition, 9j, for a catalyst having N, active sites, will be
given by the consumption rate of the I' monomer over the total consumption rate of the N..
monomers:
NNN
ya Ya
m /Y,
Rk, RkM, (3.25)
k=l i=l k=l
while, the respective cumulative copolymer composition is accordingly defined by:

Ns /k=l Ns
Z4k
F 4k, (3.26)
a
k=1
1.1
Degree ofpolymerization
The number and weight averagedegreesof polymerization, DP. and DP, of the copolymer
chains are calculated in terms of the leading moments of the TNCLD.
N j /j
DP,, 210
ýk/j4k
DP, =. 42k 4k (3.27)
k-I k-I k-I
I
k-I
Molecular weight
Based on the above expressions of the degreesof polymerization of the "bulV polymer and
defining the average molecular weight of the repeated monomer units in the polymer chain
as:
Nm
Tf- W
w = 2: (DiMwi (3.28)
i-I
where Mwi is the molecularweight of monomer T, then the number and weight average
molecularweight of polymerchainsaregivenby:
Mn :--DPnMW Mw = DPwMW (3.29)
53
Polydispersity index
Finally, the polyclispersity index (PD) will be given by the ratio of the weight average over
the number average molecular weight.
PD = Mw/Mn (3.30)
It is well known that the direct on-line measurementof the polymer molecular properties is
not practically feasible (Kammona et al., 1999). Thus, easily available on-line measurements
of melt index (MI) and density (p) are often utilized to control the "polymer quality" in a
polymerization reactor. In the literature, several correlations (McAuley and MacGregor,
1991; Kozub and MacGregor, 1992; Me et aL, 1994; Ogunnaike, 1994) have been proposed
to relate MI and p with the weight average molecular weight and copolymer composition,
respectively. In the present study, the following semi-empirical equations were employed:
(D. /C2)
p=c. + c, exp(-
Ml=aMw b (3.32)
The values of the CO,Cis C2, a and b parameters were calculated by fitting industrial
on MI and p to off-line measurements of M,, and Oj (i. e., the cumulative

measurements
copolymer composition of comonomer).
3.3 Macroscale Level
A large number of publications have appearedlately in the open literature trying to approach
the combined phenomena taking place in a FBR both from micro-, meso- and macroscale
point of view. The attempts to explain and describe the dynamic operation of the fluidized
bed reactors led to the development of many mathematical models with distinctive
differencesin the mixing patternandthe numberof phasesconsideredin the reactivezoneof
the fluidized bed.Precisely,thereare five featuresthat differentiatethe fluidized-bedreactor
mathematicalmodelsappearedin the literatureso far (Yiagopoulos,2001).
1. Numberofphases.The numberof phasesin the bed rangesfrom I to 4. The simplest
case is of course that of a single "pseudo" phase where bubbles, emulsion and solid
54
are perfectly mixed. The most complex case on the other side is that where four
hypothetical phases appeared in the reaction zone of the bed, namely the bubble
phase,the emulsion phase,the cloud phaseand the solid phase.
2. Reaction. In the majority of mathematical models it is accepted that the

polymerization reaction is taking place exclusively in the emulsion phase since the
bubble phase is free from solid particles, namely from catalyst active sites. However
there are some models where reaction is assumedto occur both in the emulsion phase
and the bubble and cloud phase.
3. Heat and mass transfer between the phases. According to the number of phases
considered by the various models different bifacial layers are created affecting the
heatand masstransferbetweenthe phases.The majority of the mathematicalmodels
employ some heuristic correlationsdescribingheat and masstransfer only between
the emulsionandthe bubblephase.
4. Isothertnal operation of the reactor. Due to the assumption of isothermal operation
of the fluidized bed reactor in the majority of the models, the energy balance is often
omitted releasing significantly model's complexity.
5. Mxingpattent in the bed. There are several mixing patterns between the hypothetical
phasesin the reaction zone of the bed. Therefore, the mixing of these phasesmay be
ideal (e.g. plug flow, or well-mixed) or non ideal (Yiannoulakis, 2001).
Based on the remarks and the observations of many investigators so far the operation of the
fluidized bed reactor (FBR) of a catalytic gas-phase olefin polymerization can be
schematically depicted in Figure 3.3. From this figure becomes apparent that the catalytic
bed of the FBR consists of two distinct phases,namely, the "bubble" phase, which is formed
at the gas distributor and then the bubbles are growing progressively as they rise trough the
bed, and the "emulsion" phase. In the catalytic olefin polymerization processes,catalyst is
the base upon which starts the molecular development of the polymer and therefore the
contacting and mixing patterns of the bubble phase with the catalyst at the beginning, and
with the emulsion phase next, are of major importance for the description of the FBR
operation. Due to the great complexity and difficulty in describing the hydrodynamic
behaviour of the two-phase FBRs, more than forty years of extensive studies were needed,
resulting in various mixing models. Concerning the flow characteristics of the bubble phase,
assumptions ranging from plug flow to perfect mixing have been made, although the
55
application of the former has more often been cited (Kunii and Levenspiel, 1991; Bukur et
al., 1974; Werther, 1992). On the other hand, the flow behaviour of the emulsion phase has
been the subject of serious debate among various investigators (Bukur et al., 1974; Kato and
Wen, 1969).
The two-phase model of Toomey and Johnstone (1952), the bubbling-bed model of Kunii
and Levenspiel (1969) and the bubble-assemblagemodel of Kato and Wen (1969) were the
first attempts of a mathematical representation of the fluidized bed reactor. For the
description of the complex mass and heat transfer phenomena within the emulsion, bubble
and cloud phases,Halwagi El- and Rifay El-(1988) recently developed a multicompartment
to
Catalyst
Product
Q.
. t., -, f -- 0'. *, '-: .. '. LI
Monomer gas
inlct
U., [Milin
Figure 3.3: Schematic representationof the fluidization profile in a catalytic gas-phase
olefin polymerization FBR.
56
three-phasemodel while additionalimprovementswere madeby Shiau and Lin (1993) and

Tabis and Essekat(1992)on the bubble-assemblage
model and the multicompartmentthree-
phasemodel respectively.Although the introductionof the cloud-wakephasein modelling
the fluidized bed reactor has been suggestedby many investigatorsmentionedabove,the
practical importance of such a consideration has not clearly been demonstrated. Thus there
are many caseswhere this separatecloud phaseis omitted (Sheplev and Luss, 1979; Werther,
1980; Choi and Ray, 1985; Talbot 1990, McAuley et aL, 1994; Hatzantonis ct aL, 2000). In
parallel with the emulsion and bubble phase, Bukur et al. (1974) and Sheplev and Luss
(1979) introduced in their models an additional phasefor the solid particles in the bed.
Choi and Ray (1985) were the first who developed a fluidized bed polyethylene reactor
model that considers temperature and concentration gradients within the gas in the bed. They
proposed a two-phase constant bubble size model consisting of perfectly mixed emulsion
phase and a plug-flow bubble phase to describe the dynamic behaviour of the FBR. A very
simplified kinetic model for ethylene homopolymerization was considered in order to study
the problem of temperature control in terms of steady-state multiplicity and bifurcation
phenomena. Their study was carried out under constant bed height and it was focus on the
influence of fluidization gas velocity, feed gas temperature,catalyst activity and catalyst feed
rate on reactor's dynamic behaviour. Prompted by the work of Choi and Ray, Talbot (1990)
modified the same model by considering dynamic change of the bed height with time.
McAuley et a]. (1994) compared the two-phase (bubble and emulsion phase) with the well-
mixed single-phase steady-statemodelling approach of polyethylene FBRs. They evaluated

the effect of fluidization phenomena,heat and mass transfer resistances,particle and bubble
size on steady state operating conditions and they realized minor deviations between the two
model predictions. Although they employed a very simplified kinetic model, comprehensive
correlations were used for the bubble fraction in the bed, the voidage of the emulsion phase
and the maximum stable bubble size. Finally a few years later Hatzantonis et al. (2000)
developed an improved bubble-growth mathematical model, which is a more realistic
approach to the bubble phasemixing pattern, and concluded that the two models of McAuley
et al. and Choi and Ray were two limited casesof their model.
The problems of phase multiplicity, heat transfer phenomena and operating profile in a
polyethylene FBR was recently studied from a different point of view. Jiang et al.
(1997a,b,c) investigated the "condensed mode" operation of the FBR where a liquid phaseis
fed in the reactor through a partially condensedrecycle stream. Various operating policies in
57
terms of, the level of condensation of the recycle stream in a vertical heat exchanger
connected to the polyethylene FBR, splitting scenarios of the liquid and vapour streams
before reintroduced in the reactor and introduction point of the liquid stream in the reactive
zone of the FBR were examined in order to achieve a more efficient heat removal and to
optimise the space-time yield of the polymerization reactor.
3.3.1 The Fluidized-Bed Olefin Polymerization Reactor

The fluidized bed reactor consists of a reaction zone and a velocity reduction-polymer
disengagementzone, where entrained particles drop back into the bed. For further reduction
of particle entrainment, a cyclone located either in the disengagement zone or outside the
reactor can be used (Figure 3.4). A typical value of the height to diameter ratio in the
disengagementzone is about 2: 1; the respective ratio for the reaction zone ranges from 2.7: 1
to 4.6: 1, while broader ranges can be applied depending on the desired production capacity
time (Jenkins et aL, 1985; Jenkins et al., 1986). The fluidized bed in the
and residence
reaction zone comprises growing polymer particles, existing formed polymer particles and
A good dispersion of catalyst throughout the reaction zone is
small amounts of catalyst.
formation localized hot spots. For the same reason it is essential
essential to prevent the of
that the bed always contains polymer particles to entrap and distribute the powdery catalyst.
Therefore, during the start-up the is

reaction zone usually pre-charged with a bed of polymer
before gas flow is initiated and catalyst introduction into the bed starts only after the
particles
fluidization conditions. Various techniques applied for the catalyst
establishment of stable
injection into the reactor at a point where good mixing of polymer particles is ensured.
Usually, catalyst is continuously fed into the bed carried by an inert gas, such as nitrogen,
which provides a means for pressurecontrol in the reactor.
The bed fluidization is supported and maintained by a recycle stream or fluidization medium,
generally made up from feed and recycle fluids. The recycle stream enters the reactor
through a distributor plate in the bottom section of the reactor, which aids in the uniform
fluidization. To maintain a viable fluidized bed, the gas superficial velocity (40-100 cm/s)
through the bed is about 3-8 times the minimum fluidization velocity (Chinh et al., 1996).
Howeverit is commonpracticein industries,in orderto achievesufficient heatremovalfrom
the bed,to operatethe reactorwith a greatervelocity than that requiredfor fluidization, but
still lower than a critical velocity where particle entrainmentphenomenacannot be reined
58
Chapter 3_ Catalytic Gas-PhaseOlefin Polymerization Fluidized Bed Reactor Model
Bleed Stream, FbIeed
Stream, F,,, o
Compressor
Fluidized bed
Catalyst
feeder
Ileat exchanger
Nitrogen feed, FN,

Inflow, Fw
Total Innow, Fi. Feed
Make-up feed,
F.,.,,,,F., on2
Figure 3.4: Gas-phaseethylene polymerization FBR unit.
neither in the disengagementzone, nor in a possible external cyclone. Under these conditions
the rate of gas recycle through the bed is about 50 times the feed rate of make-up fluid. The
make-up stream consists of monomers and hydrogen (used as chain transfer agent) and is
usually fed in the reactor together with the recycle stream or separately (particularly the
hydrogen stream). The composition of the make-up stream is determined by a gas-analyzer
located at the exit of the recycle stream from the reactor. The gas-analyzer measures the
composition of the recycle stream and the composition of the make-up stream is adjusted
accordingly to maintain an essentially steady state gaseouscomposition within the reaction
zone. A slight but not negligible pressure drop of the recycle stream through the bed is
59
causeddependingon the geometryof the reactorand the load of the bed with typical values
of operatingpressuresrangingfrom 10-40bars.The pressuredrop of the recycle streamis
made up in an external compressorlocated usually before the heat exchanger,where the
recyclestreamis releasedof the heatof the reactionbeforeit is returnedto the bed,in order
to control the bed temperature.Therefore, the temperatureof the reaction zone remains
constantin a steady-stateoperationand dependingon the density of the producedpolymer
it
grade ranges between75-115 'C. Although a uniform temperatureprofile along the bedis
a
noticeable, temperature gradient appears to exist in the bottom of the fluidized bed in the
regionabove the gas-distributor
plate,as a result of the temperature difference of the recycle
stream,entering the reactor, and the reactionzone. (Griffin et aL, 1995). This temperature
gradientin industrial-scalereactorsis smoothly damping within a layer of about 15-30cm
abovethe gasdistributor.
Finally it is pointed out that commercial-size reactors contain thousand of kilograms of
polymer solids at any given time. In a dynamic operation of the reactor this polymer mass is
a blend of polymer of different molecular characteristics, therefore the residence time of
polymer in the fluidized bed, which depends on the reactor geometry, is a crucial parameter
for the discharge of a particulate polymer product from the reactor. Product removal occurs
at a point near the gas distributor, and the fluidization medium removed together with the
solids or remained sorbed, is separated and removed or recycled back to the reactor.
polymer
In what follows next, a unified modelling approach is developed to describe the dynamic
behaviour of a well-mixed single gas-phase multisite catalytic ethylene-I -butene
copolymerization FBR. The selection of the well-mixed model among the others fluidization
patterns was made both for simplicity and it was also encouraged by the remarks of
mixing
McAuley et al. (1994) and Hatzantonis et al. (2000) regarding the validity of the well-mixed
model prediction. The main modeling assumptions are as follows:
1. The fluidized bed is approximated by a single-phase continuous stirred tank reactor

(CSTR)(McAuley et al., 1994).
2. Negligible massand heat transferresistancesbetweenthe polymer particlesand the
gasin the bed.
3. Since no bubble phase is included in the model, the bed void fraction, Cbed,
accounts
for the overall gas volume fraction in the bed.
4. Polymerization occurs only in the polymer volume fraction of the bed.
5. Uniform temperatureand component concentrations throughout the bed.
60
Chapter 3 Catalytic Gas-PliaseOlerin Polymerization Fluidized Bed Reactor Model
6. The concentrationsof all the speciesin the catalyst active site are equal to the
respective bulk concentrations.
7. Constant cocatalyst concentration in the bed.
8. The samekinetic mechanismappliesfor all the activecentresof catalyst.
9. No solid elutriationoccurs.
10. The feed streamsare free of impurities.
Based on the above assumptions, a generalized formulation of the unsteady-state material
and energy conservation equations can be derived.
3.3.2 Dynamic Mathematical Model

A modified/simplified kinetic scheme(compared to the analytical model presentedin section
3.2.1) corresponding to the needsof the present work is employed. A simpler two-site kinetic
model describing the molecular and compositional developments of the gas-phaseethylene

copolymerization with 1-butcnc over a Zicglcr-Natta catalyst, used in this work is presented
in Table 3.2. This kinetic mechanism includes catalyst activation, propagation, catalyst
deactivation and chain transfer reactions and therefore the kinetic rates expressions, the
function rates and the "pseudokinetic" rates are properly adapted to comply with this kinetic
mechanism of Table 3.2. Analytic developments of the kinetic rate expressions

corresponding to this kinetic schemeare presentedin Appendix A.
Table 3.2: Simplified kinetic mechanism of ethylene copolymerization over a

Zieeler-Natta catalvst.
Description Reaction
Activation: kkA
by Aluminum Alkyl (A): Sk +A ý pok
p
Propagation:
P, +mP,
Initiation: 01 ij
kk
pk +Mj pk
Additional units: n,i n+l. j
Deacrivario 1:
Spontaneous: pk kk
dSp Ck k
d+Dn
Chain Tranj&rL
kk
Spontaneous: pk t.9p[ ýpk
nj un+Dk
kk
by Hydrogen (1-12):
pk +H 2 IHI ) pk
nJ 0n+Dk
by Monomer(M.): kk
pk +M tm'iJ_>pk +Dk
nj i Ij n
61
Based on the above assumptions, the following unsteady-state molar balances for the two
monomers, hydrogen and nitrogen were derived:
Monomeri:
(I-C [Mi ]A dh
d[Mi] Fjý,Xm in -F,,, Xm QO[Mi] bedJ)N
j. I 2Rk (3.33)
dt MW Vbed Vbcd F-bed k-I
mi - Vbed
dt
iC bed
Hydrogen:
[H2
dIH21 FH2 +Fin XH
in -
Free XH
2_I- F-bed JRk QO [H21 ]A A
2,
HI (3.34)
dt MWH2 Vbed C Cbed Vbcd Vbed dt
bed k=l
Nitrogen:
FN2 +Fin XN2, [N21 [N2 ]A A
dIN21 in-FrecXN2 QO
Vbed
(3.35)
MW Vbed 6 Vbed dt
dt N2 bed
where Rk,, Rk are the monomer and hydrogen consumption rates at the catalyst active
M H2
site of type T. Xi and Xi, the fractions of species T in the recycle and input
in are mass
Similarly, the mass balances for the potential catalyst sites, [Sk ], and
streams, respectively. P
k, k, k)
all other molecular species
yk, (yk : pk Xk Xk Xk
0t 01 1,2tgO
91 92 can be derived:
ýP1c, ts kpI kk ]A
ý[S kp )I Q0
F,at /b cat bed in
p dh
+RkSP (3.36)
Vbcd Vbcd dt
dt
dyk Qo yk yk A dh
k (3.37)
=Ry
-7t Vbed Vbed dt
Rk
where ypdenotes the net formation rate of the molecular species yk and Sk, is the
, in
concentrationof activesitesof type T in the catalystfeed stream:

[Me]
[Sk,
p in]=fk site
(3.38)
where [Me] is the active metal in

concentration the catalyststream,and fk is the fraction of
metal that can form catalyst active sites of type 'k' (see Appendix B).
62
The symbols h, Vbed,and A denote the bed height, the volume and the cross sectional area of
the bed, respectively. Since the moments of the total number chain length distribution of
polymer chains are calculated independently of the ending monomer unit (i. e., ethylene or
butene), in order to calculate the cumulative copolymer composition, (Di,during a dynamic
reactor operation, the following dynamic mass balance equation needsto be solved:
d(M p(Di)
Fp, (Di, - Fp, (Di + Ybed (I - F-bed)Rp Yj (3.39)
dt in in out
where MP, FP,

i, and Fp, denote the total polymer mass in the bed and the input and output
o.t
polymer mass flow rates, respectively.
Accordingly,onecanderivethe unsteady-state
massbalancefor the polymer in the bed:
dh ( N, Vbcd Fcat- QO (I - Fbcd)P

ERk MW2) (3.40)
-dt ml Mw I +jRk M2 0- tbed)
k=l k-I pA pA
where p and p,,, are the corresponding densities of the polymer and catalyst.
t
The dynamic energy balance for the reaction mixture in the bed is written as:
dT (Hgas, - Hgas. - Hprod, + Hgenr) TAA

in out out (3.41)
-= Haccum Vbcd dt
dt
the terms Hgas, Hp,.d,,,,, and H,,,,,, denote the enthalpies of the input, output
where h,, t,
streams and the heat of polymerization, respectively. Assuming that the
and product removal
dynamic behaviour of the external heat exchanger (see Figure 3.4) can be approximated by a
series of N,. well-stirred zones for the recycle stream and a single well-stirred zone for the
coolant, the following energy balancescan be written:
dT.
M CP = F,,, Cpm... (Tj. Tj) Qj, i (3.42)
j
gas, mcandt o 1 - -
NN
2Qj 2ýUjAj(Tj » (3.43)
Q= = -T,
j=I j=I
dT
MaqCP. = F Cp (T,. i - T )+Q (3.44)
dt
63
It is pointed out that the above energy balance is derived neglecting the dynamics of the heat
exchanger as far as compositional and accumulated mass changes of the coolant and the
components of the recycle stream in the heat exchanger are concerned. Therefore, the
amount of both the coolant and the gas in the heat exchanger are constant while the
composition of the gas mixture in the well-stirred zones of the heat exchanger follows the
compositional changer of the recycle stream. In Appendix B the numerical values of the
reactor and heat exchanger design parameters and the physical properties of the various
components and their mixtures are reported respectively. During the model development no
high-index problem was faced. Finally it is noticed that a more detailed and comprehensive
analysis is adopted for the development of the dynamic model of the polymerization FBR in
a following chapter where the model validity is given special consideration.
3.4 Summary
Within this chapterthe activity of the mathematicalmodel developmentfor a catalytic gas-

phaseolefin polymerizationfluidized bed reactor was extensivelyanalysedpresentingthe
full dimension and the different levels of this composite task. Despite the recognized
importanceof the different modelinglevels and the interactiverelationshipbetweenthem it
is crucial to realizewhat this model servesfor in order to give greateremphasison someof
these modeling levels as far as the detail and accuracyof the mathematicalmodel is
concerned.At this point of this study various simplifications and assumptionswere made
during the mathematical model build-up without serious impact, to the author's
understanding,on the solution approachof the operationaland control problemsthat will be
handled next. However, the space for further improvementof the model accuracyand
credibility has been already highlighted and deeperelaborationtowards this direction is
attemptedin a subsequent chapter.
64
3.5 Literature
Achilias, D.S.; Kiparissides,C. (1992)Toward the developmentof a generalframeworkfor
modelingmolecularweight and compositionalchangesin free-radicalcopolymerization
reactions. J.M. S.-Review of Macromolecular Chemistry and Physics, C32(2), p. 183.
Boehm, L. L. -, Berthold, J.; Franke, R.; Strobel, W.; Wolfmeier, U. (1986) Ziegler
polymerization of ethylene: Catalyst design and molecular weight distribution. Stud. Surf.
Sci. Cat., 25, p. 29.
Bohm, L. L. (1978) Reaction model for Ziegler-Natta polymerization. Polymer, 19, p. 545.
Bukur, D. B.; Wittman, C.V.; Amundson, N. R. (1974) Analysis of a model for a
nonisothermal continuous fluidized bed catalytic reactor. Chem.

Eng.Sci., 29, p. 1173.
Carvalho de, A. B.; Gloor, P.E.; Hamielec,A.E. (1989) A kinetic mathematicalmodel for
Zieglcr-Nattacopolymerization.Polymer,30, p. 280.
heterogeneous
Chen, C.M. P. (1993) Gas phase olefin copolymerization with Ziegler-Natta catalysts. PhD
Thesis, University of Wisconsin-Madison.
Chin, J.C.; Filippelli, M. CH.; Newon, D.; Power, M. B. (1996) Polymerization process. U.S.
Patent 5541270, July 30.
Choi, K. Y.; Ray, W.H. (1985) The dynamic behaviourof fluidized bed reactorsfor solid
catalysedgasphaseolefin polymerization. Eng
Chem. Sci., 40, p. 2261.
Floyd, S.; Heiskanen, T.; Ray, W. H. (1988) Solid catalyzed olefin polymerization. Client.
Eng. Prog., 84, p. 56.
Galvan, R.; Tirrell, M. (1986) Molecular weight distribution predictions for heterogeneous
Ziegler-Natta polymerization using a two-site model. Chein. Eng. Sci., 41, p. 2385.
Griffin, J.R.; DeChillis, M. L.; Muhle, M. E. (1995) Process for polymerizing monomers in
fluidized beds. U.S. Patent 5462999, Oct. 3 1.
Halwagi El-, M. M.; Rifai El-, M. A. (1988) Mathematical modeling of catalytic fluidized bed
reactors: The multistage three phasemodel. Chein. Eng. Sci., 43, p. 2477.
Hatzantonis, 1. (1999) Mathematical simulation of heterogeneouspolymerization of olefins

in a gas-phasefluidized bed reactor. PhD Thesis, Aristotle University of Thessaloniki. (In
Greek)
65
Hatzantonis, H.; Yiannoulakis, H.; Yiagopoulos, A.; Kiparissides, C. (2000) Recent

developments in modeling gas-phase catalyzed olefin polymerization fluidized-bed
reactors: The effect of bubble size variation on the reactor's performance. Chem. Eng.
Sci., 55, p. 3237
Hutchinson, R.A.; Chen, C.M.; Ray, W. H. (1992) Polymerization of olefins through

heterogeneous catalysis X: Modelling of particle growth and morphology. J. Appl.
Polym. Sci., 44, p. 1389.
Jenkins III, J.M. III; Russel, L. J.; Jones, T. M. (1985) Fluidized bed reaction systems. U.S.
Patent 4543399, September24.
Jenkins, III, J.M.; Jones, R.L.; Jones, T. M.; Beret., S. (1986) Method for Fluidized Bed
Polymerization. U.S. Patent 4588790.
Jiang, Y.; McAuley, K. B.; Hsu, J.C.C. (1997a) Effects of operating conditions on heat
removal from polyethylene reactors.AlChE J., 43, p. 2073.
Jiang, Y.; McAuley, K.B.; Hsu, J.C.C. (1997b)Heat removal from gas-phasepolyethylene
model.Ind. Eng. Chem.Res.,36, p. 1176.
reactorsin the supercondensed
Jiang, Y.; McAuley, K. B.; Hsu, J.C.C. (1997c) Nonequilibriurn modeling of condensedmode
cooling of polyethylene reactors.AIChE J., 43, p. 13.
Kammona,0., Chatzi, E.G., & Kiparissides,C. (1999). Recentdevelopmentsin hardware

sensorsfor the on-line monitoring of polymerization. Journal of Macroniolecular Science
- Reviews in Macronzolecular Chemistry and Physics, C39, p. 57.
Kato, K.; Wen, C.Y.; (1969) Bubble assemblagemodel for fluidized bed catalytic reactors.
Chenz.Eng. Sci., 24, p. 1351.
Kozub, D.J., MacGregor, J.F. (1992). Feedback control of polymer quality in semi-batch
copolymerization reactors. Chemical Eng. Sci., 47, p. 929.
Kunii, D.; Levenspiel, 0. (1969) Fluidization Engineering. Wiley Eds., New York.
Kunii, D.; Levenspiel, 0. (1991) Fluidization Engineering. 2ndEd., Butterworth-Heinemann.
Lorenzini, P.; Bertrand, P.; Vilermaux, J. (1991) Modelling ethylene and a-olefin
copolymerization using Ziegler-Natta catalyst. Can. J. Chem. Eng., 69, p. 682.
McAuley, K.B., MacGregor,J.F. (1991). On-line inference of polymer propertiesin an

industrial polyethylene reactor. AlChEkunzal, 37, p. 825.
66
McAuley, K. B.; MacGregor, J.F.; Hamielec, A. E. (1990) A Kinetic Model for Industrial
Gas-PhaseEthylene Copolymerization. AICHE J., 36, p. 837.
McAuley, K. B., Talbot, J.P., & Harris, T. J. (1994). A comparison of two phase and well-
mixed models for fluidized-bed polyethylene reactors. Chem. Eng. Sci., 49, p. 2035.
Nagel, E.J.; Kirrillov, V. A.; Ray. W. H. (1980) Prediction of molecular weight distributions
for high density polyolefins. Ind. Eng. Chem. Prod. Res. Dev., 19, p. 372.
Ogunnaike, B. A. (1994). On-line modelling and predictive control of an industrial

terpolymerization reactor. Int. Journal Control, 59, p. 711.
Ray, W. H. (1991) Modelling of addition polymerization processes-Freeradical, ionic, group
transfer,andZiegler-Nattakinetics.Can.J. Chem.Eng.,69, p. 626.
Shaffer, W.K.A.; Ray, W.H. (1997) Polymerizationof Olefins Through Heterogeneous

Catalysis.XVIL A Kinetic Explanationfor UnusualEffects.J. Appl. Polym.Sci., 65, p.
1053.
Sheplev, V. S.; Luss, D. (1979) Steady-statemultiplicity of fluidized bed reactors: The solid-
circulation model. Chem. Eng. Sci., 34, p. 515.
Shiau, C. Y.; Lin, C. J. (1993) An improved bubble assemblancemodel for fluidized bed
catalytic reactors. Chen?.Eng. Sci., 48, p. 1299.
Tabis, B.; Essekkat, A. (1992) Three phase m ul ti -compartment model for fluidized-bed
catalytic reactors: Autothermicity and multiplicity of steady-states.Chem. Eng. Sci., 47,

p. 407.
Talbot, J.P. (1990) The dynamic modelling and particle effects on a fluidized bed
polyethylene reactor. PhD Thesis, Queen's University.
Toomey, R.D.; Johnstone,H.F. (1952) Chem. Eng. Prog., 48, p. 220.
Werther, J. (1980) Modeling and scale-up of industrial fluidized bed reactors. Chem. Eng.
Sci., 35, p. 372.
Werther,J. (1992)Scale-upmodelingof fluidized bedreactors.Client.Eng. Sci.,47, p. 2457.
Xie, T.; McAuley, K. B.; Hsu, J.C.C.H. -, Bacon, D. W. (1994) Gas phase ethylene
polymerization: Production processes,polymer properties, and reactor modelling. Ind.

Eng. Chenz.Res., 33, p. 449.
67
Xie, T.; McAuley, K. B.; Hsu, J.C.C.; Bacon, D. W. (1995) Modeling Molecular Weight
Development of Gas-Phasea-Olefin Copolymerization. AICHEJ., 41, p. 1251.
Yiagopoulos, A. (2001) Micro- meso- and macroscale dynamic simulation of polyolefin

fluidized bed reactors. PhD Thesis,Aristotle University of Thessaloniki (in Greek).
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in heterogeneous catalytic polyolefin fluidized bed reactors. PhD Thesis, Aristotle
University of Thessaloniki (in Greek).
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chemical reactors. PhD Thesis, University of Wisconsin-Madison.
68
CHAPTER4
Process Design and Control Optimisation
Process design is a multifaceted problem composed of various combinatorial and interacted
sub-problems, which require continuous reconciliation and reconsideration during a general

process synthesis problem, in order to achieve the desired steady-state or dynamic process
performance at any stage of process lifetime. It encompassesactions clearly inducing process
ability to meet environmental, safety, processing and product specifications in an economical
viable manner. Precisely, there is a number of branches come under the broad term of
processdesign involving the following vital decisions over:
" the processoperating mode (continuous or batch),
"a viable candidate process structure,
" an appropriate configuration and topology of process units and their interconnections,
" economically optimal processunit design parameterssuch as processunit sizes,
" an appropriate control system synthesis,
" economically optimal operating conditions and operating dynamic profiles, as well as
operating schedule and other issuesrelated to processoperability.
In the remainder of this thesis, process control synthesis and process operability are studied
under a model-based approach in relation to an industrial Ziegler-Natta catalytic gas-phase
ethylene polymerization FBR, utilizing the dynamic model developed in the previous
chapter. The lower levels of processdesign, as presentedabove, corresponding to the process

configuration and unit dimensions are considered predetermined and preset to their optimal
values under a heuristic-based analysis. Investigation of the impact of these process design
decisions on respective decisions of higher level of process design stages is not considered
and the analysis presentednext is entirely independent.
69
Chapter 4 ProcessDesignand Control Optimisation
4.1 Problem Statement
Present market needs combined with the broad range of polyolefin applications have forced
the polyolefin industry to operate under frequent grade transition policies. This trend has led
the polyolefin industry to move away from large continuous production of a single polymer
grade to a more flexible production scheme comprising a number of polymer grades of high
quality but low volume. In fact, in a polyolefin plant few tens of polymer grades can be
produced. For example the Philips plant produces as many as 50 different grades of polymer
(McDaniel, 1988). Consequently, under such market-driven operating schedules, the
minimization of off-spec polymer production and grade changeover time are prerequisite to
any profitability analysis of the process. Commonly, the optimal solution to this problem is
based on the minimization of a suitable objective function defined in terms of the grade
changeover time, product quality specifications, process safety constraints and the amount of
off-spec polymer. However, optimal operation of a polymerization plant in terms of higher
yield and better product quality at reduced cost can only be achieved when the process is
operated under well-controlled conditions. In fact, a thorough selection of feedforward and
feedback controllers is an essential requirement for the faithful implementation of an optimal
control policy in a polymer plant.
The problem of process control and process operation in a polyethylene FBR is faced by this
work from the perspective of grade transition operation of the polymerization reactor. It is
first priority for a process engineer to obtain a general view of process dynamics and come
up with a detailed drawing of process control synthesis problem and only then to combine
and revisit this problem on the basis of the transient operation of the reactor.
Control of fluidized bed polymerization reactors has long been known to be a difficult and
composite task. The high nonlinearity of the polymerization reactions, traced mainly in the
expressions of the kinetic rate constants, process dynamics of different time scales and the
strong interaction of the reactor variables leading to multiple and simultaneous intensive
changes in the reactor, amplify the polymerization reactor control problem. Great deal of
effort is needed to track the control problem of solid catalysed fluidized-bed polyethylene
reactors, which are prone to unstable behaviour, and exhibit steady-state multiplicity,
bifurcation phenomena and temperature oscillations and runaway (Choi and Ray, 1985;
McAuley and MacGregor, 1993; McAuley et aL, 1995; Dabedo et aL, 1997; Ali et al., 1999).
The principal control problem arising in such reactors is related to the fact that the reactors
70
Chapter 4 Process Design and Control Optimisation
are operating very close to the softening point of polymer being formed (in order to ensure
the maximum feasible productivity). If through poor process control the polymer particle
reaches the softening temperature, then the free flowing polymer powder begins to
agglomerate, to stick to the internal reactor surface rendering the reactor's shut down
unavoidable. Hence, most commercial gas-phase fluidized bed polyethylene reactors are
operated in a relatively narrow temperature range, and temperature excursions outside this
range must be avoided to preserve the polymerization system from low catalyst productivity,
undesirable product properties changesand abnormal reactor operation.
Evidently, the smooth operation of the process in terms of the reactor temperature and other
process variables (that will be studied analytically next) is prerequisite to create a safe
operating envelope where the grade transitions will be carried out.
4.2 Control Synthesis Problem
Part of the constructionof processflow sheetunder the processdesign procedure,is the

synthesisof the processcontrol architecturesystem.Despitethe multiple dimensionsof this
problem, most of the effort by several researcherswas oriented toward the design of a
controller for a specifiedset of inputs and outputsdiminishing like that the problemsinceit
hasbeenrecognizedthat the performanceof a processcontrol systemis ultimately limited by
the choice of manipulated and measuredvariable rather than the implementedprocess
controller (Morari, 1987; Narraway, 1992). In other words, a thoughtlessselectionof a
control structurewith simultaneousexclusionof other candidatestructureslimits the overall
performance of the control systemand thereforean integratedand global examinationof the
problemis requiredinstead.
4.2.1Five-StepProcessControl Synthesis
The procedure of process control system development is entirely described by the following
five action points reflecting the multistage character of this problem:
1. define a set of control objectives,

2. detennine a set of variables to be controlled to achieve the control objectives,
3. identify a set of variables which can be measured for monitoring the process
behaviour,
71
.
4. determine a set of manipulated variables and

5. find the appropriate connections between measured and manipulated variables
(control loops) (Nishida et al., 1981).
From the hierarchy of these steps it is evident that the set of control objectives is a
deterministic factor for the overall process control synthesis, since all the remaining decisions
of controlled, measured,manipulated variables and control structure are clearly driven by the
requirement for the best attainment of these control objectives. Control objectives should be
identified on the base that the resulted control system is robust, accounts for process
dynamics and makes sure process stability. Then with the smooth operation of the controller
prearranged, the control objectives are usually comprise the satisfaction of safety aspects,
environmental and related regulations, operational requirements and process constraints,
product quality specifications and finally economic related targets.
A different criterion of the control system performance is process controllability, which

defines a different strategy for the control system development. Processcontrollability can be
examined individually, however it is more desirable during a process control synthesis to

satisfy the above objectives while maintaining good controllability characteristics.
4.2.2 Process Controllability

Process controllability and switchability (usually considered together under the term
"controllability") is process regulatory capability about a steady state and ability to switch
between operating modes. It is an inherent property independent of the particular designing
of the process controller or/and its parametersand it is a qualitative criterion of how well the
process rejects disturbances, how severely the multiple variables interact and how easily the
system moves from one operating point to another. The definition given for controllability by
Skogestad et al. (1991) as the "best quality of response which can be obtained by feedback
control" implicates all the factors affecting the control synthesis problem to the
controllability analysis.
The influence on controllability by the conceptual stagesof process design, where screening
of process flow sheet alternatives, sizing of process equipment, identification of

economically important disturbances are studied, was examined in a series of publication by
Fisher et al. (1988a,b,c), under a general framework of the interface between design and
control. However such a preliminary consideration of process controllability is out of the
72
scope of this thesis, since the alternativesrelated to the first stagesof processdesign
procedureare fixed while attentionis focusedon the control structureselection,as part of
processdesign,and its dramaticeffect on processcontrollability. Luyben M. and LuybenW.
(1995)presenteda two level studyof designandcontrol in a complexprocessof two reaction
units, three distillation columns and recycle streamsbetweenthem. At a first level they
determinedan economicallyoptimal steady-statedesignthat balancesoperatingand capital
costsasa trade-offbetweenthe sizesof the reactionsectionsandthe flow ratesof the recycle
streams.Both heuristicand nonlinearoptimizationapproacheswere employedfor the design
procedure.Then, at a second level, for a predeterminedprocessdesign they developed
various control systemsin order to illustrate the effect of the control structureon process
controllability. However, all the control structure alternativeswere derived heuristically
defining someof the degreesof freedomas manipulatedvariablesor static designvariables.
There is extensive published work in the past decadesdevoted on the developmentof
controllability analysistools, such as right half-planetransmissionzero analysis(Holt and
Morari, 1985; Morari et aL, 1987), singular value analysis (Johnstonand Barton, 1987;
Banerjee and Arkun, 1995; Cao and Biss, 1996), relative gain array (Bristol, 1966),
structuredsingularvalue (SkogestadandMorari, 1987;Lee et al., 1995)for control structure
selection.Thesetools can efficiently evaluatethe perforrnanceof a control schemewithout
perfon-ningcontroller design and closed-loop simulation. Perkins and Walsh (1994)
summarizeda numberof methodsfor controllability assessment,
control structureselection,
andintegratedprocessandcontrol systemdesign.
A recognizable disadvantage of controllability analyses when used in design studies is that
the performance indices may not be compared directly with the process economics
(Narraway 1992). This leaves the design engineer with the decision of trading-off an abstract
controllability index against improved steady-stateeconomics. However, there are only a few
papers to suggest algorithmic synthesis procedures, which include some measure of
controllability as part of the objective. Morari and Perkins (1994) in an interesting review
paper they presenteddifferent schools of thought over the area of process controllability, the
interaction of process design, control and operation, based on steady-state, linear dynamic
and nonlinear dynamic models. Some of these works were orientated by strictly economic
criteria. Narraway and Perkins (1993,1994) explored the selection of process control
structure for two case studies basedon linear and nonlinear dynamic economics respectively.
They formulated a mixed integer Iinear-nonli near optimal control problem (MILP and
MINLP) to addressthe generation and efficient assessmentof the potential control structures
73
4 ProcessDesignand Control Optimisation
_Chapter
in order to come up with an economically optimal multiloop process control scheme.

Kookos and Perkins (2001) presented also an algorithmic procedure for the simultaneous
process design and control applied in various case studies, such as an evaporator process, a
binary distillation column and a reactor-separator-recyclesystem. Their approach was based
on a steady-state relaxation of a combined dynamic problem accounting for process

uncertainties, and utilizing a purely economic objective function they aimed in finding the
optimal plant topology and control structure and design, on the base of a multivariable PI
control scheme. On the other hand, Luyben and Floudas (1994a) worked on a trade-off
approach between process economics and controllability. They illustrated a multiobjective
mixed-integer nonlinear (MINLP) algorithm in order to determine a best compromise
solution among various process economic and open-loop controllability objectives in the
synthesis of binary distillation columns. The incorporation of the open-loop steady-state
controllability measures within the mathematical programming approach could be achieved
through the maximization of the minimum singular value of the process, the minimization of
the condition number, the disturbance condition number, the distance to one of the
nonnegative RGAs, or any other controllability index. Luyben and Floudas (1994b) applied
also the same framework to study the design of a system consisting of an isothermal reactor
followed by a distillation column, whose distillate stream is recycled back to the reactor.
Similarly, Seferlis and Grievink (2001) developed a method for a rigorous screening and
ranking of process flow sheet and control system configuration defined in terms of selected
controlled and manipulated variables in a process similar to that described by Luyben and
Luyben (1995). The steady-statedisturbance rejection characteristics of the nonlinear process
as a representative static controllability performance index was considered in conjunction

with economic criteria for the alleviation of poor design and control structure alternatives.
The literature review presentedso far by no means is considered exhaustive. It is recognized

that several other approaches of the composite problem of process control and process
operation under the general framework of process design have appeared in the open
literature. However, the purpose of this survey is to highlight the different branches of this
problem and demonstrate and identify the actual dimensions of this problem as it appearsin
the case study investigated by this thesis, which is the polymerization reactor system and the
catalytic olefin polymerization FBR in particular. More specific literature survey over the
solution of the optimal control problem on such polymerization systems will appear later in
this chapter as well as in chapter 5.
74
4.3 Control System of the Ethylene Polymerization FBR
The control synthesisproblem is examinedin this paragraphin relation to the catalytic gas-
phaseethylene-I -butenecopolymerizationFBR presentedin the previous chapterand the
Appendix A. The conceptualprinciples ruling this problem, as they were demonstrated
before,they are revisedhereand they are adaptedto the flow sheetof the reactorsystemand
its operatingprofile. It hasbeenstatedbeforethat the operationof the reactorduring a grade
transition is the operatingmode of interest for this work where advancedprocessdesign
methodswill be applied on, in order to achievebetterreactorperformance,recognizingthe
economicimportanceof this operatingstatusin real industrialprocesses.
4.3.1 Control Objectives

In a grade transition operation of the reactor the production of the desired polymer grades is
sought. Polyethylene grade specifications are generally quoted in terms of polymer density
(p) and melt index (MI), which are associated with both processing and end-use polymer
characteristics, such as rheological properties, stiffness, transparency, hardness,etc. Polymer

density and melt index are two commercially indexes of polymer quality in the polymer
processing industry, which are tightly related with polymer molecular properties (copolymer
composition, chain branching distribution, average molecular weight and molecular weight
distribution, seeChapter 2) as far as the polymer production engineer is concerned.
Therefore, adopting the hierarchical procedure of Nishida et al. (1981) (see paragraph 4.2.1)
referring to the first step of this procedure, polymer density and melt index represent two of
the control objectives classified in the polymer quality specifications and as it will be proved
later they are connected with economic related targets as well. Environmental regulations
might be needless for this study both because gas-phase processes are relatively
environmentally friendly and because introduction of environmental related restrictions
wouldn't serve the targets of this work, however, there are some safety and operational
aspects that need to be taken into account in the identification of the control objectives.
Recalling the operating features of the gas-phasepolymerization FBR the control system is
to
responsible retain the rector operation within a tight temperature range. Similarly, apart
from reactor temperature, excursion of reactor pressure over an upper bound is a continuous
menace for process safety, while it is pointed out that during both steady-stateand transient
operation of the process extreme variations of bed level are unwelcome reflecting to
75
abnormalfluidization of the bed with known consequences in processoperationas described

in previouschapters.Finally, anotherrequirementthat needsto be fulfilled during the
steady-
stateoperationof the processis to meetthe marketdemandfor every polymer grade.Thus,
an additional control objective is the quantitativesatisfaction(togetherwith the qualitative
one-productquality specifications)of the polymer market and the flexibility of process
capacityto efficiently keepstepwith possiblevariationsof marketneeds.
4.3.2 Control and Measure Variables

The identification of the control objectives assists the definition of the appropriate
controlled
variables for the effective attainment of the above requirements by the control system. Hence,
for process safety and operability, the reactor temperature (T) and pressure (P) as well
as the
bed height (h) need to be maintained at specified operating points. Regarding the product
quality, the polymer density (p) and the melt index (MI) are usually controlled. Finally, the
polymer production rate (Rp) is the appropriate variable to be controlled in order to maintain
the reactor productivity at a desired level constituting a set of six controlled variables of the
process. The assumption that these controlled variables are measured variables as well is
made. This assumption holds absolutely true for the bed height, the reactor temperature and
pressure, as well as the polymer production, however, the key quality variables, such as
polymer density and melt index, need on-line analysers that are not yet a commercial reality.
Therefore, frequent sampling and laboratory analysis of polymer samples in discrete time
intervals are interposed, continuously updating the controller actions in order to adjust
polymer quality. Although this lack of robust and reliable on-line polymer characterization
devices is an inhibitory factor for the attainment of polymerization reactors control
(Kiparissides et al., 1987), it is assumed that the overall sampling and laboratory analysis
time is small relative to the dynamics of the cumulative polymer properties.
4.3.3 Degreesof Freedom-Manipulated Variables

The set of the manipulated variables is a subset of the degrees of freedom of the
uncontrollableprocess.Someof thesedegreesof freedomare staticcorrespondingto process
designand operatingvariablesand they are fixed to adjustprocessequipmentsizes,process
constraintsandprocessoperationin orderto achieveoptimal processperformancein termsof
certain objectives.The remaining degreesof freedom provide the potential manipulated
variablesfor the processcontrol.
76
Considering the mathematical model developed in Chapter 3 and the schematic
representation of the catalytic gas-phase olefin polymerization FBR depicted in Figure 3.4
one can identify the set of the degreesof freedom of the process. All the inflows and outflows
of the process, namely, the monomer and comonomer mass flow rates (17moni,
FmonDin the
make-up stream; the hydrogen, nitrogen and catalyst mass flow rates (FJJ,, Fiqý, F,,,t); the
mass flow rate of the bleed stream (Fbleed);

the mass flow rate of the product removal stream
(F,,,,t, including both polymer and gases), the recycle stream (17', and the mass flow rate of
c),
the coolant water stream to the heat exchanger (F, ); need to be adjusted in consistency to the
desired operating point and the produced polymer grade with simultaneous attainability of the
control objectives. Furthermore, the steady-state operating conditions of the reactor need to
be assigned according to the safety and operational control objectives. From these variables,
the flow rate of the recycle stream depends on the superficial velocity of the gas stream
through the polymer bed in the reactor, which is a static design variable, and consequently
the recycle flow rate is fixed. Besides, the steady state value of the bleed flow rate, whether
the bleed flow rate is used as manipulated variable or not, is a fixed predefined operating
variable to avoid unnecessary bleeding from the recycle stream. Therefore, the set of the
manipulated variables consists of the following eight variables (MV: Fmoni,Fmon2s
FH, FN,
P 9
F,, Fw, FcatvFbIced),
which can selectively be used to control the six output variables (i. e., the
ut,
three process variables (T, P and h), the two "polymer quality" variables (p and MI) and the
polymer production rate, Rp).
4.3.4 Control Structure Selection

Considering that poor control performance does not necessarily indicate that the system
controllability is poor, as the use of better controller or superior tuning of the same controller
may significantly improve the performance, the control structure selection is a mean of
restoring process controllability. The set of the potential manipulated variables seems to be
to
adequate provide process operating and product quality control, hence the screening of the
alternatives control structures can initiate. The relative gain array (RGA) and singular value
decomposition (SVD) can be used to eliminate proposed control structures that will have
significant interactions in the control loops. Although a dynamic analysis is required to find
the best control structure alternatives, at this point of the thesis a preliminary static analysis is
to
only sought provide the bounds on the performance of the advanced process control that
will be demonstratedin a subsequentchapter of this thesis.
77
The static relative gain array is used as a widespread controllability index for the assessment
of different control structures of a square multiloop single input single output (SISO) control
scheme. The RGA analysis, first introduced by Bristol (1966), is a systematic approach for
the analysis of multivariable process control problems, which requires only steady-state
information and the linearized expression of the model, and provides two important items of
information:
0a measureof processinteractions,
0a recommendation concerning the most effective pairing of controlled and
manipulated variables (Seborg et aL, 1989).
Bristol approach is based on the concept of a relative gain. For a square plant 0 the RGA
between controlled variables Ci and manipulated variables Mi is defined as the dimensionless
ratio of steady state "open-loop" and "closed-loop" gains:

(acilamom
=gjj(s)-[G-'(s)], j (4.1)
T
Taci/ami
c
The symbol (aCj1aMj)m denotes a partial derivative that is evaluated with all of the
manipulated variables except Mj held constant (open-loop gain between Ci and Mj) and
(acilDMA is evaluatedwith all the controlled variablesexcept Ci held constant
similarly
(closed-loop gain between Ci and Mj). The RGA matrix can be computed at any frequency
using the formula
(G
A (s) = G(s) x " (s)y (4.2)
where the symbol x denoteselement by element multiplication.
It is obvious that the available manipulated variables are more than the controlled variables,
while a square control system is desired. Some heuristic rules coupled with the sequential
attempts of testing different sets of six manipulated variables from the available eight, were
applied in order to designate first which six of the eight manipulated variables will be used,
and then the best control pairing of the controlled and manipulated variables.
78
Table 4.1: RGA matrix over the first operatingpoint.

j F FNý %, F., Ratio FH2 1
ý ý,
T 1.0267 0.0140 0.0000 -0.0029 -0.0011 - 0.0276'
P -0.0021 1.0080 0.0000 0.0000 0.0000 -0.0059
h 0.0000 0.0000 1.0000 0.0000 0.0000 0.0000
Rp -0.0048 -0.0002 0.0000 1.0047 -0.0006 0.0009
p 0.0008 0.0002 0.0000 -0.0018 1.0057 -0.0048
MIJ 0.0214 -0.0220 0.0000 0.0000 -0.0040 1.0474.
L- j
Table 4.2: RGA matrix over the secondoperating point.

1 F FN2 F,., F., Ratio Fliý 1
ý,
T 1.0310 0.0155 0.0000 -0.0029 -0.0021 - 0.0415«
P 1.0234 0.0000 0.0000 0.0001 -0.0183
-0.0052
h 0.0000 0.0000 1.0000 0.0000 0.0000 0.0000
A2 =ý
Rp 0.0000 1.0063 -0.0011 0.0015
-0.0065 -0.0002
p 0.0008 -0.0001 0.0000 -0.0034 1.0063 -0.0036
Mlý 0.0214 -0.0220 0.0000 0.0000 -0.0040 1.0474.
. L- j
The linearization of the mathematical model over two different operating points
(corresponding to two different polymer grades) was carried out in FORTRAN, while the
RGAs, between controlled and manipulated variables for the controllability assessmentof the
process were derived using MATLAB. Tables 4.1 and 4.2 depict the values of the relative
gain arrays between the six controlled and the six manipulated variables over the two steady-
state operating points. Note that prerequisite for this analysis was the system stability, hence
the control of the bed level, as a pure integrator of the process, was necessary.Therefore, the
pairing of (h) with the product withdrawal rate (F,,,j was heuristically predefined. Table 4.3
shows the "best" control pairings resulted from the RGA analysis over both operating points.
Whenever this control scheme is employed, the remaining two control variables (FblcýdjFc'j
are defined as operating variables. FbIced

is fixed at its steady-state value and Fc.t is held
constant at its optimal value found via the solution of a static optimisation problem that
maximizes the monomer conversion satisfying the polymer quality specifications, the
(i.
operating conditions e., T, P, h) and the polymer production rate (Rp). According to Table
4.3, the first four manipulated variables (i. e., F.,,t, F,,, FN, F.,,,,,) are employed for the
,
control of the bed height, temperature,pressureand production rate, while the remaining two
(i. e., Ratio, F., ) are used for the control of the "polymer quality" variables (i. e., p, MI).
79
Table 4.3: Best pairings of manipulated and controlled variables basedon static RGA
analysis.
Manipulated Variables Controlled Variables

Cooling water feed rate (F, ) )I Temperature (T)
Nitrogen feed rate (FN, )0 Pressure(P)
Product withdrawal rate (Fo,t) Bed height (h)
Monomer feed rate (F.,, 1) Production rate (Rp)
Comonomer ratio (Ratio) Density (p)
Hydrogen feed rate ( FHý) Melt Index (MI)
4.4 Dynamic Process Optimisation
Economic aspects are seriously implicated in the process design and process operation
problem, which comprises a wide range of actions as it was defined at the beginning of this
chapter. Therefore, running the process in an optimal way satisfying certain economic criteria
is a cbmmon task for the process operator. When grade transition operation of the process is
also involved, the task complexity tremendously increases due to the inherently dynamic
character of the transient process operation. Thus, due to the importance of the time varying
behaviour of the process, economically optimal regimes for the plant call for dynamic
optimisation techniques. However, the intricacy of the polymerization processes and the
multiple interacted process parametersrequire simultaneous inspection of many aspectsand
an integrated and systematic strategy to efficiently deal with this problem. Hence,
experience-based recipes are deficient to carry out the dynamic process optimisation
depriving the full exploitation of plant's potential and consequently, model-based
optimisation techniques, mobilizing advanced mathematical programming, are used instead.
Establishing such a mathematical formulation capturing as many as possible dimensions of
the problem is a difficult task that needsto be fulfilled in order to achieve an optimal process
operation in a dynamic-economic region.
In what follows next, the theoreticalsynthesisof the gradetransitionproblemin the catalytic

gas-phase olefin polymerization FBR is illustrated.
80
4.4.1Outline of the Grade Transition Problem

It is often the casethat the material producedduring the transition from one steadystate
operatingpoint to anotherdoesnot meet the product specificationsfor either of them. It is
thereforeimportant to considerhow this transition can be effected with as little economic
penalty as possible.Productquality is a very complex issuein polymerizationthan in short
chain reactions(Ray, 1986)and thereforeconductinga gradetransition in a polymerization
plant, which is so tightly related to product quality, is a very complex task as well. The
reactordesign,the runtime per grade,the residencetime and the residencetime distribution
of polymer,plant safetyandinstantaneous
propertiesof the polymer arecritical aspectsof the
processbehaviour that need to be incorporatedimplicitly or explicitly in the economic
objective in order to guaranteesatisfactoryand efficient grade changeover,in terms of
minimum off-specproductionandswift transition.
Despite the need for a quick changeover,in order to reduce the period of less valuable
polymer production, all the changesin a polymerizationreactor during a grade transition
should be done safely, avoiding drastic operations, such as process overshooting or
undershooting,becauseit may result in runawayin the polymerizationreactor.Besidesthis,
at the end of the gradetransition, the averagepolymer propertiesare the criterion of good
processperformance.Thus, the smoothnessor the sharpnessthat a gradetransitionis carried
out with, affectingthe instantaneous
polymerproperties,reflectsto the mechanicalproperties
of polymer, by influencing both the molecularweight and compositiondistributions.Hence,
grade transition strategiesthat causeexcessiveovershootsin instantaneousMI and density
shouldbe avoidedbecausethey havean uncontrollableeffect on the propertydistributionsof
the overall polymer in the reactor.Thereforethe end-usepolymer propertiessubstantially
differ from the correspondingonesthat the polymer would have if it were producedunder
steady-stateconditions. Consequently,the actual time required for the completion of the
transitionis longersincereestablishment
of the desiredpropertydistributions,which depends
on the polymerresidencetime, is needed.
Regarding the residence time, it is known that in gas phase polyethylene reactors, the
residence time of polymer in the bed is from 3 to 5 hours (Choi and Ray, 1985). This means
that a long time is neededfor the reactor content to be changed over which is imperative for a
transition from one grade to another. Consequently a greater amount of off-spec polymer is
produced and taking into account the frequency that grade changeovers can occur (it can be
every few days), the potential of producing large amounts of off-specification polymer is
81
large. An indicative example that points out the lost production time and off-specification
product during changeover from one grade to another is derived from Sinclair (1987) and is
describedin Figure4.1.
As shown in Figure 4.1 from the beginning of the transition a sharp drop on the
polymerizationrate to 88% of the nameplatecapacity is observedensuringsafe operating
reactorconditions.As long as the reactorconditionschangetoward the new valuesrequired
for the new grade, the polymerization rate is reduced until point b. From point c the
polymerization rate increasesprogressively and not as sharply as it was reduced from point a
to b so as not to disturb the new operating conditions that have been settled in the reactor
corresponding to the new grade. At point d the polymerization rate reaches the lower limit of
the desirable band while the new steady state conditions are finally satisfied from point e
onwards. From to
point a point d the produced polymer is off specificationsand the amount
of this productis given by the areabelow the productionrate curve. Moreover, as long asthe
plant producesoff-spec product the economic loss is twofold for the since
process, this is a
lost productiontime of low profitability, during which the reactorcould haveproducedany
of the desired high value polymer products. Therefore, the appropriate formulation of the
in
economic objectives order to reflect the actual market conditions attributing higher
economicimportance to fast grade switches or to low off-specproduction levels may drive to

different transition operating profiles.
SPECIFICATION
LIMITS
A
GRADE
w IDEALCHANGEOVER
8
GRADE
ýýIoo \Loý
z PRODUCTION
0 CL d
TIME
0 bv
4GE
>J- /C COMPLETED
0
CL
80
23
TIME, hr
Figure 4.1 Grade changeover schemefor ethylene polymerization.
82
In the course of minimizing the off-spec product and/or the time of grade transition, many
strategies have been suggested and reported by Debling et al. (1994). Overshooting the
reactor concentration of monomer, hydrogen or inert, or deinventorying the reactor contents
are well known strategies in industry with known consequencesin the instantaneouspolymer
properties. Moreover, since the off-spec product cannot be recycled and can only be blended
with the on-spec product, deinventorying the on-spec product prior to adjusting reactor
conditions can lead to off-spec reductions. While all these are some heuristic grade transition
strategies, a set of features that a good grade transition policy, derived from a solution of a
dynamic optimization problem, is expected to exhibit, are presentedbelow:
" short period of time for the product properties to reach their new target values, and
small quantity of off-specification polymer production,
" safe operation of the reactor during the changeover; excursions above the sticking
temperature and disruptions of fluidization, and mixing are unwanted,
economically desirablesteady-stateconditions at the end of the transition; reactor

temperature,polymer productionrate, bed level and gas bleedflow rate shouldsettle
at pre-specified final values. (McAuley and MacGregor, 1992)
In conclusion, a trade-off among safe operation, plant stability, minimum off-spec
production, minimum transition time and market demand arc distinguishable elements of a
good grade transition. Particularly it is pointed out that the balance between the market
demand and the off-spcc product and/or transition time minimization strategy is very
sensitive in the sense that in high-markct demand periods the balance should be in favour of
minimum transition time paying less attention to the off-spec production, while in low market
demand periods the balance should be in favour of minimum off-spec production.
4.4.2 Research Over Grade Transition Dynamic Optimisation

The significant economic importance of product quality optimisation has motivated extensive
in the development of optimal control policies for the transient
research efforts aiming
responseof different polymerization processes.Thus, a great number of studies on open-loop
optimal control of polymer quality (e.g., number and weight average molecular weights,
polydispersity index, copolymer composition, molecular weight distribution, etc.) have been
reported for batch and semi-batch polymerization reactors (Thomas and Kiparissides, 1984;
Cawthon and Knabel, 1989; Choi and Butala, 1991; Crowley and Choi, 1997). Moreover, in
a number of published reports, the actual implementation of the calculated optimal control
83
policies in laboratoryand industrial polymerizationreactorshas beendemonstrated,through

correctivefeedbackcontrol, recursiveon-line parameterand stateestimatorandcontinuously
updatingof the optimal operatingprofiles accountingfor processdisturbancesand process-
model mismatch(Chenand Huang, 1981; Ponnuswamyet al., 1987;MacGregoret al., 1984;
Kravaris et al., 1989; Kim and Choi, 1991; McAuley and MacGregor, 1991; Kozub and
MacGregor, 1992; McAuley and MacGregor, 1993; Kiparissideset al.,1994; Ogunnaike,
1994;Kiparissideset al., 1996;Mourikaset al., 2002).
The calculation of optimal grade transition policies in catalytic olefin polymerization
processeshas been the subject of several publications. Cozewith (1988) studied the effect of
step changes in chain transfer agent and monomer feed rates on the number average
molecular weight (MJ, polydispersity index (PD) and copolymer composition for a
continuous flow stirred tank polyolefin reactor. He clearly demonstrated that the direction
and magnitude of the transition greatly affected the transient responsesof the polymer quality
variables (e.g., melt index, density). Moreover, he showed that a steady-state reactor
reinstatement following a reactor start-up was substantially faster than the establishment of a
new steady state during a grade transition operation. This was explained by the slow dynamic
response of the polymer quality variables during a grade transition due to the accumulated
polymer in the reactor. Despite this observation, shutting down and restarting the reactor to
produce a new polymer grade, is a much more expensive practice than the slower reactor
transition from one grade to a new one. Thus, the calculation of time-optimal control policies
to drive the reactor from one steady state to a new one in minimum time is a problem of
significant economic importance to the polyolefin industry.
McAuley and MacGregor (1992) investigated the optimal grade transition problem for a gas-
phase polyolefin FBR. A simple kinetic model was assumedto describe the molecular weight
developments in the FBR and the control vector parameterization method was employed to
calculate the optimal transition policies under predetermined switching times. No constraints
on the state variables were imposed. They showed that the calculated optimal transition
policies were strongly dependent on the functional form of the selected objective function
and the presenceof hard constraints on the optimisation variables, while they pointed out the
importance of simultaneous feedback control when implementing on-line a grade transition
optimal profile calculated off-line.
Debling et al. (1994) applied a heuristic approach based on industrial practice to solve the
"optimal" grade transition problem in a variety of processesincluding solution, slurry, liquid
84
pool and gas-phase olefin polymerization processes. No optimization principles were

employed, while for the assessmentof process performance, in terms of the amount of the
off-spec product and how swiftly the grade transition can be conducted under different grade
transition strategies, the POLYRED simulation package was used. These strategies
comprised heuristic-based actions, such as simple step changes of process inflows, quick
reactor venting, bed de-inventorying and selective overshooting of reactants concentration in
the reactor, as well as combination of these actions. Through their investigation, they
demonstrated the effect of various parameterson the grade transition performance including
reactor design, polymer residence time and residence time distribution by exploring this
problem in several reactor systems.
The time optimal control problem during a grade-changeperiod was studies also by Lee et al.
(1997) accounting for both the off-specification product and the minimum transition time in a
methylmethacrylate-vinyl acetate copolymerization CSTR. The novelty of their work was a

so called two-level hierarchical time-optimal control methodology based on the discretization
of transition time interval and application of genetic algorithms combined with heuristic
constraints, promising faster convergence and better results. Their methodology was
compared against the iterative dynamic programming (IDP) and the sequential quadratic
programming (SQP) both for equal and variable size time intervals exhibiting better
performance and highlighting the deficiency of SQP methods to be entrapped into local
minima.
Dabedo et al. (1997) and Ali et al. (1998) studied the stability and multiplicity of steady
states in industrial gas-phase polyolefin FBRs in terms of the temperature of the coolant
water, the catalyst feed rate and the superficial gas velocity. Their research is not explicitly
related to the grade transition problem, since it was focused on the assessment of different
types of non-linear model-based controllers (e.g., error trajectory and model predictive
control). However, they compared the process performance under these control systems with
that obtained under conventional PID control in terms of both process stabilization in the
presenceof disturbances, and their capability to provide servocontrol and set point tracking,
which is the baselinefor the gradetransitionprocessoperation.
Recently Takeda and Ray (1999) studied the optimal grade transition problem in a multistage
process with two polyolefin loop reactors in series. In their model-based approach of the
grade transition problem, they assumedthat the reactor temperature was perfectly controlled,
thereby bypassing a major issue for such catalytic polymerization systems. They tested
85
different formulations of a multiobjective performance index accounting for polymer
specifications in both reactors and they introduced product specification bands to force the
polymer properties first to go on-spec, and then to reach their target values at the end of the
changeover time. The control vector parameterization method was used to solve the dynamic
optimization problem while different but predetermined time division was applied for each
one of the decision variables.
An integrated optimal grade transition control system was proposed by Wang et al. (2000).
They combined the control vector parameterization method, in order to find optimal grade
transition trajectories for both process inputs and outputs, with a nonlinear model predictive
controller taking care of disturbances and model mismatch when the optimal input sequences
found off-line are used as feedforward signal in an industrial slurry ethylene polymerization
reactor. The grade transition between three polymer grades was examined considering the
different switching times of the optimisation variables as additional decision variables. The
problem of the optimal grade changeover control integrated with on-line sensing and
scheduling techniques was a research field for Ohshima and Tanigaki (2000) as well. They
pointed out how indispensable it is for product quality control in polymer plants to integrate
technologies in the process control, monitoring and optimisation area. Their work was based
on an inferential system developed by McAuley and MacGregor (1991) for on-line
estimation of MI and density of LLDPE polymer from process variables such as temperature
and concentrations in the reactor and a feedforward-feedback control framework. The
feedforward control was used to introduce the off-line calculated optimal trajectories of the
manipulated variables to drive the process from one grade to another and the feedback
controller to take care of process deviation from the desired optimal profiles of the controlled
variables.
Finally, the most recently contribution in the area of dynamic optimisation for grade
transitions in a polyethylene plant came from Cervantes et al. (2002). They presented a
model-based investigation of the grade transition problem in an industrial high-pressure
LDPE tubular reactor system. The dynamic optimisation problem was solvcd using a
simultaneous nonlinear programming method where the orthogonal collocation on finite
elements method was applied for the full discretization of the continuous state and controlled
model variables. It is pointed out that the dynamic mathematical model required to deal with
such a dynamic optimisation problem derived from a steady state model under various
simplifying assumptions, while a relative simple performance criterion was employed based
86
on the compositionof the chain transfer agent (butane)in the reactor recycle streamfrom
which the productquality can be inferredthroughvariouscorrelations.Table 4.4 summarises
the different approachesdiscussedbefore over the grade transition dynamic optimisation
problemhighlighting somespecialfeaturesof eachapproach.
4.4.3 Existing Methods for the Time Optimal Control Problem

The inherent dynamic character of the grade transition problem requires advanced dynamic
optimisation techniques in order to find the optimal trajectories of the decision variables that
will drive the process efficiently (according to the specification discussed so far) from one
grade to another. The main difficulty though with the dynamic optimisation problems is that
they are infinite dimensional. This is becausethe control, the state and other processvariables
are functions of time rather than simple one-valued quantities. Moreover, some of the process
constraints apply at all-infinite points of the time domain [0,,r], where the problem is studied.
Thus, mathematical methods for solving dynamic optimisation problems converting this
infinite dimensional system to a finite dimensional one are essential.
87
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The general mathematical form of the dynamic optimisation problem is stated next adapted
to the context of the problem considered here, highlighting the infinite dimensional nature of
the problem:
)
Min J=G(x(tf), y(tf), d, tt +f t'L(x(t), d, t)dt
y(t), u(t), (4.3)
u(c),d, tr t
I
S.t. f (i( t ), x (t), y (t), u (t), d, t)=0 vtEltoftf
VtE [to I
h(x(t), y(t), u(t), d, t) =0 9
tf
ho(i(to), x(to), y(to), u(to), d, to) =0 (4.4)

liostf]
g(i(t), x(t), y(t), u(t), d, t) :50 Vtr=
gi (i(ti ), ), ),
x(tj y(t, u(t, ), d, )
tj :50 VtIE[toitfl i=l N
whereto and tf denotethe initial and final transitiontimes. G and L are scalarfunctionalsof
the state, x, control, u, and output, y, variables.The functions f, h, and gi comprisethe
modelling equality and inequality constraintsthat must be satisfied at all times or at some
interior points of the total time horizon,while horepresentsthe setof the initial conditionsof
the differential algebraic equation (DAE) system. Note that the optimisation problem might
contain inequality constraints that should fulfilled at interior points or at the end point of the
time domain, which is usually discretized into a finite number of N time intervals. The vector
u(t) denotesa time optimal control trajectorythat forcesthe processto follow an admissible
state trajectory, while minimizing a certain objective function J. The vector d denotesthe
valuesof the model designtime invariant variablestogetherwith somemodel uncertainties
or disturbances.It shouldbe notedthat the total transitiontime, tf, can be treatedeitheras an
additionaldecisionvariableor asa predeterminedconstantparameter.
In the literature a number of different solution approaches to such dynamic optimization
problems have been proposed. A substantial subset of these methods are based on the idea of
modifying the infinite dimensional optimisation problem using discretization techniques and
applying then well-known nonlinear programming (NLP) methods to find the optimal
solution of the resulted system of the non-linear algebraic equations. The solution techniques
in this area fall into two categories.
Methods of the first category are known as simultaneous or infeasible methods. In
simultaneous approachesboth the control profiles and the state variables of the DAE system
are fully discretized and approximated with a suitable polynomial functions leading to a
large-scale but finite dimensional NLP problem. This approach is mainly advocated by
90
Biegler's group (Biegler, 1988) and despite initial work based on finite difference
approximation to the system constraints (Cannon eLal., 1970), global orthogonal collocation
on finite elements is the most dominant method applied for the DAE system discretization
and transformation into an NLP (Cuthrell and Biegler, 1987; Renfro 1987; Logsdon and
Biegler, 1989; Tjoa and Biegler, 1991; Cervantes et al., 2000; Biegler et al., 2002; Sage and
White, 1977). The latter can be solved with conventional nonlinear programming tools such
as generalized reduced gradient method (GRD) and successive quadratic programming

(SQP) (Edgar and Himmelblau, 1988). Based on the framework of this approach, the solution
of the DAE system is coupled with the solution of the optimization problem and
"simultaneous" convergence is achieved. Therefore the DAE system is solved only once, at
the optimal point, while intermediate iterations will generally be meaningless,justifying the
term "infeasible" attributed to this method. This means that no computational effort is wasted
in obtaining feasible DAE solution away from the solution of the optimisation problem. The
major advantage of the simultaneous approach to the dynamic optimization problems is the
potential for easy incorporation of path constraints oil both state and control variables. Due to
the global discretization, this method handles efficiently path constraints because all
variables are available at all times within the NLP and hence, the optimiser can see the
constraint violations at all discretization points along the path of the optimisation (Rowe,
1997). However, the complete problem discretization, considering that it results in exploding
problem size and ill-conditioning of the resulting NLP, making stiff the problem
convergence, raises the need for advanced specialized methods for efficient solution.
The methods of the second category, known as sequential or feasible methods, tackle the
above problems by confining the discretization in the space of the decision-control variables
only. Since discretization of the control variables is only necessarythese methods are called
control vector parameterization methods. The time domain is divided into a finite number of
intervals and the control variables u(t) are approximated for convenience by a set of
Lagrange polynomials describing the time change of the controls in every interval, while
piecewise constant and piecewise linear functions are the most common expressions.Starting
from an initial guess for the u(t), the values of the other decision variables and given the
initial conditions it is then possible to integrate the underlying DAE system applying well-
tested integration algorithms so as to evaluate the objective function (1) and the constraints
(11)that have to be satisfied by the solution. Then an outer optimisation loop, utilizing this
information from the DAE integrator, computes updated values for the parameters in the
control vector parameterization using a nonlinear programming solver until the optimal
91
solution is found. In this way a two level "sequential" optimisation is carried out with
intermediate solutions of the DAE system along a "feasible path" at each step
of the
optimization algorithm (Pollard and Sargent, 1970; Sargent and Sullivan, 1979; Morison,
1984; Gritsis, 1990; Vassiliadis et aL, 1994 a,b; Barton et aL, 1998). The sequenceof the
steps followed by this method is described in Figure 4.2. First an initial set of parameters,p,
are guessed and used to construct the manipulated variable trajectories u(t). These
trajectories are fed to the dynamic model, which after integration provides the 1-csulting
trajectories of the state variables. The latter are used to calculate the performance index,
which is fed to the optin-lizer, together with necessarygradients for the sensitivity analysis, to
choose a new improved set of parameters and the procedure is repeated until the optimum is
reached within a specified tolerance.
The sequentialapproachresults in a smaller size optimisation problem comparedto that

obtained by the simultaneousapproach, while it additionally offers the advantageof
efficiently controlling the discretization error by adjusting the size and order of the
integration stepsusing well-establishedODE/DAE integration techniques.It is acceptable
that the feasiblesolution methodshave a relative inability to deal with the inequality path
constraintscomparedto the simultaneousmethods.This is overcomeby establishingan
approachwhich relies on the definition of additional processvariables representingthe
constraint violations over the entire time horizon and penalizing theseviolation directly in
the objectivefunction or forcing
0 these variablesto zero throughend-pointconstraints.
Manipulated
Variable C
Trajectory--- (Construct Parameters
-
U(t)
Integrate
Optimiser
Model
Calculate
performance nde
State
and Gradients Per ormance
Variable
Index &
Trajectories
Gradients
Figure 4.2: Embedded model approach to dynamic optimisation under the sequential
method.
92
For the needs of the study worked out in this thesis, the sequential optimisation approach is
employed for the control parameterization based on a successive quadratic programming

NLP solver coupled with a backward-difference formula (BDF) for the time discretization-
integration of the DAE system. These tools are embeddedand well interfaced in the
gPROMS/gOPT (Process Systems Enterprise Ltd., London) computational tools for
modelling and dynamic process optimisation purposes.
4.4.4 Mathernatic Formulation of the Grade Transition Optimisation Problem

A thorough mathernatic statement of the optimisation problem is crucial for the faithful
representation of the grade transition problem. It should fully capture both the objectives and
the restrictions ruling the system, while incorporation of the designer intuition and
knowledge of the process is necessaryin order to constrain the process variables to lie within
the plant capabilities. It has been apparent throughout this chapter that the numerical solution
to the optimal transition problem should be based on the minimization of a suitable objective
function defined in terms of the changeover time, product quality specifications, process
safety constraints and the amount of off-spec polymer, using dynamic optimisation methods.
In the case of a grade transition between any two polymer grades for an ethylene-I butene
copolymerization FBR the performance measure should be an index of process profitability.

However, in order to avoid pure economic terms, such as on-spec and off-spec product value,
raw material cost operating and inventory cost etc., and creating a hypothetical scenario in
terms of time fluctuated market demand for different polymer grades and time horizon that
the process produces each grade, an implicit expression is developed instead. Since melt
index and density are indicative of polymer quality, and product with properties out of an
acceptable range over some desired values of MI and p is considered off spec, an integral
quadratic objective function is used as performance index penalizing deviations of polymer
MI and p from these desired final values over a time period.
tr (0 Mif
MI(t)
-
(P(t)-P,), (4.5)
to
mi
-
Mif
, Po -pf
The subscripts 0 and f denote the values of the corresponding "polymer quality" variables at
the start and the final time of a grade transition.
Suchan objectivefunction is very efficient for the needsof the gradetransition.Requiringby

the optimiserto minimize this function we demanda control variableprofile that minimizes
93
the deviations from the targets, namely the off-spec product. Additionally, by integrating
these deviations, the optimiser searches for the minimum time needed to reach the new
target, since the final time, tf, is treated as an additional control variable, ensuring a quick
transition. Therefore, both the major economic objectives during a grade transition (i. e., the
off-spec product and the transition time, which reflect to process profitability) are implicitly
incorporated within this performance criterion, and they are treated under equal relative
importance. Needless to say that additional terms (e.g., cross correlations,the polydispersity
index, the amount of off-spec polymer, etc.) or weighting factors on some objectives could
be included in the objective function modifying the optimisation problem, giving selectively
higher importance to some terms, resulting finally in alternative optimal profiles. The
performance criterion of Eqn (4.5) is written in terms of the cumulative polymer properties,
that is the properties of the total polymer in the reactor influenced by the reactor dynamics.
However, within this chapter it was discussed the importance of the instantaneousproperty
variations on the mechanical properties of the final product during a transition and they
should be properly included in the mathematical formulation of the problem. The dynamic
changes of the instantaneous properties, affected by the polymerization kinetics, are
significantly faster compared to the ones of the cumulative properties. In order to exclude
terms of different dynamic change levels from the objective function, that would make the
problem stiffer, process constraints have been selected to account for the restriction related to
the instantaneousproperties.
There are several aspects related to the trajectories of the control variables that will be
handled by the optimiser to drive the process from one grade to another. Under the control
vector parameterization dynamic optimisation method, the polynomial functions for the
approximation of the control profiles as well as the discretization of the time profile into a
finite number of intervals should be considered together. The knowledge of process
dynamics is necessary in order to assesswhether a certain number of changes (equal to the
number of time intervals) of the controls obeying a piecewise constant or pieccwise linear
profiles are adequate to achieve the optimum value of the performance index or a polynomial
function of higher degree and further discretization of the time horizon are needed. During
this study, the piecewise constant profile of the controls, supported by the gPROMS/gOPT
(Process Systems Enterprise Ltd. ) modelI ing-opti misation tool, is employed while a number
of time discretization scenarios (5,10,15,20 constrained or equally spaced intervals) were

tested in order to conclude that a policy of ten constrained time intervals is a good
compromise between the computational effort needed to solve the optimisation problem and
94
the "best" optimal value of the performance index that could be achieved. Comprehension of
process dynamics is required for the definition of the constraints imposed on these intervals,
and particularly on their minimum values, because for a relative short interval and sharp
variation of the decision variables, the process controllers wouldn't be able to follow such a
change setting in danger the process safety.
It is apparent that extreme changes of the control variables prompted by the optimiser in
order to accelerate the transition and lead the process faster to the desired grade are
detrimental both for product quality and implicitly for process economics and safety.
However these effects are not recognizable by the optimiser under the current expression of
process performance index. In order to make up for the deficient description of product
quality (e.g., the absence from the objective function of a penalty term for the deviation of
the MWD from a desired profile), constraints on the control variables, appropriate for each
time interval, are imposed accounting for the safety objectives, the operational capabilities of
the controllers and the restrictions related to the variations of the instantaneousproperties.
Through the constrained parameterization of the control variables it is expected that no path
constraints on the state variables (i. e., temperature, pressure, etc.) are needed to make sure
the safe process operation. However end-point constraints on a subset of the state variables
are essential to force the process to end-up after the transition in a desired steady state
corresponding to the desired polymer grade. With these constraints the mathematical
formulation of the optimisation problem is completed capturing efficiently a broad field of
the grade transition related aspects.
4.5 Conclusions
This chapter presented various schools of thought to address the multilevel process design
problem. The multiple dimensions were this problem is extended to (i. e., operability,
controllability, sizing and topology of the units, etc.) were discussed emphasising the
involvement of economic aspectscrucially affecting the approach applied to deal with such a
problem. Then, the process design problem was visited with respect to a grade transition
operation of the catalytic ethylene copolymerization FBR, and the theoretical-conceptual

background was built in ten-ns of dynamic optimisation algorithms and the mathematical
formulation of the problem, in order to prepare the substrate to deal with some practical
problems in the following chapters.
95
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101
CHAPTER 5
Optimal Control and Grade Transition

Operation of a PE FBR
It has been repeatedly emphasized in previous chaptersthat polymerization plants, in order to
satisfy the diverse product quality specifications required by the broad range of polyolefin
applications, are forced to operate under frequent grade transition policies. When dealing
with such process operating scenarios, the necessity of dynamic optimisation methods
applied on properly constructed optimisation problems that account for the changeover time,
the product quality specifications and the process safety constraints, was well demonstrated
in the previous chapter. However, considering the great impact that a given control structure
configuration can have on the process operability and product quality optimisation, the time
optimal grade transition problem needs to be addressed in parallel with the optimal design of
a closed-loop control system responsible to maintain the process within a safe operating
envelope and to apply the set-point trajectories proposed by the optimiscr changing the
product characteristics to comply with a new grade specifications at the minimum economic
cost.
In this chapter a Mixed Integer Dynamic Optimisation (MIDO) approach is applied to the
catalytic gas-phase ethylene- I -butene copolymerization fluidized-bed reactor (FBR)
presented in Chapter 3, in order to calculate both the "best" closed-loop control configuration
and the time-optimal grade transition policies. The gPROMS/gOPT computational tools for
modeling and dynamic optimisation, and the GAMS/CPLEX MILP solver are employed for
the solutiQn of the combined optimisation problem. Simulation results arc presentedshowing
the significant quality and economic benefits that can be achieved through the application of
the proposed integrated approach to the optimal grade transition problem for a gas-phase
polyolefin FBR.
102
Chapter 5 Optimal Control and Grade Transition Operations of a PE FBR
5.1 Integrated Solution of the Grade Transition Problem-MIDO
Due to the twofold nature of the grade transition problem, where both process controllability
and process operability issues are involved, traditionally, a sequential approach was adopted
to deal with these aspects. This means that a control system architecture was first assumed
or/and identified based solely on controllability or steady-stateeconomic criteria and then the
optimal open- or/and closed-loop control problem was solved. There is a large number of
publications, appeared in the open literature by several investigators, handling under the
above sequential philosophy the combined problem of optimal controller selection and
process optimisation during a grade transition in polymerization plants (Kravaris ct al., 1989;
Kozub and MacGregor, 1992; Ogunnaike, 1994; Meziou et al., 1996; Dabcdo et al., 1997; Ali
et al., 1998 Oshima and Tanigaki, 2000). However, the inherent dynamic character of the
grade transition problem is a strong incentive for an integration of dynamic controllability
and economic aspectsinto the calculation of the optimal processtransient operation.
When the discrete decisions involved in the problem of the control structure selection are
coupled with the identification of the appropriate dynamic profiles of the polymerization
process manipulated variables under the general concept of process optimality in terms of
both the discrete and continuous decisions, an advanced mathematical algorithm is required
to handle in a systematic way these issues. The growing recognition of the importance of
hybrid discrete/continuous dynamic systems motivated the investigation of appropriate
algorithms, capable of optimising a dynamic system coupled with discrete decisions, i. e.

classes of mixed-integer dynamic optimisation problems. The algorithm for Mixed Integer
Dynamic Optimisation (MIDO) problems is a strategic approach that optimally hands out
simultaneously discrete and continuous decisions, while it is extensively applicable to the

general process design problem and to the problem studied in this chapter in particular.
5.1.1 The MIDO Problem Formulation

The mathematicalstructureof a MIDO problem is very similar to that of a conventional
dynamic optimisation problem presentedin Chapter 4, Eqns (4.3) & (4.4).
fto'fF(x(t),
Min J=G(x(tt), y(tf), d, b, tf)+ y(t), u(t), d, b, t)dt
u(t), d, b,tf
103
Chapter 5 Optimal Control and Grade Transition Operations or a PE FBR
s.t. f (i(t), x(t), y(t), u(t), d, b, t) =0VtE [t., t, I
h(x(t), y(t), u(t), d, b, t) =0VtE [to

9tf]
ho(i(to), X(to), y(to), u(to), d, b, to) =0
hi(i(t), X(ti), Y(ti), U(ti), d, b, ti) =0 Vtj E [to, tf i=1 N

(5.1)
gi (i(t), X(ti), y(t), u(ti), d, b, ti ) tj e [to, tf I N
.50V ......
llb(b, d)= 0
gb(b, d) :50
beB= {O,Iln"
However, the presence of the integer variables, b, required for the mathematical
representationof the discretedecisions,togetherwith the continuousvariablesincreasesthe
problem's complexityand calls for properly modified solutionalgorithms.This featureof the
problem is additionally complicatedconsideringthat the 0-1 variablesappearboth in the
objective function and the processinequality-equalityconstraintsincluding the differential
equations.
5.1.2 Solution Approaches for MIDO Problems

The general idea behind the developments of a solution strategy for MIDO problems is to
formulate sequencesof rigorous sub-problems, which are easier to solve than the original
problem. These sub-problems will provide valid (upper and lower) bounds to the optimal
solution, similar to standard MINLP algorithms, leading to convergence within a finite
number of iterations. Therefore, an analogy of the algorithmic approaches to MINLP
problems has been developed to deal with mixed integer dynamic optimisation problems.
Floudas (1995) presented an excellent review on MINLP solution algorithms with detailed
and analytical discussion on these algorithms. Several popular approachesused for MINLP
problems have been examined to MIDO problems as well. Two representative classes of
algorithms for MINLP problems that have been extended to apply to MIDO problems arc the
branch-and-bound and the decomposition techniques.
A distinctive feature of the a branch-and-bound approach to MIDO problems is the need for a
continuousrelaxationof problem (5.1) togetherwith the ability to solve this relaxationto

global optimality. However, both theoretical and practical difficulties arise from the required
104
relaxation to such problems since there are problems described by a DAE system, which
might be solvable for integer values of b but not solvable for one or more values of the
relaxed bE (0,1). Besides, the relaxation of the integer variables poses some numerical
problems on the solution of the DAE system related to the index of the system. Allgor and
Barton (1999) noted that the index of the mathematical problems (5.1) can vary locally when
b lies in the interval (0,1) even though the index may be well defined for integral values of
b. These index variations usually give rise to severe numerical problems to the solution of
high index DAEs (Feehery and Barton, 1996). Androulakis (2000) proposed a branch-and-
bound algorithm for solving MIDO problems that arise when attempting to systematically
reduce the complexity of kinetic mechanisms, ending up with a dynamic optimisation

problem with relaxed binaries b. The author, recognizing the deficiencies of the branch-and-
bound technique, acknowledged that this algorithm is unsuitable for all but very small MIDO
problems since it will typically involve the solution of a much larger number of dynamic
optimisation problems. This is becausethe branch-and-bound approach to MIDO problems is
doomed to explicitly enumerate the branch-and-bound tree. In contrast, the decomposition
approach does not require a global solution of the dynamic optimisation problem, while it
additionally offers the potential to avoid complete enumeration of the discrete space.
Decomposition approaches to MIDO problems follow the developments of MINLP
algorithms with appropriate extensions to account for the DAE system. Therefore the basic
solution philosophy is maintained, that is iterative formulation of rigorous upper and lower
bounds by decomposing the problem into sequencesof a "primal" sub-problem with fixed
binary variables and a "mastee, sub-problem respectively, which determines a new binary
configuration for the next "primal" problem. Convergence is achieved when the upper and
lower bounds approach within a desired tolerance. However, the current solution techniques
for MIDO problems differ, at first level, on their treatment of the DAE system in order to
transform the dynamic optimisation into a conventional NLP problem.
One approach is to completely discretize the system (in consistency to the "simultaneous"
solution approach-seeprevious chapter) using a technique such as the orthogonal collocation

on finite elements. Then the problem (5.1) is directly converted into an M INLP problem and
solution is ensured applying well-known methods such as the Outer Approximation and its
variant, Outer Approximation/Equality Relaxation/Augmented Penalty (OA/ERJAP)

(Viswanathan and Grossmann, 1990; Avraarn et al., 1998,1999) and the Generalisedbenders
Decomposition (GBD) (Geoffrion, 1972; Mobideen et al., 1996). This approach to MIDO
105
problemsexhibitsthe sameadvantages and drawbacksof the "simultaneous"solutionmethod

to simple dynamic optimisation problems.Therefore,the large size of the resulted NLP
problem composed by the complete discretization, which might render the problem
intractable,sets this approachunsuitable for large dynamic systemsand prompts for an
alternativeapproach.
This alternative approach employs the control vector pararneterisation technique for the
treatment of the system of DAEs of the MIDO problem. In this case, for given u(t) and
values of the time invariant search variables d, the DAE system is integrated using standard
algorithms and accordingly the problem decomposition technique is properly modified to
adapt to the current approach of the MIDO problem under the "reduced spacediscretization".
Therefore the "primal" problem corresponds to the dynamic optimisation problem under a
fixed set of integer variables, while the necessary gradient information with respect to the
objective function and constraints is obtained through integration of the sensitivity equations
(Vassiliadis et al., 1994a,b) or solution of the adjoint equations (Bloss et al., 1999).
The construction of the "mastee, sub-problem under this approach poses the second
difference among the MIDO solution methods. The formation of the "mastce'sub-problem is
based either on the OA/ER/AP or the GBD method. In the first case lincarisation of the
objective function and the is

constraints applied (Schweiger and Floudas, 1997) in contrast to
the GBD method where the solution of the "primal" sub-problem and the corresponding dual
information are required (Mohideen et al., 1997; Allgor and Barton, 1999). Although the OA
methods require the solution of fewer "primal" problems-computationally demanding

dynamic optimisation problems-the GBD method dominates over the former in the sensethat
the OA methods are restricted only to problems where binary variables appear linearly and
separately in the objective function and constraints (Schweiger and Floudas, 1997).
In this work a decomposition solution method is applied for the MIDO problem, related to
the grade transition problem, based on the control vector parametcrisation technique, as far as
the DAE is
system concerned, and the GBD method for the construction of the "master" sub.
problem. However, an innovative alternative approach of this decomposition method of

MIDO problems has been adopted for problem solution with less computational effort. This
solution method contributes in the expansion of the handiness and the applicability of the
MIDO algorithm as a powerful tool for complex process system engineering problems.
Extensive description of this method as it has been applied in the current work is presented in
Appendix C.
106
5.2 The Combined Optimisation Problem
Themain disadvantageof the sequentialapproachto the gradetransitionproblem discussed

at the beginningof this chapteris that the control structureis selectedindependentlyof the
optimal transition problem and, therefore,the optimality of the selectedcontrol structure
cannotbe guaranteed.Underan integratedrevisionof this problem,attemptedin this chapter,
the dynamic optimisation problem is coupled with the selection of the optimal control
structure. To addressthis issue, the grade transition dynamic optimisation problem is
reformulatedas a mixed integer dynamic optimisation (MIDO) problem and the innovative
algorithm describedabove is employed to calculate simultaneouslythe optimal control

configuration and the optimal transition policy. Optimal continuous decision variables
(correspondingto the optimal control trajectoriesand the tuning parametersof the feedback
controllers) and optimal discrete decision variables (correspondingto the "best" control
pairings) are identified within the combined optimisation problem of considerable
complexity.
Recalling the grade transition problem in relation to the olefin polymerization FBR process
described in previous chapter, under the MIDO framework applied in the current approach
the two "product (i.
quality" variables e., p and MI) were held under optimal feedforward
the remaining four (i.

process variables e., T, P, h, and Rp) were kept under PI
control, while
feedback control. A multivariablc control configuration among the six controlled variables
(Yj: T, P, h, Rp, p, MI) and the eight manipulated variables (Ui: F.. ni, Ratio = F.. n2/F..,,,,
FH,,FN, Ft, F.,,t, Fbleýdand F,,) was identified using a MIDO approach. The discrete
,
decisions emerge through the identification of the manipulated variables that will provide
product quality and safety control to the process in a multivariable control scheme.
Therefore, the selective control linking-pairing of the control and manipulated variables is
representedvia the integer variables. The values of these time invariant binary variables, bij,
in the "master" sub-problem. The binary variable bij was set equal to I when
were calculated
the T manipulated variable was coupled with the 'j' controlled variable. In any other case,
the value of bij to The GAMS/CPLEX MILP algorithm was employed for
was set equal zero.
solving the "master" sub-problem. In the "primal" sub-problem the time optimal control
trajectories of the two "product quality" feedforward controllers and the tuning parameters
(i. e., gains and integral times) of the four PI feedback process controllers were estimated
PSE Ltd. Accordingly, the overall control action for the T
using the gOPT optimiser of
107
manipulatedvariable was calculated by adding the contributions of both feedback and

feedforwardcontrollers:
Ui, (t) Ui, (t) + Ui, (t)

total -: feedback feedforward (5.2)
or
4t6
(t) býj(Ke ij (Ej (t) +If Ej(t) dt 1: fbi. Uj,. 1 (5.3)

ui, + j
tow j=l ,, TI, ij 0 j-5 P,
Kc,ij and Tq denote the gain and integral time of the PI feedback controller for the (ij) pair of
manipulated-controlled variables. The difference term Ej (=Yj,, p-Yj) is the error between the
set-point and measured values of the 'j' controlled variable. Ui, is
f,,df,,,., d the time optimal
trajectory for the T manipulated variable calculated by the gOPT optimiscr, as a sequenceof
piecewise constant values.
It is importantto point out that the total numberof possiblecontrol combinationsbetweenthe

six controlledand the is
eight availablemanipulatedvariables prohibitively large.Therefore,
heuristic rules based on physical limitations on the possible control alternatives were
to
employed eliminate infeasiblepairings (i. e., the pairing of bed heightwith the coolantnow
rate)and reduce the binary search space in the "master" sub-problem.
5.3 Mathematical Problem Formulation
For a documentary evaluation and assessmentof the MIDO approach, the grade transition
problem was perceived from two perspectives. Specifically, the time optimal control problem
for the transition between two grades, from grade A to B and back to A, was solved first
under a fixed process control scheme, following the conventional sequential approach and
then under variable control configurations, following the MIDO approach. Despite the
conceptual differences between these approaches, there are though some mathematical
similarities in the problem formulation, which are treated together.
Commonly, in grade transition problems the time optimal trajectories of the control variables
are sought to drive the process from one grade to a new one. The mathematical statement of
the problem invokes the formulation of an objective function, the minimization/
maximization of which captures the optimisation issues related to the proccss-switching
108
problem from grade A to B and back to A. The performance criterion employed in this study
was presentedand fully commended in the previous chapter:
tr ( MI(t) )2 (P(t) )2 Idt

-mlf -pf
j=
f
t.
Mio
-mif Po -pf
(5.4)
This objective function is minimized subject to a system of differential and algebraic

equations (DAE system of 34 differential and 309 algebraic equations) corresponding to the
process mathematical model, developed in Chapter 3 and Appendix A, which describes the
process dynamics and the polymerization mechanism. The selected product spccifications
for grades A and B as well as the corresponding operating conditions at steady state are
reported in Table 5.1. As can be seen, the transition from grade A to B results in a polyolefin
having a higher melt index, MI, and a lower density, p. An opposite behavior is obtained for
the transition from grade B to grade A. Note that for polymer density and MI a range of
± 0.05% and ± 4% respectively over their desired values is defined, denoting an acceptable
area of quality properties within which the produced polymer is considered on spcc. From the
set of the potential manipulated variables, FbIecd
when not used as manipulated variable is
fixed at its lower bound to, avoid unnecessary bleeding of the recycle strcarn since it was
assumedthat all the feed streams were exempted from impurities.
Table 5.1: Operating conditions and product specifications for gradesA and B.
Operating
Grade A Grade B
Conditions
h,p (m) 6.0 6.0
T. p(K) 360 360
P,,p (bar) 21 21
Rp,,p(g/s) 2390 2390
FbIeed (9/S) 0.1 0.1
F,,ýc(g/s) 1.33 105 1.33 105
Product specifications
M,,, (g/mol) 3.8 10' 2.9 10'
02 0.024 0.046
P (g/cm, ) 0.9299 (±0.05%) 0.91904 (±0.05%)

ml 0.01376 (±4%) 0.03604 (±4%)
109
However, in case FbIeed

is selected as manipulated-optimisation variable then its final value at
the end of every transition is constrained to equalize its lower bound. The remaining process
input-outputs (i. e., F, FN Fut, Fm. 1,Ratio, F F,. t) were treated accordingly, while their
2, H2,
values derived from a steady-state maximization of process conversion, with the product
specifications used as equality constraints, in order to ensure maximum profitability at
steady-stateprocessoperation.
In the formulation of the dynamic optimisation problem it is pointed out that no path
constraints were imposed on any of the process variables to avoid computationally surcharge
the optimisation problem. However, to compromise the previous simplification in order to
guarantee a safe operating envelope for the process during the transition, path constraints
were imposed on the optimisation variables, which were easier handled by the optimiser. On
the other hand, upper and lower end-point constraints on selective variables were
unavoidable. Precisely, end-point constraints on T, P, h, Rp, p and MI were set to ensure the
satisfaction of the specified values at the final time, tf, and completion of the transition at the
desired operating point. It is important to point out that, due to the slow dynamics of MI
caused by the polymer mass accumulation, an end-point constraint on the time derivative of
MI was also introduced to ensure the attainment of a steady state. In the present study, the
gOPT sequential optimiser of PSE Ltd was employed for the solution of the time optimal
control problem.
5.3.1 Fixed Control Structure Approach

In this case, a multiloop single-input, single-output control configuration was first identified
via the application of the RGA analysis to a linearized form of the process model. For the
RGA analysis, six controlled variables (i. e., T, P, h, p, MI and Rp) and eight manipulated
(i.
variables e., F.. Ratio, FH, FNý Fat, F. Fblýed
and F,,) were considered, as it was
ni, , t,
'
discussedin details in Chapter 4, where the resulted "best" control pairings from the
applicationof the RGA analysiswere presented(seetable 4.1). The remaining two control
variables (FbIeed, )
F,., were held constantat their optimal values found via the solution of a
static optimisationproblem that the
maximized monomer conversion. According to the RGA
results,the first four (i.

manipulatedvariables e., Fw, FN, F.. F. were employedfor the
, t, nI)
feedback control of the reactor temperature, pressure, the bed height, and production rate,
110
while the remaining two control variables (i. e., Ratio, F11.) were chosen for the dynamic
optimisation of the "polymer quality" variables (i. e., p and MI).
The calculation of the time optimal trajectories for the comonomer to monomer ratio and the
hydrogen feed rate and the optimal values of the tuning parameters (i. e., gain and integral
time) of the four PI feedback controllers, were calculated by solving a dynamic optimisation
problem for minimization of the objective function (5.4). A piecewise constant profile was
employed for the time varying optimisation variables under the control vector
parameterization technique, while the time domain was discretized into 5 intervals for each
transition (either A -+ B, or B -> A) with the length of every interval used as optimisation
variable. Therefore, the total number of calculated discrete control moves and single-value
control parameters together with the time interval durations was 38, while for any additional
time varying control variable, depending on the structure of the control scheme, that number
was increased by 10. In general, 3040 iterations were required for the convergence of the
sequential optimiser to the optimal solution.
In Figures5.1 and 5.2, the calculatedoptimal trajectoriesfor p andMI (markedby the broken
lines, OPI) are plotted with respectto time. As can be seen,for the A to B gradetransition,
the time requiredfor the "polymer quality" variablesto reachtheir correspondingend-point
specificationsis lessthan 300 min. However,the optimisercontinuesto updatethe set-point
valuesof the feedforward"polymer quality" controllerstill the FBR reachesa steadystate.
the FBR undergoesa reversetransitionfrom gradeB to gradeA.
Subsequently,
It is important to point out that the time required for a grade transition largely dependson the
direction of change of polymer properties. More specifically, the transition time required for
a decrease (i.
of a polymer property e., p, MI) from its current value to a lower one, is in
general larger than that for a corresponding property increase. In fact, when the polymer
density decreasesduring a grade transition (e.g., A -4 B), the butene composition in the bed
increases,leading to an increaseof the transition time due to the lower polymerization rate of
butene. On the other hand, when the density increases (e.g., B --)A), the transition time
decreasesbecausethe polymerizationrate of ethylene is higher than that of butene.The

resultsof Figure 5.1 are in full with
agreement the previouskinetic justification. In the case
of MI, its increaseor decreaseis directly relatedto the weight averagemolecularweight of
the polymer(seeEqn (3.32)),which is controlledby the hydrogenconcentrationin the bed.
Thus, when the polymer melt index increasesduring a gradetransition(e.g., from A to B),
the hydrogenconcentrationin the bed increases,which lowersthe value of M,. On the other
III
hand,a decreasein MI leadsto a decreaseof hydrogenconcentrationin the bed. However,

due to the faster dynamicsof hydrogenconcentrationrepletion, the transition time for an
increasein MI will be faster than that required for a correspondingdecreaseof MI (see
Figure5.2).
To further reduce the transition time, alternative heuristic approaches based on "best"
industrial practice, were investigated. Thus, besides the two control variables identified by
the RGA analysis (F.., Ratio), additional control variables including the bleed flow rate,
FbIeed,
and the set points of the bed height, h,p, and production rate, Rp,,p, feedback controllers
were considered for solving the optimal grade transition problem. Several combinations of
hp and Rp, were examined in order to
the five control variables (i. e., F.., Ratio, FbIeed, ýp)
minimize the total transition time and the amount of off-spec: polymer produced during the
grade transition sequence from A to B and back to A. The best performance was obtained
when, in addition to the time optimal trajectories of FH, and Ratio, the set points of the bed
height and production rate PI feedback controllers were optimally varied with respect to time.
0.932
0.930 Grad ....

...... eA
...................... ...i
........................................... .........................
: ±0.05%
Density-OP1
0.928
Density-OP2 70 min
I
6-100.926 I
I
0.924
0.922
0.920 *.+0.05%
........ ..
Grade B
................................................................
0.918
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.1: Calculated optimal density profiles for the transition from grade A to B and back
to A for a fixed control structure obtained via the RGA analysis.
112
Chapter 5 Optimal Control and Grade Transition Operations or a PE FBIZ
0.040-
0.038 -
6raie ............................ ............
0.036- .
. ........... f ... .......... I--
0.034- :.+4%
0.032 -
All-OPI
0.030-
50 mins -All-OP2
0 028-
.
0.026-
0.024-
0.022 -
0.020- 20 min
0.018
0.016
0 014 . ................... t ...........
. if
ra eA ............... ........... ......................... .
............... .
0.012 ...................... ........... ........................
0 100 200 300 400 500 600 700 800

Time (min)
Figure 5.2: Calculated optimal MI profiles for the transition from grade A to B and back to
A for a fixed control structure obtained via the RGA analysis.
80
..................... Z. 4 tn ------------
7( ........................ ................................
6C
50
A."
40
55 min.
30
20
10 Offspe C-OPI
Offspec-OP2
0
0 100 200 300 400 500 600 700 800 900
Time (min)
Figure 5.3: Calculated amount of off-spec polymer production for the transition from grade
A to B and back to A under fixed control structure for the optimisation policies OP I& OP2.
113
In Figures 5.1 and 5.2, the optimal profiles (marked by the solid lines, OP2) for p, and MI are
plotted for the "besf' alternative grade transition policy. As can be seenwhen the four control
variables are used to minimize the objective function (5.4), the total transition time as well as
the amount of off-spec polymer are reduced by 5.4% and 6%, respectively as it is
demonstratedin Figure 5.3.
5.3.2 Variable Control Structure-MIDO Approach

Subsequently,the time optimal grade transition problem was solved in combination with the
optimal selection of the feedforward and feedback control loops, using a MIDO algorithm. In
the "primal" sub-problem, the dynamic optimisation problem was developed alike to the one
used in the fixed control-structure problem based on the same objective function (see Eqn
(5.4)). In addition, a set of continuous time invariant search variables, b, were introduced to
integer ý, identified in the "master" sub-problem. Upper

represent the equivalent variables,
and lower end-point constraints on the process and "polymer quality" variables were imposed
as discussed in the fixed control-structure case.
In the "master" sub-problem,a new objective function was formulated in terms of the
objectivefunction and the Lagrange
multipliers, co,identifiedat the "primal" sub-problem:
L(b) = Jopt + (OT(b - b) (5.5)
A set of equality and inequality constraints were imposed binary ýjj, to

on the variables
ensure that all the process variableswere held under feedback control and a manipulated
variable could be used for the feedforwardcontrol of only one "product quality" variable.
Note that the initial binary searchspaceincluded2 16combinations.In Table 5.2, the imposed
constraintson the binary variablesare As
reported. can be seenthe coolant flow rate, F, and
the product removal, F,,u,, are only used to control the temperatureand the bed height,
respectively. Moreover, the comonomer/monomerratio and the hydrogen feed rate are
alwaysusedin the respectivefeedforward controllersof the polymer densityand melt index,
is
which consistentwith the resultsof the RGA analysis.
114
Table 5.2: Constraints imposed on the bij binary variables.

T Ph RP P MI
F., 1 0 0 0 0 0. EbIj 51
-:
F, 0 (0, 0 0 0 0 b2j 51
2
Fý, 0 0 1 0 0 0 2:
6.,
b34 51
0 (0,1) 0 (0,1) 0 0 Eb, 51

j:
Ratio (0,1) (0,1) 0 (0,1) (011) (0,1) 2: b, 51

j:
F, 0 0 0 0 (0,1) (011) Fbj: 51

, J. 5
6
Fbkcd 0 0 0 0
(0,1) (0,1) 2: blj: 51
F, (0,1) 0 0 (0,1) (0,1) (0,1) Z bsj

at , -51
- J-5
b, b43 2t 1 bi., 2:1 bi. 2t I 2: bj, 2t I

2 5 6
i
Table 5.3: Calculatedoptimal control structurefor the A to B gradetransition.
IT MI JIT P h Rp MIIIT P h Rp p mil

P h Rp p p
F 1 0 0 0 0 0 1 0 0 0 0 01 0 0 0 0 0,
FN, 0 1 0 0 0 0 0 1 0 0 0 00 1 0 0 00
F. 0 0 1 0 0 0 0 0 1 0 0 00 0 1 0 00
,
F. 0 0 0 1 0 0 0 0 0 1 0 00 0 0 1 00
,
Ratio 0 0 0 0 0 1 0 0 0 0 1 01 0 0 0 10
FH, 0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 01
Fbleed 0 0 0 0 0 0 0 0 0 0 1 00 0 0 0 10
F 0 0 0 1 0 0 1 0 0 0 0 01 0 0 0 1 0-
a. Initial control structure b. Control structure I c. Final control structure

(OPTINIAL)
115
In Table 5.3, the initially guessedcontrol structuretogetherwith an intermediateone and the

final-optimal one calculatedby the MIDO algorithm are reported for the transition from
gradeA to B. As canbe seen,in the optimal control structurethe polymerizationtemperature
is controlledby three manipulatedvariables(i.e., F, Ratio, F,. while the polymer density
t),
and melt index are controlled by the set of variables (Ratio, FbIeed, F,.t) and the FH'
,
respectively. It is pointed out that 3 iterations were required for the convergence of the
MIDO algorithm to the optimal solution. Analytically, 'the algorithm convergenceprocedure
is described in Table 5.4.
Initially, one of the competitive control structures was arbitrarily chosen as the most
promising one. As can be seen, the main difference of the initially guessedcontrol structure
with the one obtained by the RGA analysis is the incorporation of Fct as manipulated
variablewhich is quite reasonableto be usedfor the feedbackcontrol of polymerproduction
rate. Furthermore, the pairings of p-Ratio and MI- FH were intentionally inverted to test the
2
algorithm capabilities. The first "primal" sub-problem was conducted returning an upper
bound of the final solution, optimal tuning of the controllers and optimal trajectories of the
optimization variables, as well as a set of Lagrange multipliers to the first "master" sub-
problem. The next "Primal-Master Solutions" were derived accordingly until the third
iteration when the algorithm convergencewas achievedand the optimal solution denotedby
the third "primal" sub-problem.It should be noted that the samecontrol structuresequence
was verified as the optimal one for the reverse transition from grade B to A.
Table 5.4: MIDO algorithm convergencecharacteristics for the transition form grade A to B.
Iteration 1 2 3
Primal-Problem Solutions:
Control Scheme Table 5.3 (a) Table 5.3 (b) Table 5.3 (c)
Objective Function 5.5805 5.04816 4.97985
Upper Bound 5.5805 5.04816 4.97985
Master-Problem Solutions:
New Control Scheme Table 5.3 (b) Table 5.3 (c)
Lower Bound 5.042312 5.047902 5.052534
UB - LB < 10-5 NO NO YES-STOP
116
In Figures 5.4 and 5.5, the calculated by the MIDO algorithm optimal profiles for p and MI
(marked by the broken lines, OPI) are plotted with respect to time. To further reduce the
transition time, the set-points of the bed height, h,,p, and production rate, Rp,ýp, feedback
controllers were treated as additional control variables. The optimal profiles for p and MI
(marked by the solid line, OP2), derived under the second optimisation policy, are also
plotted in Figures 5.4 and 5.5, respectively. It is apparent that the use of the two additional
control variables significantly improves the performance of the system, resulting in a
decrease in the total transition time by 5 %. At the same time, the amount of off-spec
polymer is further reduced by 7.7 % (see also Figure 5.6).
Figures 5.7-5.10 depict the calculated time optimal trajectories of the four optimisation
(i.
variables e., Ratio, FH, hsp,Rp,, Note that the calculated trajectories for the Ratio and
, p).
FH,represent the feedforward contributions of the two control variables to the multivariable
controller given by Eqn (5.3), while the calculated trajectories for h,p and Rp,.p are applied to
the respective PI feedback controllers as piecewise set-point changes.
0.93,
...........
0.93C Grade A
......................... ..........
........................... f ....................... ...... ....................
±0.05%
0.928
U.92(j -70 min
0.924
Density-OPI
0.922 !-35 min Density-OP2
0.920 +0.05%
..... ... ...
.......................... ....................
0.918
0 100 200 300 400 500 buo luu buu
Time (min)
Figure 5.4: Calculatedoptimal densityprofiles for the transitionfrom gradeA to B and back
to A for a variablecontrol structureobtainedby a MIDO algorithm.
117
Chapter 5 Optimal Control and Grade Transition Operations
of a PE FBR
^
U. Vel
0.03 1-1%11-OIjP2
Nil-OPI
JL...
0.031 ........... .... .................. ... -I
. Grade B
0.0,34 .......... ............................... ....
4%
0.01
0.03(
0.021
0.02E
0.024
Z
0.022
0.020 --. 70 min
0.018
0.016
0.014 f
.............. ............................ ......
................................ I .........................................................
0.012 : -+4%
0.010
luu wuu 300 400 500 600 700 800
Time (min)
Figure 5.5: Calculated optimal MI profiles for the transition from grade A to B and back to
A for a variable control structure obtained by a MIDO algorithm.
70
................................ ........................................ .............

-5 tn Grade A
61
.............................................................
5(
C60
4C
t
960 ........................ .......
3C .................
Grade B
ttI 30 min
020 ..........
10 Offspec-OP1
Offspec-OP2
0
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.6: Amount of off-spec polymer produced under different optimisation policies
using a MIDO approach.
118
Chapter 5 Optimal Control and Grade Transition0perations of a PE FBR
Grade A Grade A
: Grade B
0.14
1.0
0.8-,,
cl
1%
0.6=
ein
e- 0.08 460
0.4c
.........
0.06
D.2
0.04
............. ...............
0.0
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.7: Time-optimal control policies of the comonomer/monomer ratio and the
hydrogen flow rate for the transition from grade A to B and back to A.
14.0
Grade A : Grade B Grade A
---------------- -------------------
4.0
3.5
Q
3.0
..........
0
460
2.5
2.0 u
I
1.5
0 1.0
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.8: Time-optimal control policies of the bleed and catalyst flow rates for the
transition from grade A to B and back to A.
119
nnr
4.0ý;
Grade A : Grade B Grade:A
2.6C
2.55
2.50
"a 2.45
S
1.
2.40
L I'
2.35
2.30
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.9: Time-optimal set-point trajectory of the production rate feedback controller and
time variation of the respective controlled variable.
60! Grade A Grade B Grade A*
60C
595
590
585
580
575
570
565
560
all
555
550
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.10: Time-optimal set-point trajectory of the bed height feedback controller and time
variation of the respective controlled variable.
120
In Figure 5.7, the optimal trajectories for Ratio and F., are illustrated for the total transition
from grade A to B and back to grade A. It is apparent that for the A to B transition (e.g.,
increase of MI and decreaseof p), the comonomer to monomer feed ratio increases, leading
to a decreaseof the polymer density caused by the higher incorporation rate of 1-butene in
the copolymer chains. Similarly, the hydrogen feed rate initially increases, which brings
about an increase in the H2 concentration in the bed, resulting in a decreaseof the molecular
weight of the polymer and in an analogous increase of MI. On the other hand, for the
transition from grade B to grade A, the two control variables are optimally reduced to their
initial starting values.
In Figure 5.8, the optimal variations of the bleed and catalyst flow rates are plotted. It can be
seenthat for the A to B grade transition, the catalyst flow rate increasesto compensatefor the
lower reactivity of I-butene. Moreover, the bleed flow rate increases to accelerate the
transition of the comonomer and monomer gaseousconcentrations to the desired values. For
the B to A grade transition, the catalyst flow rate is optimally reduced to its starting value,
while the bleed flow rate initially operates at its upper limit to speed-up the change of the
comonomer/monomer composition in the gas phase to its optimal value. I Towever,the end of
the transition, it also returns to its initial operating value.
Figures 5.9 and 5.10 depict the calculated optimal set-point trajectories of the two process
controllers as well as the actual values of the respective controlled variables. It should be
noted that the polymer production rate PI controller closely follows the set-point changes.On
the other hand, the bed height P1controller exhibits significant overshooting when a decrease
in the bed height is required. From the results of Figures 5.9 and 5.10, it can be concluded
that, independently of the direction of the grade transition, an increasing policy with respect
to the production rate and a decreasing policy with respect to the bed height are always
required to reduce the changeovertime.
Finally, in Figure 5.11, the off-spec amount of polymer produced under both fixed and
is
variable control structures plotted with respect to the transition time. It is evident that a
significant improvement in the reactor performance is obtained when a MIDO approach is
employed for the solution of the combined optimal grade transition problem and the selection
of an optimal control structure. In this case, the total transition time as well as the amount of
off-spec polymer are reduced from their respective values obtained under a fixed control
structure, by 17.7 % and 15 %, respectively.
121
i
7c. .............................. .........................................
10 tn
6C. .............................
=
1.-ý
5c
gw
40
....................... ...... ......
-6 M
30
........... 150 min
20
10
Fixed Control Structure
-MIDO
0
0 100 200 300 400 500 600 700 800 900
Time (min)
Figure 5.11: Amount of off-spec polymer produced under a fixed (RGA) and a variable
(MIDO) control structure.
5.4 Post-Optimality Analysis
It is evident throughout this chapter that this optimization study of the dynamic operation of
the PE fluidized bed reactor during a grade transition was carried out under an off-line
optimization framework. This means that this study ignores primarily a possible mismatch
between the model and the real process, attributed either to model inability to correctly
describe the process operation in real time, or to inaccurate parameters used in the model to
mathematically representsome process features.
However, a reasonableway of assessingthe handinessof this work is by testing the

optimality of the operatingschemeproducedso far in the sameprocessbut this time under
the presenceof uncertaintyon various model parameters.Such a post-optimalityanalysis
would correspondto a hypotheticalscenarioof applying the optimal trajectoriesderived by
this study directly on a real process,wherethe presenceof disturbancesdeviatingthe model
inputs from their nominal values is the actual case. From this analysis some useful
conclusions can be drawn related to the capability of the model-based optimization scheme
122
Chapter 5 Optimal Control and Grade Transition Operstiom of a PE FBR
derived off-line in terms of damping and tolerating the model's uncertainty. Assessing the
degree of uncertainty and the change frequency of various model parameters this
optimization scheme might be used under proper modi f icati ons-simplif i cations in order to
apply the iterative model predictive control algorithm on this process.
In what follows next, this post-optimality analysis is applied on the PE fluidized bed reactor,
given the optimal trajectories obtained by the MIDO approach under the secondoptimization
policy (OP2) as it was presented in the previous section. The major sourcesof uncertainty in
such polymerization systems are traced in the catalyst processing stage, affecting the catalyst
morphological characteristics. Precisely, the catalyst activity (which is a measureof the metal
concentration in the catalyst that is active and can provide potential catalyst sites) and, in the
case of multi-site catalysts, the fraction of each catalyst site, are very common modeling
parameters enclosing a serious degree of uncertainty. In addition to that, the temperature of
the coolant stream fed in the external heat exchanger used to remove the beat of the reaction,
is another point of modeling uncertainty.
In the post optimality analysis attempted here the impact of the above uncertainties on the
process operating profile under the most efficient optimization scheme (MIDO-OP2) is
examined introducing separately a degree of deviation for each one of the above parameters
at a time. In Figures 5.12-5.14 the impact of uncertainty on catalyst activity is presented for
various degrees of deviation from its nominal value, in terms of MI, density and off-spee
production respectively. Given the acceptable range of properties, within which the polymer
is
product considered on spec, the polymer density seems to be unaffected by any degree of
deviation of catalyst activity from its nominal value (Figure 5.12). However, in caseof MI on
the other side, the optimization scheme can afford a catalyst activity deviation up to 2%
(Figure 5.13). Since both these polymer properties are taken into consideration for the
classification of a polymer product as on spec or off spec, from Figure 5.14 it is understood
that the current optimization scenario is valid only when the uncertainty on the catalyst
activity is up to 2% and the transition happens to be carried out more profitably since the
amount of the off-spec polymer is reduced by I ton approximately compared to the case
where the catalyst activity has its nominal value. For higher degree of uncertainty a
readjustment of the is
optimization scheme necessary.
123
Chapter 5 Optimal Control and Crade Trallsitioll Operatiolls of a PE FRR
rl rio I)
U. U, 3ý
0.93C ---------------------------- .................... .... - ..... ... ...................

- GradeA
........................... ......... ........... --------------------------------------
0.05R.
0.92E
0.926
I
Cat. activity noiiiiial %ahic
0.924 -----Moca(. activitý deviation

4*/,, cat. activit) dc%ialion
Cat. acliN ih (lc%illioll
0.922 lo, voeat. aokif) deNialion
0.920 0.05"
ýE o
.................
Gral...B.... ------------ -------
..................................................... 1.
0.918
0 100 200 300 400 500 600 700 800
TiRw (njin)
Figure 5.12: Impact of uncertainty of catalyst activity on the polymer density profile under a
predefined optimal operating policy.
0.040-
0.038 -
0.036- ---------- ----- -------------
4" o(i radc 13
n mA ............. J.
...........
V
0.032- Cat. activity: nominal valtic
0.030- 2"/,, cat. acfivilý deviation
Increasing
increasing cata lyst
catalyst
0 028-
a ct", ty uncertainty
4% cat. acti%itý deviation
. activity u ncert,'inty
"o 0.026 5'N, cat. acti%it %dc%iafioll
-
0.024-
10%,,cat. acti%if% (lc%iatioll
o-- 0.022
, -
0.020 -
0.018-
0.016-
0.014- - ....
---- (ý .... .... ..................
-- --*,. - '- ,"
.. - ------- 1 - .... * ----------
0.012- 4%
0.010
0 100 200 300 400 500 600 700 800

Time (min)
Figure 5.13: Impact of uncertainty of catalyst activity on the polymer MI profile undcr a
predefined optimal operating policy.
124
Chapter 5 Optimal Control and GradeTransition Operations of a 11FFRR
110
100
90
80
70-
tn
60 - Grade A
Z-1 ------------
........... ..........
50-
r.ý
40
301 -Cat. activity: nominal i alue

rade 13
2% cat. acti%ity deviation
20 4% cat. activily de%iation
-
- 5%, cat. activity deNiation
10
- 10%, cat. acliN ity de%ialion
0 100 2ýO 300 400 500 600 700 800

Time (min)
Figure 5.14: Impact of uncertainty of catalyst activity on the off-spec polymer production
under a predefined optimal operating policy.
Similar analysis is repeated for the case where uncertainty is introduced in the model llirough
the fraction of the catalyst sites of the two-site catalyst considered in this study. A range of
deviation of the catalyst site fraction from its nominal value up to + is examined. Once
again, although the polymer density is untouched by this type of model uncertainty (see
Figure 5.15) the transition ends up in off-spec product in terms of' MI (see Figure 5.16) for
any deviation of the catalyst site fraction higher than ± 2.5% from its nominal Value. In
terms of the off-spec polymer produced during the transition xNlien the catalyst site fraction of
the catalyst batch fed into the reactor is reduced by up to 2.5(Y,,from Its 110111111al
Value the
transition is completed with a benefit of up to 3 tones less of' off-spec polyrner, ýNlille a
respective increase of this fraction call result in an increase of' the otf-spec product by III) to
15 tones throughout the transition (see Figure 5.17).
125
Chapter 5 Optimal Control and Grade Transifion Operatiom ol'a Pl,. FBR
0.932-,
0.930 - ---------------------------------------------------- /,-*

Grade A±0.05'ý'o
iI..........................................
........................... .....................
0.928-
0.926-
CA Cat. site fraction:

I-- 0.924- I nominal %ahje
2.5%, deviafion of cal. site fraction
..... 2.5"Yo deN ia(ion of caLsite fraction
.
0.922- i -- 5%, deNiation ofcal. %itc fraction
deNiation of caLsitc fraction
0.920-
..........................
Grade B±0.05"o........................
......................... ..........................
0.918
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.15: Impact of uncertainty of the fraction of the active sites ofcatalyst oil tile
polymer density profile under a predefined optimal operating policy.
0.042-
0.040
0.038-
------------ Grade 13
0.036
0.034- ..............
0.032-
-Cat. site fraction: iloillillal %allic
0.030-
- 2.51%,deviation of cal. site fract ioo
0.028- 2.5%, deviation of cat. sile fractim
------
0.026- 5,vo deviation of cat. sile fraction
0.024- de%iafloii of cal. sile fractioo
0.022
0.020
0.018-
0.016
0.014- T! 0
............................. .................
0.012-
0.010
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.16: Impact of uncertainty of the fraction ofthe active sites of catalyst of] the
polymer MI profile under a predefined oplinial operating policy.

126
Chapter 5 Optimal Control and GradeTran-sitimi Operafions ol'a llpý FBR
110
100-
90-
80- 15 tn
C ...................... ........................................ ..... ......
70-
W3 tn Grade A
60 -
-------- ............. i-, ******'** ................ . ...... .
...................................... ....... eý. ....... . ------------------
2,50-
40-
30-
-Cat. site fraction: nominal ialue
Grade B
- 2.5'Vodeviation ofcal. si(e fraction
20-
------ 2.5(V(,deviation ofcal. sile fraction
10- 5% deviation ofcal. site fraction
deviation ofcat. sile fraction
011
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.17: Impact of uncertainty of the fraction ofthe active sites ofcatalyst on the off-
spec polymer production under a predefined optimal operating policy.
Finally, the last source of uncertainty in the model is introduced considering a sinusoldal
coolant temperature profile (amplitude 2 degrees and frequency (80 minutes)-') instead ol'a
constant one (see Figure 5.18). From Figures 5.19 and 5.20 it IS Concluded that the
optimisation scheme can easily handle such a model uncertainty. The transition end', Up III
on-spec product in terms of both density and Ml without serious dillercrices froin the profiles
obtained when the transition is carried Out Under the nominal Value of' the coolant
temperature.
In conclusion from this analysis it can be said that the optimisation scheme derked by the
MIDO algorithm can be applied under a short range ofuncertainty ofsonle model parameters
(]i.e. catalyst activity and the fraction of different active sites in the catalyst). HoAever, this
optimisation scheme can successfully drive a real process throughout a grade transition under
a significant uncertainty on the value of the coolant temperature. This nicans that the selected
control structure and the tuning of the respective feedback controllers was such that it can
afford some uncertainty on the model inputs (i. e., the coolant temperature) relaining the
process under optimal performance. A different perspective for the exploitition-cvAtiation of'
127
the optimization strategy presented in this chapter is that it can provide the off-line optimal
profiles of the process outputs as desired trajectories for the real process operating under a
model predictive controller. The latter based on a reduced space model, derived from the
original one, will take the necessary corrective actions for the control variables accounting
for disturbances on the catalyst activity and the fraction of catalyst active sites, in order to
minimise the deviation of the process outputs from the desired ones. Considering also that the
tra.ectories of the control variables are also known off-line, the model predictive controller
to
will need make small changesof the controls from these trajectories, depending always on
the degree of the disturbances.
294
-Nominal
Sinusoidal
9 292
ci
lw
ew
2 290 AA
288
VVVV
286
284
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.18: Temperature

profile of the coolantin the heatexchanger.
128
Chapter 5 Optimal Control and Grade Transition Operations of a PE FIIR
0.932
0.93C
0.92E
0.926
0.924
9z
0.922
0.920
0.9184
0 100 200 300 400 500 600 700 800
Time (min)
Figure 5.19: Impact of uncertainty of the coolant temperature on the polymer density profile
0.04(
0.03f
0.03E
0.034
0.032
0.03C
0.028
10
0.026
0.024
0.022
0.020
0.018
0.016
0.014
0.012
0 100 200 300 400 500 600 700 800

Time (min)
Figure 5.20: Impact of uncertainty of the coolant temperature on the polymer MI profile
129
5.5 Concluding Remarks
The optimal grade transition operation of a polymerization plant in terms of increased
productivity and improved product quality can only be achieved when the process is
effectively controlled. Since the close-loop control system configuration substantially affects
the calculation of the time-optimal control policies, it is of paramount importance the
simultaneous solution of the combined optimal grade transition problem and the selection of
the "best" closed-loop feedback/feedforward controllers for the plant. In the present study, a
mixed integer dynamic optimisation (MIDO) method was applied to a gas-phase olefin
copolymerization fluidized-bed reactor (FBR) to calculate the time optimal control policies
for a sequence of grade transitions and to identify the "best" closed-loop feedforward and
feedback controllers in order to maintain the process within a safe operating envelope and
ensure the faithful implementation of the calculated optimal control policies to the plant.
Based on the results of the MIDO analysis, four feedback controllers were identified to
control the three process variables (i. e., temperature, pressure and bed height) and the
polymer production rate. For the control of the "polymer quality" (i. e., polymer density and
melt index), two feedforward controllers were identified. The six output variables were
controlled by the combined action of eight manipulated variables (i. e., F, l7m, F. t, F.
* 1,
Ratio, FH, Fbjeed
and F,. t). To further reduce the transition time and the amount of off-spec
,
polymer produced during a grade transition sequence (i. e., A --> B -4 A), the set-points of
the bed height and production rate feedback controllers were treated as additional control
variables, which significantly improved the overall process performance. Moreover, it was
shown that the simultaneous solution to the combined problem of optimal grade transition
and selection of closed-loop control structure resulted in a superior performance of the FBR,
in terms of both reduced transition time and amount of off-spec polymer, over that obtained
under a fixed control structure derived by the RGA analysis.
The reduction of both the transition time and the amount of the off-spec product reflects to
economic gain for the process. Considering this profitability guaranteed for the process when
its operation is addressed within an integrated framework, this philosophy of accounting
simultaneously for various related process systems engineering problems of chemical

processes is adopted to handle, in the following chapter, another operating problem of the
same ethylene polymerization process.
130
5.6 Literature
Algor, R.J.; Barton,P.I. (1999).Mixed-integerdynamicoptimisation1:Problemformulation.

Comput Chem. Eng., 23, p. 567.
Ali, E.M.; Abasaeed, A. E.; AI-Zahrani, S.M. (1998). Optimization and control of industrial
gas-phaseethylene polymerization reactors. Ind Eng. Chem. Res., 37, p. 3414.
Androulakis, I. P. (2000). Kinetic mechanism reduction based on an integer programming
approach.AIChE J, 46, p. 36 1.
Avraam, M. P.; Shah, N.; Pantelides, C.C. (1998) Modelling and optimisation of general
hybrid systems in the continuous time domain. Computers Chem. Eng., 22 Suppl., p.
S221.
Avraam, M. P.; Shah, N.; Pantelides, C.C. (1999) A decomposition algorithm for the
optimisation of hybrid dynamic processes.Computers Chem. Eng., 23 Suppl., p. S45 1.
Bloss, K-F.; Biegler, L. T.; Schiesser, W. E. (1999) Dynamic process optimization through
adjoint formulations and constraint aggregation. Ind Eng. Chem. Res., 3 8, p. 42 1.
Dabedo, S.A.; Bell, M. L.; McLellan, P.J.; McAuley, K. B. (1997). Temperature control of
industrial gas phasepolyethylene reactors.J Proc. Cont. 7, p. 83.
Feehery, W. F.; Barton, P.I. (1996) A differentiation-based approach to simulation and

dynamic optimisation with high-index differential-algebraic equations. In M. Berz, C.
Bischof, G. Corliss, & A. Griewank, Computational differentiation. Philadelphia: SIAM.
Floudas, C.A. (1995) Nonlinear and mixed-integer optimization. Oxford University Press,
New York.
Geoffrion, A. M. (1972) Generalized benders decomposition. J OpfimLz. Theory & 4pplic.,

10,p. 237.
Kravaris, C.; Wright, R.A.; Carrier, J.F. (1989) Nonlinear controllers for trajectory tracking
in batch processes.Computers Chem. Engng., 13, p. 73.
Kozub, D. J.; MacGregor, J.F. (1992). Feedback control of polymer quality in semi-batch
copolymerization reactors. Chem. Eng. Sd, 47, p. 929.
131
Meziou, A. M.; Deshpande, P.B.; Cozewith, C.; Silvennan, N. T.; Morisson, W.G. (1996).
Dynamic matrix control of an ethylene-propylene-diene polymerization reactor. Ind. Eng.
Chem.Res.,35, p. 164.
Mohideen, M. J.; Perkins, J.D.; Pistikopoulos, E.N. (1996) Optimal design of dynamic
systems under uncertainty. AIChE J., 42, p. 225 1.
Mohideen, M. J.; Perkins, J.D.; Pistikopoulos, E.N. (1997) Towards an efficient numerical
procedure for mixed integer optimal control. Computers Chem. Eng., 21 Suppl., p. S457.
Ohshima, M.; Tanigaki, M. (2000). Quality control of polymer production processes.J. of

Proc. Cont., 10, p. 135.
Ogunnaike, B.A. (1994). On-line modelling and predictive control of an industrial

Schweiger, C.A.; Floudas, C.A. (1997). Interaction of design and control: Optimization with
dynamic models. In: Optimal Control.- Theory, Algorithms and Applications, W. W.
Hager and P.M. Pardalos,Eds., Kluwer Academic Publisherts B. V., p. 388.
Vassiliadis, V. S.; Sargent, R. W. H.; Pantelides, C. C. (1994a) Solution of a class of multistage
dynamic optimization problems. 1. Problems without path constraints. Ind. Eng. Chem.
Res., 33, p. 2111.
Vassiliadis, V. S.; Sargent, R. W. H.; Pantelides, C. C. (1994b) Solution of a class of multistage
dynamic optimization problems. 2. Problems with path constraints. Ind. Eng. Chem. Res.,
33, p. 2123.
Viswanathan, J.; Grossmann, I.E. (1990) A combined penalty function and outer
approximationmethodfor MfNLP optimization. Eng.,
Chem.
Computers 14,p. 769.
132
CHAPTER 6
Optimal Production Campaign

Scheduling in a PE FBR
In this chapterthe transientoperatingproblemof polymerizationprocessesis revisitedwith

the prospectto accountsimultaneouslyfor additionallevelsof the processsynthesisproblem.
More specific,it hasbeenclearly statedthat the problemof off-specpolymerproductionand
grade transition time minimization, in terms of the off-line and/or on-line dynamic
optimisation of the transientoperatingprofiles in polymerizationprocesses,has been the
subjectof a numberof previousstudies.However,in general,the problem was restrictedto
find only some optimal trajectoriesfor the transitions, ignoring the need for production
schedulingarising from the productionof multiple products.It is known that the processing
sequencehasprofoundimplicationsfor continuousmultiproductplantssincethe switch-over
cost is processingsequencedependent.In this chapter, the optimal sequenceof grade
transitionsis examinedin relation to the Ziegler-Nattacatalytic gas-phasecthylene-l-butene
copolymerizationfluidized bed reactor (FBR) presentedin Chapter3 and Appendix A. A
two-level decompositionapproachis appliedto addressthe schedulingproblem,considering
the impact of both transientoperationand the sequenceof transitionson off-specproduction
and transition time. The combinatorial nature of the problem, where both discrete and
continuousdynamicdecisions calls
are necessary, for a mixed integerdynamicoptimization
(MIDO) approach.Simulationresultsdemonstratethe significanteconomicbenefitsachieved
in terms of off-specproductionand transitiontime througha simultaneousapproachof the
schedulingsubproblemsapplying the MIDO algorithm discussedin details in the previous
chapter.
133
Chapter 6 Optimal Production Campaign SchedulingIn a PE FBR
6.1 Problem Statement-Motivation
The productionprofile that the polymerindustrieshaverecentlyadoptedindicatesthe current

trend in the polymer manufacturing industry to move towards continuous flexible
multiproductplantsthat can respondfasterto demandchangesand to processingof a variety
of products.With the currentdemandfor polymers,whosepropertiesarenow clearly tailored
to specific applications,and the requirementfor manufacturingan increasingnumber of
different grades of a given basic polymer, the issue of how to operate polymerization
processesascontinuousmultiproductplants*in an efficient manneris growing in importance.
The multiproduct characterof polymerization plants arises primarily from the variability
observedin the market demand,which imposesfrequent grade transition policies on the
polymerizationplants.However,running a continuouspolymerizationprocessunderregular
gradechangeoverpolicies is a severebut necessarydisturbancefrom steadystateoperating
conditions.
The problems related to the transient operation of polymerization processeshave been well
documented so far in this thesis. The polymer product produced during a transition is off
spec, since it does not meet the specifications of either the initial or the final product, hence it
must normally be sent to waste treatment facilities. This problem combined with the usual
long residence time (_ 104 sec) and therefore long transition time of continuous
polymerization reactors, result in an exceptionally large amount of off-spec product and

consequently in a serious treatment and product loss problem. Due to the frequency of grade
transitions in a processproduction plan; resulted from the multiproduct nature of the process,
the economic impact of both the aforementioned problems on process performance is
seriously amplified. Therefore, these problems and any other unforeseen difficulties that
might arise should be efficiently handled in a way that renders transient operation as routine
and well managed as steady state operation. Such an objective poses a multilevel process
synthesis problem and an integrated approach is required in order to develop an economically
viable process, accounting for the significant process complexity that distinguishes the
multiproduct continuous polymer processes, where different products are produced in a
sequentialmode.
*Multiproduct plant is the plant where each product may go through the same processing sequence and in the
A is
same order. multiproduct plant usually employed to produce similar products, for instance, different grades
of the same polymer. Multil2urpos in
plant contrast, is the plant where different processors will be required for
different products, and different products may follow alternative paths through the processors.
134
6.2 Current Research Orientation
There are a number of different perspectives from which the process synthesis problem for
multiproduct plants can be viewed. Research in process design and process control is clearly
of relevance. Economic optimisation of process operation, considering the product transition
dynamics of the plant, is also a relevant section of the same problem. Finally, the need for
production scheduling arises primarily from the production of multiple products. In principle,
a systematic approach to this process synthesis problem should involve integrated
consideration of design, control, operation and scheduling issues as highly interactive and
inherently dynamic subproblems. However, it still remains one of the unexplored areasin the
open literature, since this integrated is

problem exceptionally demanding. Nevertheless, some
remarkable works have been demonstrated in the literature approaching the mazy process
synthesis problem in terms of some of the previously mentioned directions. The combined
process design and process control problem as it was thoroughly discussed in the previous
chapter, has been systematically investigated by a number of research groups in order to
come up with algorithms for simultaneous solution satisfying some economic and/or
controllability criteria. (Morari & Perkins, 1995; Perkins and Walsh, 1996; Schweiger and
Floudas, 1997; Bansal et al., 2000; Kookos and Perkins, 2001)
In the area of processoperation,there is a body of literature dedicatedto product grade

transitions in polymerization processes. The study of off-line and on-line dynamic
optimisationof transientoperatingprofiles of theseprocesseshas attractedmanyresearchers,

due to the significant economicimportanceof grade transitionsfor the polymer industry.
There are several published reports presenting the implementation of optimal control
trajectoriesto experimentalreactorsystems,applying feedbackand/or feedforward control,
while promoting alternative algorithms to find optimal operation in terms of different
performancecriteria. (Ponnuswamy et al., 1987; MacGregor et al., 1984; McAuley and

MacGregor, 1993; Lee et al., 1997; Wang et al., 2000; Ohshima, and Tanigaki, 2000;
Chatzidoukaset al., 2001).Two works standout due to their detailedand analytic approach
in
to the optimal grade transition a gas-phasepolyethylene reactor and multistage loop
(McAuley and MacGregor, 1992; Takeda and Ray, 1999). In all these
polyolefin reactors
studies both the processdesign and processcontrol were fully defined a priori, while the
multiproduct characterof the processeswas confined to the study of only two polymer
grades,or alternatively,if greaternumberof gradeswas the

considered, productionsequence
waspre-adjustedeludingto copewith the productionschedulingproblem.

135
An attempt to combine consideration of processcontrol and process operation with respect to
processoptimization during grade transition was carried out in this thesis (see Chapter 5) by
studying the grade transition dynamic optimization problem in a gas-phase olefin
polymerization FBR with simultaneous control structure selection applying mixed integer
dynamic optimization techniques, accounting both for continuous dynamic decisions and
discrete decisions as well. However, this study was limited to a partial consideration of the
macro dimension of the entire problem since it was carried out with a fixed process design
and any production scheduling issueswere avoided by considering the transition between two
polymer grades only.
The process operation-production scheduling problem has been systematically explored
particularly in relation to batch processes (Shah et al., 1993; Voudouris and Grossmann,
1993). However, the main principles applied to deal with the scheduling problem in non-
sequential multipurpose or multiproduct batch processes are applicable to continuous

multiproduct plants as well. This is attributed to the similar nature of the problems emerge
both in batch and continuous plants as far as a production plan is concerned. For example, a
set of common scheduling related problems, complicating the operation of batch

multiproduct or multipurpose processes, involve the inventory consideration, the level of
inventory of final products, possible intermediate storage, sizing of storage vesselsand other
process units, sequencing of products and parallel units operation and allocation of tasks to
equipment (in case of multipurpose plants). Most of these problems can be easily identified
in continuous multiproduct processesrunning a production campaign of different products,
where the production of every product reflects a single batch process operation, while the
transition between the products occurs continuously without intermediate shutting-down of
the process.
The group of Grossmann provided some analytic works in the area of production scheduling
of continuous multiproduct plants (Sahinidis and Grossmann, 1991; Pinto and Grossmann,
1994). They addressedthe optimal scheduling problem of multiproduct continuous plants by

formulating a large scale MINLP, accounting for inventory and transition cost between a
inventory level and cycle
number of different products, optimal sequenceof production and
time. Regarding process operation, fixed transition times and transition costs were assumed
to avoid the need for dynamic optimization. This approach required complete enumeration of
the possible binary changeovers between the different products in tenns of transition times
and transition costs. An industrial scale approach to the production-planning problem was
136
presented by Kondili et a]. (1993) for a typical cement plant. They clearly defined their
objectives and they formulated the problem as a mixed integer linear program (MILP)
accounting for the time dependence of the production schedule. The sequence dependent
changeover cost was fully defined for all the possible combinations between the different
products. Finally, Cantrell and Luyben (1996) demonstrated an integrated approach to
processcontrol, process design (in terms of storage capacity) and production scheduling in a
simple process, accounting for process dynamics. The production scheduling was limited to
finding the optimal process cycle time only, since the production sequencewas heuristically
determined. They did not account for dynamic optimisation of the transient operation of the
processand the data neededfor the transition time derived from dynamic simulation.
In the study presentedin this chaptera unified approachis attemptedconsideringprocess

control, processoperation and production planning issues.The problem is examinedin
relation to a Ziegler-Nattacatalytic gas-phaseethylene-I -butenecopolymerizationfluidized
bed reactor (FBR) operatingin a grade transition campaign.The processdesign is totally
defineda priori sincethe polymerizationsystememployedto carry out this researchis a unit
of an industrial polymer process,and no investigationof the interactionof design with the
other componentsof process synthesis has been performed. A comprehensive kinetic
mechanism describing the catalytic olefin polymerization in conjunction with a detailed
modelof the FBR anda heatexchanger developed in previous chapter(seealso Appendix A)

has been applied to simulate the processdynamics and the polymer molecularproperties.
This model providesthe platform for the study of processcontrol, dynamicoptimisationof'
the transientoperationbetweena numberof gradesand the optimal sequenceof transitions.
A mixed integer dynamic optimization (MI]DO) algorithm enablesthe above issuesto be
dealt with simultaneously,avoiding the exhaustive calculation of the dynamic optimal
profiles for all possiblebinary transitions,which might be prohibitive from a computational
point of view whena largenumberof polymergradesis considered.
6.3 Construction of the Multilevel Problem
Industrial polymerizationprocessesmay produceas many as 30-40 different polymergrades

in an annualproduction lifetime. In the presentstudy, the transitionsbetweenfour polymer
grades(A, B, C, D) havebeenselectedas a case
representative study in order to illustrate the
concept of this approachaccountingcautiously for the several dimensions related to this
137
problem. Melt index, polymer density and polydispersity were the molecular polymer
properties (PP: MI, p, PD) identifying each polymer grade.
6.3.1 Derinitions
Defining the production period as the time where the process operates on-specification for
any polymer grade and the transition period as the time where the process switches from one
grade to another, it is reasonable to expect that in a production period the process should
operate optimally. The process optimality is stated in relation to the total monomer
conversion, which should have the possible maximum value as long as any of the above
polymer grades is produced. Therefore, four optimal operating points corresponding to the
four polymer grades have been found under steady state maximization of monomer
conversion with respect to all the available model inputs. Table 6.1 shows the grade
specifications, the operating conditions and the values of the model inputs for the optimal
operating points. The initial operating point (Init) is a feasible point, similarly derived from
steady-state optimization for monomer conversion maximization and provided a starting
point of the process for the transitions between the remaining four grades.
Table 6.1: Polymergradespecifications.
Init Operating Point Grade A Grade 13 Grade C Grade D
Molecular Properties
3)
p (g/Cm 0.9250 0.9299 0.9190 0.9402 0.9130
mi 0.0700 0.0137 0.0360 0.0561 0.2500
PD 3.657 3.694 4.235 3.224 4.506
Operating Conditions
h (cm) 600 600 600 600 600
T (K) 360 360 360 360 360
P (bar) 21 21 21 21 21
Rp (g/s) 2390 2390 2390 2390 2390
Model Inputs
Ratio 0.0697 0.0526 0.1030 ' 0.0290 0.2137
F,,, (g/s) 0.1782 0.0886 0.1110 0.1880 0.2040
Fcg (g1s) 1.346 1.346 1.346 1.346 1.346
138
Chapter 6 Optimal Production Campaign Scheduling In a PE FBR
In order to relate this mathematical formulation of the problem to the actual operating life
of
the process it is assumed that the starting point (Init) was the final polymer grade of a
previous grade transition campaign and now the process is about to run a new campaign.
Since it is expected that the Init point will affect the sequence of transitions, its polymer
properties have been deliberately selected to lie in between the polymer properties of the 4
desired polymer grades. Furthermore, the polymer properties of the four grades have been
chosen in such a way that a monotonous change (either increase or decrease)when moving
from one grade to another during the campaign is impossible for the three polymer properties
simultaneously. This renders the problem more complicated, reducing the possibility of
applying heuristic rules for the selection of the transition sequence.
6.3.2 Clarification Remarks

From the way that this casestudy has beenset up, in order to efficiently reflect a possible
operatingscenarioof a real process,it is apparentthat the processdoesnot operatein a cyclic
mode since it startsfrom an initial operatingpoint and doesnot return back to that point at
the end of the campaign.This meansthat each grade is producedonce and the timely
satisfactionof the customerordersshould be settledon this basecommonlyby storingsome
polymer amounts. It is anticipated that the costs of storage of different grades are
comparable.By assumingthat they are equal, storagecost may be excluded from the
Obviously,
economicperformancecriterion whencomparingdifferent productionsequences.
consideration of inventory aspectsrelated to the storage vessels,which comprisesan
importantprocessoperationproblem,would result in a wider andglobal approximationof the
processsynthesisproblem studied here. However, the previous assumptionsignificantly
facilitatesthis study without seriouscost on the scopeof this work, which is to illustratethe
benefitsobtainedby an integratedapproachto variousprocesssystemsengineeringproblems.
Given the short-term character of the production planning attempted here, where the
production scheduling is limited to a separatecampaign involving a single batch of grades
over a short period of time, the price of polymer productsis expected to be constant,without
any time function for productpricesbeing necessary.Under this approach,it doesnot make
sensefor any product to be given priority in the production sequence.Hence, complete
flexibility in the sequenceof gradesis allowed.
In order to avoid further complicationof the performancecriterion, the productionperiods

during the campaignhave beendissociatedfrom the transition periods.Sincethe operating
139
points have been totally assigned and any transition ends up in one of these points notifying
the beginning of a production period, it is assumed that a separate control mechanism is
subsequentlyactivated,which is responsibleto run the processat steadystate:
* at the optimal operatingpoint correspondingto eachoneof the desirablegrades,
9 remaining at each steady-stateoperating point for the time horizon needed to meet the
market demand under a certain production rate,
9 eliminating any disturbance and hence preventing any deviation from on-spec
production.
As a result, the production periods between the transition periods do not need to be
considered in this study and the performance index accountsonly for the transition periods.
Considerationof processcontrol completesthe integratedapproachto the problemattempted

in this study. A predefinedcontrol structureis applied at this stage.Further analysisof this
input is presentedlater in this chapter.The structurederivedfrom a relativegain array(RGA)
analysis,on a linearized form of the polymerizationprocessmathematicalmodel over the
five operatingpoints, was appliedfor the rangeof all the transitionsof the campaignand is
responsible for holding the reactor's bed level (h), temperature(T), pressure(P) and
production rate (Rp) under control in a multiple input-multiple output configurationof PI
feedbackcontrollers(seeChapter4 andTable 4.1). The first four manipulatedvariables(i.e.,
F,,, FN,, F,, Fmoni)wereemployedfor the feedbackcontrol of the aboveprocessvariables,
u,,
while the remainingtwo control variables(i.e., Ratio, FH,) were usedby the optimiser to
track the "polymer quality" variables(i.e., p, MI and therebyPD) during a transitionto their
desiredvaluescorrespondingto eachgrade.
6.4 Illustrative Example
To exemplify the needto copewith productionschedulingandoptimal processoperationin a

grade transition accounting
campaignsimultaneously, also for processcontrol, comparison
between two candidateoptimal sequencesis carried out. The target of the comparison
betweenthe arbitrarily selectedtransition sequencesis to demonstratewhetheror not the
for
processingsequence different productshas profound implications on processeconomics
140
in terms of the off-spec product and the necessary transition time. In

other words, "is the
switch-over cost sequencedependent?" is the key question that will be clarified.
In the first transition campaign, the process starts from the Init
operating point, then it
changesto grade A, subsequently to B then to C and finally to D (Init-ýA-ýB-4C-41)). A
dynamic optimizer takes care of optimally operating the process
moving from one grade to
another minimizing a certain objective function by manipulating the hydrogen inflow and the
comonomer ratio in the make-up stream, while the control scheme described in Table 4.1
holds the process operating conditions under control. This campaign is
compared against a
second one where the process starts from the Init operating point and then produces the
grades B, then C, then D and finally A (Init--4B-ýC-->D--->A). The first alternative
outperformsthe secondone by a reduction of the objective function, the total off-spec

productionand the total transitiontime by almost 10% (Figures6.1 and 6.2). The conclusion
extractedfrom this preliminarystudyis that the productionsequencehighly interactswith the
optimal processoperationand processcontrol, and thereforethere is a strongincentivefor a
cautious planning of the process operating profile on a base of a flexible-adjustable
productionsequence.
6.5 Mathematical Model Formulation
Since both the process operation in a changeover between two grades and the sequenceof
these changeovers are highly interactive time dependant tasks of different dynamics (a faster
and a slower one respectively) in the time scale of the whole changeover campaign, they
should be both dynamically optimized together. Therefore the dynamic optimization problem
should be properly built in order to embed these two dynamic levels of the problem.
It has been stated before that when the process runs in a production period it operates at
steady state at any of the optimal operating points corresponding to the four desired grades.
Consequently, switching from a transition period to a production period occurs only when the
process has reached a steady state at one of the prescribed operating points. The total
transition time and the total off-spec production during the campaign are the criteria that
should be incorporated in the objective function for the evaluation of the candidate
alternatives. Binary variables are used to model the potential assignmentof different grades
141
Chapter 6_ Optimal Production Campaign SchedulingIn a PE FBR
250
19.27
20C
---------------------- 17-----------------------------
150
*Z
2.95 hr!
100 ------j
I
50
INIT->A->B->C->D
INIT->B->C->D->A
0FIIIiI
05 ýO A A
10 1'5 310
Time (hr)
Figure 6.1: Comparison of two arbitrary production sequencesin terms of the objective
function.
200-
180 «ý
15.36tn
160 ----------------------- f .............................
140-
120-
r- 100-
a. 80
60-
40-
INIT->A. >B->C->D
20-
------ INIT->B->C->D. >A
01
05 10 15 20 25 30 35
Time (hr)
Figure 6.2: Comparison of two arbitrary production sequencesin terms of the off-spec
production.
142
to time slots in the total time horizon. The time horizon for the campaign is divided into 20
time slots (5 intervals for each transition) both because it is believed that 5 changes of the
control variablesare adequatefor the dynamicoptimizer to efficiently andoptimally track the

process from to
one grade another, and because
the more intervals the more computationally
expensivethe problembecomes.Two integervariablesareemployedfor eachpolymergrade,
one showingwhen this gradeis a startingpoint of a binary transition andone showingwhen
this gradeis a desired-finalpoint of eachtransition.During a transitionperiod both the binary
the
variables, one indicating the startingpoint and the other showing the desircd-finalpoint,
are active in the sensethat they are both assignedto I for all the time slots that corresponds
to a certaintransitionperiod.Sincethe time topologyof the Init operatingpoint is known and
constant for all the potential campaignsand besidesit cannot be a desired grade,only one
binary variableis ascribedto this one,which thoughis known during all the time slots.IIcncc
a total numberof eight 0-1 is
variables requiredto describethe timely distribution of the four
desired grades.The notation used in the proposedmathematicalmodel following next is
presentedbelow:
NI numberof intervals,time slotsic= NI,

1,2,...,
binary variable for the initial operatingpoint equalsto I at the

beginning of the campaign only,
bI A(t) binary variable equals to I when polymer grade A is a starting
operating point of a changeover, 0 otherwise,
b2A(t) binary variable equal to I when polymer grade A is a final-

desired operating point of a changeover, 0 otherwise,
bIB(t); bic(t); bID(t);
b2B(t); b2C(t); b2D(t)

similarly definedfor the remainingpolymer gradesB. C. D.
PPjnit, PPý-A,PPý-B, desired values of the molecular polymer properties (PP: MI, p,
PPý-C,PFý-D PD) at the initial operating point and the four polymer grades
respectively,
total amountof the off-specificationpolymer producedduring the

off-spec
whole transition campaign,
143
PP-Amax, PP-Bmax, upper bounds of the constraints imposed on the polymer

PP-Cmax, PPLDmax properties at the end of each transition
PP-Amin, PP-Bmin, lower bounds of the constraints imposed on the polymer

PPý-Cmin,PPý-Dmin properties at the end of each transition,
tf total time needed for the completion of the campaign in terms of

the transition periods only ignoring the intermediate production
periods,
T, T,,,, T, in reactor temperature & upper and lower bounds for the
constraints,
PvPmaxiPmin reactor pressure& upper and lower bounds for the constraints,
Rp, Rp, Rp, polymer production rate & upper and lower bounds, for the
mu, min
constraints
d MI (d MI
jmax time derivative of MI & upper and lower bounds for the
dt dt '
d MI
constraints.
dt
In what follows next, the mathematical fon-nulation of the combined operational and
scheduling problem is presented.
tf 3
Minimize Obj=wl f 2; (PPj-transition-dev(t))dt +W2 (6.1)
(t), bIx (t), b 2XW0
offspec(tf)
i=l
VtE [to$ tf I
S.t. f(i(t), x(t), y(t), u(t), bix(t), b2X(t),d, t) =0
Vte liostf I
h(x(t), y(t), u(t), blx (t), b2x (t), d, t) =0
ho(i(to), x(to), Y(to), u(to), blx(t), b2X(t),d, to) 0

(6.2)
hi(x(ti), y(ti), u(ti), blx(t), b2X(t),d, ti) 0 vtie[tO, tfl i=l N
......
gi(x(ti), Y(ti), u(ti), bix(t), b2X(t),d, ti). -5 0 Vtje1ioqtfj i=l N
......
blx(t), b2X(t)E B
144
where, the normalizedsquaretransition deviation of the polymer properties,PP, from their

desiredvaluesis definedas:
(PPi(t) (t) (t)

-b 2A (t) PPý-A-b 2B PPý-B-b 2C PP-C -b 2D (t) PP-D)2
PPi tion-dev(t) =
-transi fbi, 12
it(t)PP-Init+
bIA PP-A -b 2A PP-A +
b113 PP-B -b 2B PP-B +
bIc PP-C -b 2C PP-C +
bID(t) PP-D -b 2D PP-D
The performancecriterion presentedby Eqn (6.1) containstwo weightedterms,the overall

off-spec productionand the time integral of the deviation of polymer propertiesfrom their
desiredvalues.w, and W2are two weightingfactors,which give different relativeimportance
on the two terms.At the beginningof eachtransition the off-spcc is the dominantterm and
therefore proper actions are taken to minimize it by reducing the transition time and
restricting abruptchangesof the control variables.However,when the processruns oil SpcC,
but still without satisfyingexactlythe quality specifications,the secondterm is zero while the
first term becomesdominantand the controls are properly manipulatedto drive the process
quickly to the steadystate.The vectorsx, y, u andd in the optimisationproblemarethe state,
output, and control time varying variables and the model design time invariant variables
respectively.The set of Eqns (6.2) representthe systemof DAEs of the ethylenc-lbutene
catalytic polymerization processdeveloped in previous chapter (see also Appendix A)
togetherwith a numberof equalityandinequalityinterior point constraintsthat stemfrom the
definition of the problemandthe needfor feasibleprocessoperation.
The nature of the problem studied in this chapter is such that various optimisation problems
with relative fast dynamics (any transition between two polymer grades) arc embodied within
an overall optimisation problem with relative slower dynamics (that is the overall grade
transition campaign). Besides, another peculiarity of the problem is that the binary variables
that used to capture the structure of the problem, are time varying with respect to the total
time horizon (corresponding to the overall transition campaign) while they are time invariant
relatively to each one optimisation subproblem, where they are assigned a constant value
until the completion of each transition. Therefore, for an effortless problem comprehension,
the mathematical development for the problem description is analysed on the discrctizcd time
domain on the basethat each grade transition is completed within five time intervals.
145
6.5.1 Steady State Constraints

In this study no path constraints were imposed on process operating variables, becausethe
control scheme used with optimal tuning of the controller parametersefficiently accounts for
this problem. However, the selection of some variables, on which cnd-point (at the end of
each transition, time slots ic = 5,10,15,20) inequality constraints should be imposed, was
required to make sure that each transition ended up at the desired stable steady-stateoptimal
operating point. Therefore, the polymer properties, the reactor temperature and pressure,the
production rate and the time derivative of MI were constrained at each end point, with the MI
derivative representing the slowest dynamics of the process.
b2A, b2A,
ic PPi-A,,,i,, +II KPPi-A..
lb2B, Ppi-Bmax
b 2B, K PPj +I
-B j,ý
K
:5 Ppi, < Ib
K
b2C, Ppi-Cmin + b2C, Ppi-CIIIiX
K K
b2D, PpiýDmin Ppi

K 2D, K ýD max
T. i,, :5T,, < T.,,
Prnin :5P, ,ýPmax (6.3)
Rp, :5RPIK: 5R
min P,max
(dMI) (dMI),,:, (dMI)

:, Vi= IJ & ic = 5,10,15,20
dt dt dt
min max
6.5.2 Auxiliary Integer Variables

In order to simplify mathematically the synthesis of the problem a new set of binary variables
was defined (ba, bb, b,, bd, b,,, bb,

2X, b,, 2X, bd,
2X) accounting for the fact that the
lx, lx, lx, lx, 2X,
initial set of the binary variables changed only once at the beginning of a new transition and
remained constant until the completion of this transition period and the beginning of -anew
one. Each of these integer variables was assigned to a group of the initially defined binaries
corresponding to five sequential time intervals (1-5,6-10,11-15,16-20) ensuring that
from to another occurred, it would last for rive time intervals

whenever a transition one grade
interval the I", the 6th, or the II th, or the 16'h. The following expressions help
with starting or
for the functionality of these auxiliary variables to become more perceivable.
146
ba, blx,,, VicE[1,5]&X=AorBorCorD,

lx,.:
ba, VicE[1,5]&X=AorBorCorD,
2X=b2X,,,
bb, = bix,, Vice [6,10]&X=AorBorCorD,
IX
b =b VicE[6,10]&X=AorBorCorD,
b.2X 2x.,,
(6.4)
br Ix =bix,,, VKE[11,15]&X=AorBorCorD,
.,
bc. = b2X, VKE[11,15]&X=AorBorCorD,
2X ic
bd, = bix,,, VicE[16,20]&X=AorBorCorD,
IX
bd, =b VKE[16,20]&X=AorBorCorD
2X 2X,K
6.5.3 Known Initial Operating Point

At the beginning of the campaign the process starts from the Init operating point, therefore:
ba, X=IA, B, C, D)
IX --=O, (6.5)
6.5.4 Assignment of a Changeover Between Two Grades to One Transition Period Only
The following constraints ensure that each polymer grade is produced once in the campaign
and the production of all the polymer grades is guaranteed.

ba, + ba, + ba, + ba, "= I
2A 2B 2C 2D
D
Z (bb. bb,
)=
2
+
IX 2X
X=A
D
E(b,, +bc,
Ix 2X)=2
X=A (6.6)
D
1: (bd,
IX +dd, 2X)=2
X=A
ba. + bb, + bc. lx + bd. IX :51 VX =A or B or C or D

lx IX
ba, + bb, + bc, + bd. 2X =I VX=AorBorCorD

2X 2X 2X
6.5.5 Sequential Transition Mode

The following constraints ensure that whenever a transition is completed a new one will start
at the operating point that was reached from the previous transition, since during any
147
production period the process operates without any deviation from the optimal operating
point.
bb, VX=AorBorCorD
IX=ba,2x
b,.Ix=bb, 2X VX=AorBorCorD (6.7)
bd,IX=bc, 2x VX=AorBorCorD
6.6 Solution Procedure
From the mathematicalformulation of the problem addressedin this chapter,it is apparent

that both continuous and discrete decisions are involved. The combined structural and
operational problem is decomposed into two interacted stages: i) develop a candidate
production structure, ii) determine the corresponding optimal operating profile and possibly
design and control for that candidate.
The philosophy behind this hierarchical approach is to efficiently screen scheduling

alternativessuchthat more intensivenumericalmethodsare appliedwhen a viable candidate
production plan has been established(Mah, 1990; Biegler et al., 1997; Rowe, 1997). In
practice, when such combined problems are carried out in a hierarchical framework, the
operationalprofile is determinedin an upperlevel involving minimization-maximizationof a
certainperformancecriterion, while the productionsequencingis carricdout in a lower level.
A mixed integer dynamic optimization (MIDO) algorithm has been employed to addressthe
current problem. The innovative approach of the MIDO algorithm (Bansal, 2000; Bansal ct
al., 2002, Bansal et al., 2003) applying the Generalised Benders Decomposition (GBD)
approach was used to mathematically decompose the problem into a series of "primal" and
"master" sub-problems in consistency to the decomposedformulation of the problem into an
upper and lower level. The former one, which corresponds to the dynamic optimization
problem, is utilized to find the optimal PI controller tuning parameters and the continuous
optimal profiles for the grade transitions taking place in a discrete production sequence
represented by integer variables. It provides an upper bound (UB) of the solution and dual
information (Lagrangemultipliers) to the "master"sub-problem.The latter is a mixed integer
linear programming(MILP) problemproviding a lower bound(LB) of the solution and new
setsof valuesof the discreteintegervariables,in an iterativeway. A differencebetweenthe
UB and the LB below a specified toleranceindicatesproblem convergence.The control
148
vector parameterization technique (Vassiliadis et al., 1994a and 1994b) is applied to solve the
dynamic optimization problem. According to this technique the time varying control
variables are discretized in order to create a finite optimization problem solved with the help
of a DAE system integrator. The time horizon of the problem is split into a finite number (20)
of elements, and each control variable is assumed to be constant in a given time element.
Manipulation of both the time interval length and the value of the control variable at each
interval, results in the desired control profiles that optimise the processoperation.
Enumerating the available decision variables in this study, the flow rate of hydrogen fced
stream (FH, ), the ratio of comonomer to monomer flow rate in the make-up feed stream
(Ratio) and the binary variables constitute the set of the time varying controls, while the
controller parameters as well as the length of each time interval are time-invariant decisions.
The commercial modelling-simulation package gPROMSO in conjunction with the gOPTO
optimisation interface (Process Systems Enterprise Ltd, London) are used for the integration
of the DAE system and the dynamic optimization of the grade transition problem.
Additionally, the GAMS/CPLEX solver is used for the solution of the MILP problems,
resulting0 form the "master" problem in the MIDO algorithm.
6.7 Results
The total number of binary parameters after the discretization of the time horizon into 20
intervals is (8 binary variables x 20 time intervals =) 160. However, the introduction of the
auxiliary integer variables reduces the binary space into 32 parameters.Applying the MIDO
in binary space, one can come up with as many as 32 2= 1024 binary
algorithm such a
combinations. Activating the integer constraints, described in a previous section, the field of
possible production sequencesbetween the four products is narrowed to 4! = 24.
6.7.1 Optimal Transition Timing

Four iterations betweenthe primal and mastersub-problemswere adequatefor the MIDO
algorithm to locatethe optimal solution.Table 6.2 presentsthe optimal timing of the integer
variables demonstrating the sequenceInit-ýC-4A-413-41) as the optimal production
schedule.Table 6.3 illustratesthe remainingthree productionsequencesderived during the
four iterationsof the algorithm; a comparisonbetweenthemin termsof the time horizon,the
149
objective function and the total amount of the off-spec product, reveals the excellence of the
optimal sequence.
6.7.2 Optimal Profiles

Figures 6.3-6.5 display the optimal profiles for MI, p and PD during the transition campaign.
It is remarkable that in the production sequencefound as the optimal one the processoperates
in a continuously descending mode in ten-ns of polymer density and continuous ascending
mode in terms of polydispersity. A simultaneous monotonous change is impossible for MI

during the campaign. However, it is observed that the most demanding and expensive MI
change, that is the transition to grade D (with high value of MI) from any of the remaining
grades, has been left for the end of the campaign avoiding a reverse change to any lowcr-Ml
polymer grade with additional off-spec production.
Table 6.2: Optimal production sequence.

b1A b1D b2A b2B b2C b2D
Intervals blj3 bic
1-5 0 00 000 10
6-10 0 01 010 00
11-15 1 00 001 00
16-20 0 10 000 01
Table 6.3: Comparison between the proposed sequences.

Sequences Time horizon Objective Function Off-spec Product
Init-ýA--ýB--ýC-41) 31.35hr 193.05 162tn

Init-+C-ýA->B->D 27.16hr 166.28 1321n
Init--)D----)A-ýC--)B 30.63hr 221.038 181tn
Init-)D-413--ýA-4C 34.13hr 185.963 153tn
150
Chapter 6- Optimal Production Campaign SchedulingIn a PE FBR
I I Grade D
0.25 ymer MI
0.20
0.15
0.10
Pet
I Initial point
Grade C
0.05 I Grade B
. .............
Grade A
0.001 1- -, IIIIIII
05 10 15 20 25 30
Time (hr)
Figure 6.3: Optimal MI profile under the optimal production planning.
0.945
Polymer DensLY11
0.940-
Grade C
0.935 -
Grade A
0.930 -
0.925-
Initial Point
0.920- Grade B
0.915-
Grade D
0.910-- I
05 10 15 20 25 30
Time (hr)
Figure 6.4: Optimal density profile under the optimal production planning.
151
4. E
4.6
4.4
4.2
e 4.0
10
3.8
3.6
3.4
3.2
05 10 15 20 25 30
Time (hr)
Figure 6.5: Optimal PD profile under the optimal production planning.
Besides the monotonous change of polymer properties, it is interesting to notice the direction
of change particularly for the polymer density. The sequence Init--ýC-ýA-ýB-ýD is the
reverse sequenceof Init-ýD--)B->A--)C, which has been tested by the MIDO algorithm and
found deficient compared to the first one. Therefore, although a monutonuus change was
ensured for both production schedules, the direction of the change defines which one is the
optimal. A reasonable explanation for this is given in terms of density, thinking that the
progressive decreaseof density goes in parallel with a progressive comonomer concentration

increase. In general it is known that a depletion of a component from the reactor is much
more expensive than a repletion of the reactor with this component. Furthermore, the need for
an increased butene concentration in the reactor leads to an increaseof the transition time due
to the lower polymerization rate of butene. Therefore, the point where the direction of the
transitions interferes to the optimal production plan is understood on the baseof the previous
remarks.
An interesting comment is extracted from the comparison of the four sequencesin terms of
the off-spec production in parallel with the on-spec period during the transitions (Figure 6.6
and Table 6.4). From the graph of off-spec production vs. time it is observed that at the end
of each transition the off-spec production reachesa plateau, while a region of sharp increase
152
Chapter 6 Optimal Production Campaign Scheduling in a PE rBR
has preceded. At the area of constant amount of off-spec polymer, the process operateswithin
the specifications still though Cindertransient operation since the optimal operating point has
not been reached. Table 6.4 exhibits the on-spec periods as a percentage of the total time
horizon for the set of the four campaigns. There are two conflicting perspectives from which
this information can be viewed. The negative point of view is that the higher is this on-spec
period the more the process operates under supervisory control, even if it runs on-spec, until
the steady state reinstatement, which indicates the end of the transition period and the official
Table 6A On-spec periods during the transition campaigns.

On-spec period
(% of total
Sequences
time horizon)
Init->A--ýB-*C-ýD 39.7%
lnit-+C-ýA-+B-ýD 42.3%
Init-ýD-4A-4C--ýB 30.5%
Init-ýD--ýB--+A-+C 47.0%
200
180
160
c
140
'3 120
100
80
60
Init->A->B->C->D
40 Init->C. >A. >B->D
Init->D. >A. >C->B
20
Init->D->13->A->C
0
05 10 15 20 25 30 35
Time (hr)
Figure 6.6: Comparison of the four campaigns in terms of the off-spec production.
153
Chapter 6 Production Campaign SchedulingIn a PE FBR
_Optimal
beginning of the production period. The positive viewpoint is that the higher is this on-spec
period, the more the process produces on-spec polymer during the transitions even if not
operating at maximum steady state conversion. The significance of this comment becomes
valuable when it is considered in conjunction with the market demand. In particular, in
periods of high market demand it is obvious that the polymer manufacturers need to produce
polymer even not at the maximum yield, while in periods of low market demand they want to
produce polymer at the lowest possible cost, hence with the best possible yield.
6.8 Problem Revision-Further Control Consideration
So far researchin the area of processcontrol consideredsimultaneouslywith process

operationand productionschedulingwas limited only to finding the optimal tuning of the PI
controllers to carry out the transition campaign.The structureof this control schemewas
predefinedseparately,simply basedon somecontrollability criteria suchasthe RGA analysis
and not in conjunctionwith the operationaland schedulingissues.Thereforethereis still an
opportunity for a more integratedapproachto the processsynthesisproblem, since there
might exist an alternativecontrol structurecapableof tracking the processin suchtransition
campaignsin a more efficient and profitable way. In order to incorporatewith the research
that has beendone so far, a parallel researchtowardsthe processcontrol direction, a third
level shouldbe embeddedin the decompositionapproachthat hasbeenimplemented.
In a previous chapter, the two level problem of process control and process operation in the
same polymerization process was addressed,resulting in an optimal control structure for a

transition between the first two grades only, A to B and back to A. An optimal multivariable
control structure was one outcome of the MB)O algorithm implementation. According to this
scheme the process operating conditions were held under feedback PI multivariable control
and the polymer properties under optimal feedforward control by the hydrogen feed stream
flow rate, the ratio of comonomer to monomer flaw rate in the make-up stream, the bleed
flow rate and the catalyst feed stream flow rate (Table 5.3)
In the remainder of this study the optimal control structure found in the previous work is
employed to conduct the grade transition campaign applying the production sequencethat
proved to be the optimal one using the RGA-based control scheme. Substantially, both the
process control and the production planning are fixed to their optimal configuration found
154
though under a partial management of the three level problem by two bi-level subproblems
(process operation-processcontrol & process operation-production scheduling).
In Figures 6.7 and 6.8 the optimal transition campaigncarried out under the RGA-bascd
control structureand the optimal transitioncampaigncarriedout underthe "optimal" control
structureare demonstratedin termsof the value of the objective function and the amountof
the off-spec polymer produced. Significant reduction of the performance criteria (objective
function, off-spec production and transition time by 11%, 11% and 13.5% respectively) is
achieved when the potentially optimal control scheme is employed compared to the RGA-
based scheme. Thus the effect of different control structures can be significant and a full-
integrated approach involving scheduling, transition optimization and control structure
selection may result in a better process performance with different optimal construction of
processcontrol andproductionsuccession.
180
................................ ........................................
160 18.6
................................ ...............
140
120
loo ...... 3.7 hr

r;k
80
:P 60
0
40
20 RGA Control
Optimal Control
0 rI "--T- I
05 10 15 20 25 30
Time (hr)
Figure 6.7: Grade transition campaign under two alternative control schemes-Objective
function comparison.
155
14C
.......................... ............................................
14.8 tn
12C
.......................... .............................
100
80
10
0
LW
r.4 *, . 10
ei 60
cu
Mw
40
20 RGA Control
Optimal Control
0
05 10 15 20 25 30
Time (hr)
Figure 6.8: Grade transition campaign under two alternative control schemes-Off-spec
production comparison.
The multidimensional nature of the process synthesis problem has been highlighted in this
chapter on the base of an industrial scale olefin polymerization FBR operated in a grade
transition campaign. A detailed dynamic model of the FBR in conjunction with a
comprehensive polymerization kinetic mechanism and polymer properties model was
employed to conduct this study. Dynamic process operation and production scheduling have
been presented as partial subtasks of the process synthesis task and the potential benefits of
dealing with both problems in an integrated way were highlighted. A decomposition method
was applied to address these combined problems on the basis of an advanced MIDO
algorithmaccountingfor both continuousanddiscretedynamicdecisions.
Process control, from the control structure point of view, was introduced as a third level of
the process synthesis problem. A control scheme that was found as the optimal one from a
previous chapter was employed and the grade transition campaign problem was revisited.
Comparison of these strategiesmotivated a global approach of the processoperation, process
control and production planning problems.
156
6.10 Literature
Bansal, V. (2000). Analysis, design and control optimization of processsystemsunder

uncertainty.AD Thesis,Imperial College,University of London.
Bansal, V.; Perkins, J. D.; Pistikopoulos, E. N.; Ross, R.; and van Schijndel, J. M. G. (2000).
Simultaneous design and control optimisation under uncertainty. Computers Chem.
Engng., 24, p. 26 1.
Bansal, V.; Perkins, J.D.; Pistikopoulos, E.N. (2002) A case study in simultaneous design and
control using rigorous mixed-integer dynamic optimization models. Ind. Eng. Chem.Res.,
41, p. 760.
Bansal,V.; Sakizlis, V.; Ross,R.; Perkins,J.D.; Pistikopoulos,E.N. (2003)New algorithms

for mixed-integerdynamicoptimization.ComputersChem.Eng.,27, p. 647.
Biegler, L. T.; Grossmann, I. E.; Westerberg, A. W. (1997) Systematic Methods of Chemical

Process Design. Neal R. Amundson (Eds.), Prentice Hall PTR, New Jersey, Chap. 6.
Ind.
Cantrell, J.G.; Luyben, W.L. (1996). Design of rapid-transitionmultiproductprocesses.
Eng. Chem. Res., 35, p. 2624.
Chatzidoukas, C.; Perkins, J.D.; Pistikopoulos, E.N.; and Kiparissides, C. (2001). Dynamic
simulation and optimization of an industrial olefin polymerization FBR using the

0/gOPTO computational tools. DYCOPS 6th IFAC Symposium, Jejudo Island,
gPROMS
Korea.
Kondili, E.; Shah, N.; Pantelides, C.C. (1993). Production planning for the rational use of
in
energy multiproduct continuous plants. Computers Chem. Eng., 17, S123.
Kookos, I. K.; Perkins, J.D. (2001). An algorithm for simultaneous process design and
control. Ind. Eng. Chem. Res.,40, p. 4079.
Lee, M. H.; Han C.; Chang, K. S. (1997) Hierarchical time-optimal control of a continuous co-
polymerization reactor during start-up or grade change operation using genetic

algorithms. Computers Chem. Eng., 21 Suppl., p. S1037.
MacGregor, J.F.; Penlidis, A.; Hamilec, A. E. (1984). Control of polymerization reactors: A
review. Polymer Proc. Eng., 2, p. 179.
157
Mah, Richard S.H., (1990) ChemicalProcessStructuresand Information Flows. Howard

Brenner (Eds.), Butterworths Series in Chemical Engineering, United States of America,
Chap.6.
McAuley, K. B.; MacGregor, J.F. (1992). Optimal grade transition in a gas phase
polyethylene reactor. AIChE J., 38, p. 1564.
McAuley, K. B.; MacGregor, J. F. (1993) Nonlinear product property control in industrial
gas-phasepolyethylene reactors.AlChEJ., 39, p. 855.
Morari, M.; and Perkins, J.D. (1995) Design of operations. In: Foundations of Computer
Aided Process Design (Perkins J.D., Ed.). Vol. 91 of AlChE Symposium Series, p. 105.
J. of
Ohshima,M.; Tanigaki, M. (2000). Quality control of polymer production processes.
Proc. Cont., 10, p. 135.
Perkins, J.D.; and Walsh, S. P. K., (1996). Optimization as a tool for design/control
integration.Computers& Chem.Eng., 20, p. 315.
Pinto, J.M.; Grossmann, I. E. (1994). Optimal cyclic scheduling of multistage continuous
multiproduct plants. Computers Chem. Eng., 18, p. 797.
Ponnuswamy, S.R.; Shah, S.L.; Kiparissides, C. (1987). Computer optimal control of batch
polymerization reactors.
Rowe A. D. (1997). Integrateddesignof distributed chemical manufacturingfacilities. PhD
Thesis,Imperial College,Universityof London.
Sahinidis,N.V.; Grossmann,I.E. (1991)MINLP modelfor cyclic multiproductschedulingon

continuousparallel lines. ComputersChem.Eng., 15,p. 85.
Schweiger,C.A.; Floudas,C.A. (1997).Interactionof designand control: Optimizationwith

dynamic models. In: Optimal Control: Theory, Algorithms and Applications, W.W.
HagerandP.M. Pardalos,Eds.,Kluwer AcademicPublishertsB.V., p. 388.
Shah, N.; Pantelides,C.C.; Sargent, R.W.H. (1993) A general algorithm for shor-term
batch operations-II.Computationalissues.Computers Chem. Eng., 17, p.
schedulingof
229.
Takeda,M.; Ray, W.H. (1999).Optimal-gradetransition strategiesfor multistagepolyolefin

reactors.AlChE J., 45, p. 1776.
158
Vassiliadis, V. S.; Sargent, R.W. H.; Pantelides, C.C. (1994a) Solution of a class of multistage
dynamic optimization problems. 1. Problems without path constraints. Ind. Eng. Chem.
Res., 33, p. 2111.
Vassiliadis, V. S.; Sargent, R.W. H.; Pantelides, C.C. (1994b) Solution of a class of multistage
dynamic optimization problems. 2. Problems with path constraints. Ind Eng. Chem.Res.,
33, p. 2123.
Voudouris, V. T.; Grossmann, I. E. (1993) Optimal synthesis of multiproduct batch plants with
cyclic scheduling and inventory considerations. Ind. Eng. Chem. Res., 32, p. 1962.
Wang, Y.; Seki, H. Ohyama, S.; Akamatsu K.; Ogawa, M.; Ohshima, M. (2000) Optimal
grade transition control for polymerization reactors. Computers Chem. Eng., 24, p. 1555.
159
CHAPTER7
Plant-Wide Issues
All the research developments presented so far in this thesis were based on an industrial
olefin polymerization plant and motivated by the operating envelope of this plant and the
operational problems rise from the need to improve the process profitability and upgrade the
competitive character of the process. Obviously, in order to deal with the problems discussed
in previous chapters, various approximations and assumptions were employed to reduce the
complexity of the plant-operating framework, while the overall plant flowsheet was actually
limited to a single reactor process unit that was the fluidized bed reactor.
In this chapter a first step is made towards the development of an accurate and detailed
mathematical model of the real dimensions of the plant confronting various processoperating
features and several modeling challenges in order to provide a potential tool to deal ulteriorly
with the problems reported so far on a plant-wide base.
7.1 Introduction-The Borstar(gýProcess
The BorstarO is an industrial scale continuous multistage olerin polymerization plant, which
produces a broad variety of polyethylene (Figure 7.1). The combination of different

polymerization processes, different reactor units and a multisite catalyst contribute to the
wide distribution of the final polymer properties. The plant consists of three reactors (two
Loop reactors and a Fluidized Bed Reactor, FBR), of different dimensions and operating
conditions, and a Flash separator.The cardinal feature of the Borstar process as a multistage
polymerization process is that the polymer produced in the first reactor unit is conveyed
sequentially to the following reactor units, where it is gradually growing under extremely
different operating conditions and polymerization processes.Thus a multilayer product with
bimodal molecular weight (MW) and copolymer composition (CC) distribution is formed.
160
r-
0.
6
10
r..)
Chapter 7 Plant-Wide Issues
Based on the polymerization process implemented in each reactor unit, the plant is divided
into two sections. The slurTy-phase polymerization section, which provides an attractive
environment for high crystalline, low molecular weight product, and the gas-phase
polymerization section, where high molecular weight, amorphous polymer is favoured. The
Loop reactors, which permit operation under high polymer concentration conditions, are
employed for the slurry-phase polymerization, while the FBR is used for the gas-phase
polymerization. The sequenceof plant units is selected to comply with safety and operational
rules considering the path of catalyst fragmentation, the gradual reduction of its activity and
the growing of polymer particles. Precisely, the Loop reactors are located at the beginning of
the plant and then follows the FBR becausethe opposite sequencewould result in dissolution
of the amorphous polymer produced in the FBR, in the liquid inventory existing in the Loop,
making the resin tacky and hard to process (Zacca et A, 1996). The Flash separatorbetween
the reactors is necessary to flash the liquid polymer mixture at the output of the Loop to
gas/solid conditions before entering the second section of the plant.
7.1.1 Catalyst System - Pre-polymerization Section

The Borstaro process utilizes a novel highly active Ziegler catalytic system, which is
designed to retain its activity along the different stagesof the plant in order to ensure high-
level productivity for all the reactor units. The peculiarity of the Borstar process, in
conjunction with its multistage character, is that there is no fresh catalyst feed to all the
reactor units. Catalyst is exclusively fed to the first Loop rractor, which is properly operated
to account for the high catalyst activity and some undesirable consequencesresulted from
that at the initiation stage of polymerization. These detrimental phenomena are efficiently
handled at a "pre-polymerization stage" of the plant, which is actually conducted in the first
Loop reactor that serves as a "pre-polymerization reactor" with short polymer residence time
and mild operating conditions in terms of monomer concentrations and/or temperature.
Generally,pre-polymerizationimplies the separationof the catalystactivationstagefrom the

actual polymerizationstage. Pre-polymerizationis carried out under mild condition, with
lower monomerconcentrationsand/orlower temperature,to reducethe polymerizationrates
in this initial stage.There are two major reasonsto use a pre-polymerizationstepbeforethe
actualpolymerizationprocess(Pater,2001).
The first one, known as the thermaleffect of catalystactivation,is the most describedreason
in the literature and is related to the thermal runaway on the particle scale during the initial
162
phaseof polymerization.In that stagethe growing particle is small and thereforehasa small
heat-exchangingsurface with the bulk phase while the reaction rate is high, as no
deactivationhas occurredand the active site concentrationis at a maximum. If the above
phenomenawere combinedwith high temperatureand monomerconcentration,then the heat
productionratewould be too largewith respectto the heatremovalrate.
The secondreasonof equal importanceis the fragmentationof the catalystsupportmaterial
with unwanted consequenceson the polymer morphology. More specifically, with the
progress of the polymerization, the catalyst support material breaks up due to internal
hydraulic pressure and stressesexerted by the polymer on this material. When pre-
polymerizing the catalyst, the support will break up slowly, to form regular structuresthat
replicate the original shape of the catalyst particle. Rapid fragmentation on the other hand,
can lead to undesiredfines with a large influenceon the powdermorphologyof the polymer
formed in the main process.Hence in the "pre-polymerizee'the critical phenomenaat the
beginning of polymerizationare easily handledand then the polymer microparticles,which
contain already activated catalyst sites, are transferred to the subsequentreactor units
allowing the polymerization to proceed.To further reducethe hazardof temperaturerunaway
due to the exothermicpolymerizationreaction,in the main reactorunits, apart from the pre-
polymerization stage, inert diluent (propane in the Loop and NZ in the FBR) are fed to
decreasethe monomer concentrationsand therefore the polymerization rate (Ferrero and
Chiovetta, 1987).
7.1.2 Plant Units - Model Consideration

The purpose of this chapter is to give an analytic description of the theoretical background
applied for the development of a mathernatic model for the dynamic simulation of the
Borstare plant. Due to the meticulous insight over the operating framework of the FBR.
developed during this thesis, and for simplicity reasons,this model accounts only for the last
two process units, that is the Flash separator and the FBR, at the cost of inaccurate
description of the overall plant dynamics.
However, theseprocessunits capturea wide range of polymerizationand thermodynamic

phenomena and besides,
their dynamic model was developedbearing in mind that they are
connectedwith the previous units of the plant via a polymer stream from the Loop reactor
continuouslyfed to the FBR through the Flashunit. Hence, there are two types of polymer in
the FBR in terms of their molecularproperties,one type of polymer coming from previous
163
units, and another type of polymer produced in the FBR. The average properties of the
overall polymer mass in the FBR derive from mixing of these two polymer types.
This model studiesthe dynamic operationof the plant over two industrial polymer grades
(gradeA& B) and demonstratesthe dynamicbehaviourof the Flashand the FBR during the
transition betweenthesegrades.The correspondingtransitiondynamicsof the first two Loop
reactorsof the plant are ignored(due to the absenceof their respectivedynamicmodels)and
the changesof polymer propertiesand the thermodynamicconditionsof the polymer stream
from the Loop are instantaneousduring the transitions, with obvious influence on the
dynamics of the subsequentunits.
The model has been developed in the gPROMS (Process Systems Enterprise Ltd., London)
modeling environment, exploiting the communication capabilities of this tool with other
modeling languages, such as FORTRAN, used particularly to carry out thermodynamic
calculations.
7.2 Mathematical Model
In this work great emphasisis given on the microscale/macroscale level approachof the
Borstare plant focusingon the study of averagepolymer properties,dynamic behaviourand
control of processunits, while somemesoscalephenomenaare also capturedto someextend.
To describethe kinetics of ethylene-I -butenecopolymerizationin the plant a unified kinetic
schemebasedon a two-site Ziegler catalystis employed.Although the mathematicmodel is
expectedto correspondto the modeling requirementsof all the reactor units of the plant,
however somespecialcommentsand equationshave beenamendedor extractedin order to
adaptthis modelto the FBR unit.
7.2.1 Polymerization Vinetics

The kinetic mechanismof ethylenewith 1-butenecopolymerizationover a multisite Ziegler
catalystcomprisesa seriesof elementaryreactions.The kinetic schemeis describedherein a
general form including site activation, initiation, propagation,site deactivationand chain
transfer reactionsin order to highlight the consistencyof this model with the one usedto
investigatethe processdesignproblemsin the FBR unit only. However, the site activation
reactiondoesnot apply for the FBR, as a reactorunit of the overall Borstarplant, sincethere
164
is no fresh catalyst feed, while all the catalyst sites conveyed with the polymer stream from
previous units are already activated. Since all the reactor units are fed with monomer and
comonomer as well, copolymerization and not hornopolymerization is taking place. The
polymer molecular properties are highly influenced by the fraction of comonomer in the
polymer chains and therefore the "live" polymer chains are differentiated with respect to the
ending monomer unit, accounting for the amount of comonomer introduced in the polymer
chains with the progress of polymerization. The symbol ý

P. denotes the concentration of
"live" copolymer chains of total length W ending in an T monomer unit, formed at the T
Sk, Pok Ck k
catalyst active site. P and d, D. denote the concentrationsof the potential and
activated vacant catalyst sites of type V and the deactivatedmoleculesand the "dead"
copolymerchainsof lengthn producedat T catalystactive site, respectively.Below follows
the set of reactionsconsistingthe copolymerizationkinetic mechanismbasedon which the
net production/consumption rates of the severalspeciesinvolved in this kinetic schemeare
derived accordingly.
Catalyst site activation (by Aluminum Alkyl):

Kk
Sk ) pok
p +Al
Chain Initiation (with monomerMj):

Kk
A +M.
10 Oi ) pk.
1 1.1
Chain Propagation:
Kk
pk +M Pu
n,i -ýpk n+l, j
Chain Deactivation (spontaneous):

k
K&P kk
pk ýCd +D,
Chain Transfer (spontaneous):

Kk
pk. "Pi ) Pok+Dk
n,i n
Chain Transfer (by hydrogen, H2):

Kk
pk tH* jpk+Dk
+H2
n,i 10n
Chain Transfer (by monomer):
Ký
pk + Mi 4 )pk j +Dk
nj I. n
165
The full exprrssions of the net production and consumption rates of the various
polymerization species,the definitions of the pseudokineticrate constantsbasedupon the
above polymerization mechanism, the polymer chain moment rate functions and the
equations for the average polymer molecular properties are thoroughly presentedin
Appendix A and Chapter3 in absoluteconsistencywith the requirementsfor the modeling
developmentsof the Borstar plant. Therefore,it is redundantto repeat this analysishere,
however the interactive relation betweenthis polymerization kinetic model and the main
dynamic reactormodel in terms of the information conveyedfrom one to the other for the
construction of the mass/energybalancesand the kinetic expressionsneed to be further
elucidatedhere.
7.2.2 Reactor Model

The reactorunit is approximatedas continuousstirredtank reactor(CSTR).This assumption
is supportedby the good mixing patternof the FBR undersufficient high supcrficialvelocity
of the gas inlet stream. The model accountsfor a two-phasepolymerization system,a
polymer-rich ("heavy"), which practically correspondsto the polymer particles, and a
polymer-lean("light") phase,which practically containsno polymer and it reflects the gas
phaseof the system. The perfect mixing approachadopted for the FBR model is appliedin
eachphaseseparatelyand uniform temperatureand concentrationprofiles can be considered
for both phases.Polymerizationis carried out in the first phaseonly, where monomersand
other components("light" components)are solute in polymer particles. Thermodynamic
equilibrium betweenthe two phasesis to
assumed settle ignoring
instantaneously, heat and
mass transfer between
resistances the phases. Although the model assumesthat the solubility
of the various componentsin polymer particles is not constrainedor retarded by diffusion
phenomena,it accountsfor the crystalline fraction of polymer particles as a bound of the
sorptionof the "light" in
species the polymer.
Polymer crystallinity has a pronouncedeffect on the polymerization since the "light"

componentsare soluble only in the fraction
amorphous of polymer particlesand to
appears be
a limiting factor of polymerization.Therefore,an effective volume (Vf) of polymerphaseis

defined andpolymerizationoccursonly there.In order to find the sorptionof the reactantsin
this volume of the polymer phasethe partial pressureof thesecomponentsin the "light"
phase is required. Hence the partial massbalancesfor the "light" componentsare written
with respectto volumeof the "light" phase,VL, andonly the polymer massbalanceis written
166
for the volume of "heavy" phase, VH, (since there is no polymer in the "light" phase).Then
applying appropriate thermodynamic calculations (see section 7.2.4) the solubility of "light"
components in the "heavy" phase is derived. Similar discretization though is not necessary
for the energy balance, which is constructed for the overall volume of bed. The unsteady-
state mass balancesfor all the "light" components Mi (I: C2114,2:C4H8,302,4: 142,5:C3118)in
the "light" phase are derived as follows:
d(Mi)
dt =Fm, +Fi,,Xi.,,i +F,. X4i -F,,, OX4i -F,, tXout,i
(dCpl dC dC XtHj (7.1)
dead
-V, fMwiiRk, M( _ +=+ i =1,2 (Ncomp-1)
k-I dt dt dt XtH. ....
N.
p
The terms at the right side of this equation represent the input and output mass flow rates of
component Mi via the make-up stream (Fm, ), the stream coming from a previous unit (Fi. ),
the gas outflow stream (F,,,,), the recycle stream that returns back to the reactor
(F,,, =F,, -Fbl,,d) and the product stream (FOJ. The last two terms show the mass transfer
(, c
rate of component Mi from the "light" to "heavy" phase under the assumption of a "pseudo"
steady state between these two phases.Under this assumption the mass transfer rate of each
k
componentMi is equal to the net consumptionrate (Vf Mw iJRm, ) of this componentin
k-I
dCp,, dCdcad XtH.

1
)
the "heavy" phase and the change rate ((dCp,,, + + of t.s
dt dt dt 13ýtHN.., v
accumulated mass in the "heavy" phase. Needless to mention at this point that the
consumption rate of the inert gases (N2 and C3H8) are zero. With known mass and
composition (XLi) of the "light" phase,
mi
xI i=1,2... (N.. 1) (7.2)
p-
mj
the pressurein the bed is calculatedbasedon the "light" phaseonly using the Sanchez-
LacombeEoS (seeAppendixD):
P: --S-Jýl(XL,i, T, PL (7.3)
fMn,t)
wherePLand XL, is the densityand the masscompositionof the "light" phase,

while T and
M,,,t is the reactortemperatureand the numberaveragemolecularweight of the total polymer
massin the bed.Therefore,the partial pressureof the "light" componentMi is:
167
P. = Xjý.., iP (7.4)
1 '
where XLm,,
I,i is the molar fraction of Mi in the "light" phase:
Mi/Mwi
Xmol,
Lj =N -; i=1,2 (Ncomp
- 1) (7.5)
T, ....
(m, /Mwj)
Accordingly the mass balances for the two types of polymer in the "heavy" phase (polymer
produced in the current reactor unit (Cpoll and polymer coming from a previous unit [CPj)
with different molecular properties can be written:
d(CP, ) cpre
FinXin. (7.6)
- = N_ -FoutXout. N...
dt Polm.
'
d(Cp., )= c
ý(Mwi 1 FoutXout, Pol
Ve Rm Nc«np polM., (7.7)
dt ,f i-1 k-1
The mathernaticexpressionfor the net consumption rate (R ki

M ) of component Mi is
presentedin AppendixA. Xjý,j, Xjj andX,,,ti arethe massfractionsof speciesT in the inflow
streamfrom previousunits, the gasoutput streamand the productoutput streamrespectively.
The model accountsalso for a possible scenarioof initially loading the reactor with an
amount of deactivated ("dead") polymer. This polymer does not participate in the
polymerization;it doesnot carry active sites and servesonly for the fluidization of the bed
during a start-upperiod. Therefore,an additional massbalanceis written for the amountof
this polymer:
d(Cdead )=_ Cdead
FoutXout.
N (7.8)
dt - Polmm
wherePolm., is the overall polymermassin the reactor:

POI "": Cdcad + Cpre + Cpol (7.9)
Mass
The cumulativemolecularpropertiesof the total polymermassin the reactorandthe polymer

in the productstrearn,result from a mixing rule of the partial propertiesof the different types
of polymer in the bed. The number and weight averagedegreesof polymerization and
168
molecular weights and the density of the overall polymer massin the bed are given by the
following expressions:
MPdead +C MPpre +C MPpj

mpt dead pre pj
=C . Molecular Property
Pol (7.10)
Mass
MP: DPngDPwgMntMw
POI
Mass
Pt = (7.11)
Cdead CPre CPOI
+ +
Pdead P P
pre pol
Accordingly, consideringthat polymerizationtakesplaceexclusivelyin the effective volume
"heavy" balances
for Sk,
of the phase,the molar the potentialcatalystsites, p the vacantactive
yk, k, k, k
sites, Pok, and all other molecular species (yk : Xk, Xk, Xk,
012 110PI 92) are derived with
respect to this volume:
d Fmt [Spj,
kkk 1+ Spk
Fýxj, + Rsp - Qocef
dt Dcat
kkk lpo 1
F,',-. j,, +Rpo -Qo 8cf
dt c
= Rky _ Qo Sefyk
dt
where Fk-
POWnand Fk-
VaC.
In are the inflows of potential and vacant catalyst sites of type T
respectivelyfrom previous units, rf is the fraction of the effective volume over the reactor
volume, Q. is the volumetricrate of productwithdrawal streamand RkRk Rs'
Y PO Pare reaction
termsderivedaccordingto the kinetic scheme(seeAppendixA).
The dynamic energybalanceis written for the total bed masssince both the "light" and the
"heavy" phasessignificantly contributeto temperaturevariationsobservedin the bed:
dfLccum Hgas, Hprod. Hgas, Hgenr

= in + pre - Hpd,, - out + (7.15)
dt ut
169
where the terms Hg., in, Hprod,pe,, Hprod,outqHg,,.,,.ut, and Hg,. r denote the enthalpy of the total gas
inflow (make-up and recycle streams), the product stream coming from the previous unit, the
product outflow from the reactor, the gas outflow at the top of the reactor and the heat
produced due to the exothermic polymerization reaction, respectively. Analytically the
mathernatic expressions of these terms are given below:
)ýiw-i II
XtH'i Cpj
H accum Mi +POIM, + POI MassCP (T-Tf) (7.16)
ass XtH, pol
Ný,
ýp
Nf lFm, CPmk, N IXL, cprec,

-1 i 2-1 i
Hgas, (Tmk -Tref )+ Frec() (Tc -Tr) (7.17)
in ý-- i mwil
1 mwil
i=I
I Ný I E--Pi. J+Xin,
p-I
X (Tpre -Tref (7.18)
Hprod,
ý Fi, Y, inj
'i
N,,,,,,, 1
pre ,, i=l
Mwi pCPp.
1N p-1
1X0ut, Cpi 1+Xout, 1
Hprod, F. CP (T - T (7.19)
out 7- i N pol t)
ut Mwj p
i=I
Cp' I(T-T..,
Nýýp-l
H gas,out 4 F,, X
L, i Mwi (7.20)
-, c f)
Hgenr = -R
pAHreac
Assuming that the dynamic behaviour of the heat exchanger can be approximated by a tube
the tube can be modelled as a series of N'. well-stirred zones
and well-stirred tank system and
of equal heat exchanging area (A) and equal amount of gas accumulated in each zone
(Mgasi),the following dynamic energy balances for the recycle gas-streamin the tube and the
coolant in the continuous stirred tank can be written:
Energy Balance for thegas in the well-stirred zones

IS,
Hgas,
j : -- Mgas, j
CP
meanj
(Th,
j - Tref)l j=2,3,..., Ný (7.22)
dHgas,
j F,, tP (Th, Tref CP (Th,
j - TrIf Qi2,3,..., N, (7.23)
= j-1 -
dt co j-1
mean, meanj
170
Ný NA
Q=2: Qj=2: jAj h,j - Tw (7.24)
j=l j=l
Th,
1 «=0*0; Trec=Th,N.; QI ýO,0; MO. l =O-O; Hg., 1 =O-0 (7.25)
,
EneM Balance for the water in the well-stirred tank
Hw =MaqCPw(T- -T. f) (7.26)
dH
Cp. (T, - Tr (7.27)
dt , f)+Q
Further analysisof the symbols used in the equationsaboveand the valuesof the several
model parametersare given in section 7.4 and Appendix B, where the model inputs are
described.
7.2.3 Flash Separator Model

A dynamic model for the Flash separator in the plant has been developed. A two-phase
mixture is formulated in the flash tank, a polymer-rich ("Heavy") and a polymer-lean

("Light") gas phase. Thermodynamic equilibrium is assumed to settle instantaneously
between the phases and the flash calculations are carried out employing the Sanchez-
Lacombe EoS. It is assumedthat no polymerization occurs in the Flash unit and therefore the
mass
unsteady-state for
balances Mi
components and the energybalances
are derived:
d(Mi)
=
FinZinJ -Fout. HXout. Hi -FouýLXIJ (7.28)
dt
U 2--MHHout. MLH. 2.3906 PV,,

H +
ut.L - s.,
(7.29)
dU N'"(Zi,
(7.30)
=F inH.in-F In ý,IAH,.p,1)-F .. -Fout.
LHoutl
where FingFout.
L and FuLH,are the flow rates of the input stream from a previous unit, the
output "light" stream recycled back to the first reactor unit and the output "heavy" stream
sentto the FBR. V,,,,., and P is the volume and the pressurein the flash tank and MH.ML is
the massof the "heavy" andthe "light" phasein the flash vessel:
171
N,
ýmp
MH 2A
2-- WH
(7.31)
i=l
N
fflp
ML =WL ZMi (7.32)
i=l
where WH and WL are the mass fractions of the two phases at equilibrium. AH,, i is the
p,
vaporization enthalpy of component T in the input stream and Hi,,, ILutH, RIAL are the
enthalpies of the input stream, with pressure Pi., and temperature Ti.,, and the "heavy" and
"light" output streams,respectively:
N, I
"nr,
(ZinCPin, (Tin Tf dVi.
Hin - + 2.3906 Pin (- - Tin (7.33)
i) dT
Pin
N1
HouLH =
ijXH,, dVH
jCPi)(T-Tref)+2.3906 P(--T-) (7.34)
i=l PH
NI
ilXLiCpi)(T-T,,, dV
HouLL'ý f)+2.3906 P(--T'JYL) (7.35)
i=l PL dT
The thermodynamic functions appearedin the equations above are calculated by the
following expressionsof the Sanchez-Lacombe
(S-L) Equationof State(seealso Appendix
D):
S-L, (Zi, T, P Mn, (7.36)

flash9 pre)
dVin S-L2(Zin,
Pin 9 = ifTinPpin9Mn, prc) (7.37)
dT
dVH dVL
WHOWLXHj9XL. S T, P, pp. M., ) (7.38)
itPHIPL9 jT-t-
dT -L3(Zi, 1, P,,,
whereZ- 7,,,
j,, XHj9XW is the massfraction of T
component in the Flash,in the input stream
Pint PpoltPH9PL9is the density of the
and the "heavy" and "light" phase respectively. Pflasho
total mixture in the flash, of the mixture at the input stream, the polymer density and the
density of the two phasesrespectively, while M,,, is the number average molecular weight
p,,
of the polymerin the Flashcomingfrom a previousunit.
172
Finally, it is pointed out that a pressureand a level PI feedbackcontrollersare employedin

the Flashtank usingF.ua andF,,utHasmanipulatedvariables.
7.2.4 Thermodynamic Model

For pressure and thermodynamic equilibrium calculations in the Flash unit the Sanchez-
Lacombe EoS is used. It is appropriate for polymer mixtures and derives from a lattice-fluid
model (Sanchez& Ucombe, 1978; Mchugh and Krukonis, 1994; Orbey et al., 1998; Yjrby &
McHugh, 1999):
+P +T In 1- P)+( 1-i p =o (7.39)

r)
_( j
where P, T and p are the reduced pressure, temperature and density of a pure component
defined with respect to characteristic values of the component, and r is the number of lattice
occupied by a molecule. To apply this equation to a mixture of components mixing rules are
used to find the characteristic values of the mixture (Tý*jx Oax

P; p*n*dxurwx, r-wx ), which are
9 9 9
necessaryfor the calculation of the reduced parametersof the mixture:
Tmix =T/Týj whcrcT*.

nux =c n-jx /R,
x
Pmix = P/Pýjx where Pýjx =6 mix /U..
ix, (7.40)
Armi, Um
p mix =p/p,, mix where p.mix = Mw mix ix)
where e. andu*is the interactionenergyper mer of eachcomponentof the mixture and the
closed-packmolar volume of a mer. When these propertiesare defined for the mixture,
mixing rules basedon the volume fraction (yi) of eachcomponentin the mixture are used,
while binary interaction (kij,
parameters nij) are employedto correct the interactionenergy
and the molar volumeof a mer of mixture.
NN
Z 4i(pjuijl
u AGE whereu*ii =0.5(u*ii +u..hu)(1-nij)

i=l j=l (7.41)
Ncnrnp
Nomm
fyigjcijuijl
r ngx Un-jx
; where cij =(cjjcj)0,5(l -kij)
i=l j=l
173
Industrial experimentaldata and data from the literature (Moore and Wanke, 2001) for the
solubility of monomersand other components(i.e. H2,N29C3118)
in PE at severalconditions
are employedto properly tunetheseinteractionparameters.
At thermodynamicequilibrium betweenany two phases,it is known that the fugacitiesof

each componentin these phasesmust be equal. Therefore for the two-phaseFlash unit
("light" (L) and "heavy" (H) phase) the fugacity relationshipsat equilibrium for every
componentI' are:
f, H = f. L C.* X! i 0! 1 LoiL
IIII
Xi (7.42)
where fi is the fugacity of componentT and XH'XL'

ii Oý andOý are the molar fractions and
the fugacity coefficientsof componentT in the two phases.For polymer-monomer-solvent
mixtures it is convenientto expressthe phaseequilibrium statementin terms of chemical
potential,pi (for further analysisover this equationof stateseeAppendix D):
giH
= IiiL ;i=1,2 N. (7.43)
IIp
At this point it is important to point out the effect of polymer crystallinity on the equilibrium
consideringthat only the amorphous fraction of polymer interactswith the other components
of the mixture. This means that in a polymer-monomer-sol vent mixture, the fraction of
polymer with the high crystalline molecular structure does not allow solubility of the "light"
components (monomer and solvent), hence all the equations related to the Sanchez-Lacombe
EoS, the mixing rules and the phase equilibrium statement are written based on the
amorphous fraction of polymer. For semi-crystal line polymers, the degree of polymers
crystallinity is expressed in terms of the volume fraction of the amorphous polymer (aj
defined as a function of polymer's density:
P'Y' -P
av = (7.44)
Pcrys - Pam
The correspondingmassfraction of crystalline polymer is derived by Kreituss and Frisch

(1981):
Pays
X.. =(I -a, ) - (7.45)
Y, p
174
where p. -y,and p.. are the densities of the crystalline and amorphous polymer respectively.
Similarly to the Flash unit, a two-phasepolymer-solvent-monomermixture exists in the

fluidized bed reactor unit. However, due to the polymerizationreaction that takesplacein
this unit, sharperand continuouschangesof the compositionof the two phasesare observed
and it takeslonger for the phaseequilibrium to settledown. Therefore,consideringthe high
EoS for the phaseequilibrium calculations
computationalcost of the Sanchez-Lacombe
(based on chemical potentials), Henry's Law is applied instead. The mass balances in the
FBR were properly derivedin orderto calculatethe sorptionof the "light" componentsin the
"heavy"-polymer phase as function of the composition of the "light" phase.Hutchinson
(1990), found an empirical correlation for the constant of Henry's Law based on
experimental observation of the effect of the critical temperature of the penetrating
componentT in the polymer andthe temperatureof the mixture:
Tci
Log(K *HJ) = ai +bi (7.46)
T
This correlation fits the Henry's Law constantfound experimentallyfor a large numberof
organiccompoundswhile it is further tunedto comply with the industrial datareferringto the
operatingcondition of the Borstar@
process. Accordingly, the total mass of the penetrating
component T in the "heavy" phase (basedon the amorphous fraction of polymer) is the
following:
Mp.,,i = Kýj Pi a,, Polm., Mwi (7.47)
where Pi is the partial pressureof component I' in the "light" The

phase. mass composition
of the "heavy" phasecan be defined with respect to both the amorphouspolymer fraction
(XH, (XtH,
i) and the total polymer mass i):
m
XHJ ýN P", i i 1,2 (Ncomp - 1)
-, ...
-1
M + POI Mass(1 -X
poij crys)
(7.48)
PO' (1-X
Mass crys
XH.
N4xwm
ymp. Pol (I xcys)
i=l i
1,+ Mass-
175
mpol'i
Xdi,
i =N-, -0 i=1,2 (Nc - 1)
ympoli ... ,. p
+ PolMass
i=l
(7.49)
X PO'Mass
tH, NODnip =
N. -1
M + PolMass
pol,i
i=l
In consistency to the definition of two different compositions of the "heavy" phase basedon
the amorphous and the overall polymer, two different mass fractions of the two phasesin the
bed are defined considering only the amorphous polymer (1,., H.. ) and the total polymer
mass(4 Ht):
GasMass
Lam == Ham=I-Lam (7.50)
I -,
Gas + Pol m., (I - x,,, )
m., Y, X tH, Nc
,,,. Ip
I
Polm.,
'ltli, Nýnr
Ht 9 Lt =I-Ht (7.51)
R Mass
where Gasm,, is the total massof the "light" phaseand Rm., is the total massthroughoutthe
bed:
N' -1
: EM. (7.52)
Gasm. =
N -1
Rm., =Gas m., +POIMass
+ YMpl, (7.53)
i=l i
Considering that the crystaine fraction of polymer is "inactive" from a sorption point of
view and from the viewpoint of polymerization (since no monomer is sorbed in this fraction
of polymer) the concept of the "effective volume" (V, f), where the polyme ri zation is taking
.
fraction the in the reactor (L,,. )
place, emerges and a of crystalline polymer mass Y, and
amorphous polymer mass (M,, f) which is used as reference mass for some calculations are
introduced:
Polm., Xcrys
Lcrys Mf (7.54)
-
R Mass =1-Lcry,
176
HamR Mref
Mass
Va = (7.55)
P H,
am
Recalling that the polymerizationis taking place in this effective volume it is crucial for the
calculationsof the kinetic ratesof the polymerizationmechanism(seeAppendixA) to define
the molar concentrations of the "light" components in this volume:
IM 1=PH, X / MW
pol,i ani HJ i (7.56)
The total bed volume is given by the fraction of the volume of the "light" or "heavy" phase
over the void fraction of the bed:
VH ý-
R Ma,, H, Ma,, Lt
VL =R (7.57)
PH,t , PL
VH VL
VR :
-- = (7.58)
(I - Void) Void
where Void is the bed void fraction. PH,,,,,,and PL are the densities of the "heavy" phase
(based on the amorphous polymer only) and the "light" phase respectively found by the
Sanchez-LacombeEoS, while PHJ is the density of the "heavy" phase based on the overall
polymer mass:
Ht
PH.t :"-- (7.59)
HamMref LaY,
+
PH,am Pays
7.2.5 Process Control Conriguration

In a previous chapterwhere a thorough discussionwas reportedover the synthesisof the
appropriateprocess control system architecture,safety, operational and product quality
specificationswere statedas the major reasonsfor intensiveprocesscontrol. In the caseof
the FBR the temperatureandpressurein the bed aretwo importantoperatingvariablesfrom a
safety point of view. The danger for thermal runaway emergeseven more seriously
consideringthe exothermicpolymerizationreactionand the sharpchangesin productionrate
due to the high activity of catalystsites in the bed. Suddenincreaseof reactortemperature
177
may drive the processto uncontrollable conditions close to polymer melting point and
consequently,to particle agglomerationand polymer buildup on the intemal reactorsurfaces
with final collapseof the fluidized bed.On the other hand,broadvariationsof pressurein the
bed set in dangerthe smoothoperationof the reactor,while it implicitly affects the product
molecular propertiesthrough its influence on the sorption of the "light" componentsin the
polymer particlesand the polymer molecularstructure.Taking into accountthe fluidization
conditions in the IFBRthe bed level is anotheroperatingvariable that should be held under
control becauseundesirablechangesof bed level is an index of abnormalfluidization of the
bed with consequences
on productentrainmentandtemperaturecontrol.
From the viewpoint of product quality, polymer density (pt) and molecular weight (M., ) for
the final product should be controlled in order to make sure that the product satisfiesthe
market specifications as long as a specific polymer grade is produced with a certain
production rate (Rp).
All the streams of process inputs and outputs, as presented in the rector model section, can
serve as manipulatedvariables for the control of the plant. Table 7.1 summarizesthe set of
controlled and the potential manipulated variables for the FBR. The mass flow rate of the
(F,,,
recycle stream c) is actually a design variable and it is excluded from the set of the
manipulatedvariables.
Table 7.1: List of controlled and manipulated variables of the FBR.

Controlled Variables Possible Manipulated Variables
1. Reactor Temperature (T) 1. Make-up monomer flow rate (Fm, )
2. Reactor Pressure(P) 2. Make-up comonomer flow rate (Fm, or Ratio)
3. Bed level (h) 3. Hydrogenflow rate(Fm,
4. Production Rate (Rp) 4. Nitrogenflow rate (Fm,
5. Polymer Density (pt) 5. Propaneflow rate (Fm,
6. Polymer Molecular Weight (M,,t) 6. Productoutput (F. t)
7. Recycleflow rate(F,. )
)
8. Waterinflow in the heatexchanger(F,,,,
(Fbid)
9. Bleedflow rate
10.Catalystflow rate (F,.t)
178
Chapter 7 Plant-NVIdeIssues
From the set of the manipulated variables enlisted in Table 7.1 the propane flow rate (Fm,
applies only for the Loop reactor and there is no need for any additional propane feed in the
FBR. Besides this, in the FBR as it has been clearly stated before, there is no fresh catalyst
feed and the bleed flow rate is set equal to zero to comply with the operating profile of the
Borstare plant. In the square control scheme of the six controlled and the remaining six
manipulated variables a "one to one" pairing between controlled and manipulated variables
has been selected based on heuristic rules, which was confirmed by the Relative Gain Array
(RGA) analysis on this set of variables (see Chapter 4, Table 4.3). The control structure
resulted from this analysis is implemented on this model while a simple Proportional-Intcgral
(PI) feedback control law was selectedto calculate the controller output (U):
It
Ui =Bias, + Kc,ij Ej +f Ej dt (7.60)
"I-ij o
where K,, TI,

ij, ij are the PI controller parameters and Ej is the error trajectory of the controlled
variable Yj from the set point value Yj,

sp:
EI =T-Tp
E2 :-- P- Psp
E3
=h -h, p
(7.61)
E4 =Rp -RP. sp
E5 =pt -ptp
E6 =Mnt
-Mnt, sp
In order to constrain both the controller output and the rate of change (CR) of this output
between upper and lower bounds, the actual control action (CA) for every controller and
finally the real values of the process manipulated variables (F,,,,,) are derived accordingly in
order to enable a process simulation with realistic dynamics.
CA i= min JUpperboundi, (Ul, )}

Lowerboundi (7.62)
max
(CR-slucki)
CRi =d =k (CA CR-sluck (7.63)
dt i- j)
d (F,,.
I,i) min JCR max(- CR...,, CRI)) (7.64)
=
dt
179
The control structureconfigurationin the Flashunit is much simpler sinceno polymerization

occursthere.The pressureof this processunit is the main variablethat shouldbe controlled
to ensurethe successfulflashing of the polymer mixture coming from the Loop reactor.The
"light"-gas output stream (F.. tL) is used to control the pressurein the flash unit undera
constrained PI feedback control configuration, similar to that usedfor the FBR. The second
available manipulatedvariable in the Flash separator,that is the "heavy" output stream
(F.ut,H)9is usedfor an implicit level control of the Flashunit. This control schemeis basedon
the hypothesisthat the amountof polymerremovedfrom the bottomof the Flashvesselto the
FBR is equalto the amountof polymergettinginto the Flashfrom the Loop reactor:
Fout,
HXtli, Ne, =Fin Zin, Nconv (7.65)
n,p
This assumptionsimplifies the dynamic behaviourof the Flash unit since the accumulated
polymer mass in the Flash tank is retained constant.
7.3 Modelling Limitations
There are a large number of model inputs necessary for the dynamic simulation of the
Borstaro plant. Within these model inputs, there are some tunable parameters that have been
introduced to confront the model's imperfection at the current version. This presupposesfull
comprehension of process operation and identification of model deficiencies relatively to

how well it represents the real plant. These model deficiencies result mainly from some
simplifications made either to avoid overcharging the model with equations, or due to a
weaknessof accurately modeling of process units.
The first tunable parameter is related to the Flash separator unit. In the Flash it is assumed
that the dynamics of phase equilibrium are very fast. In the tank there are two well-discreet
phases ("light" and "heavy" phase) and two output streams (F. t.L and FMH). Although the
composition of the "light" output stream might be reasonable to be the same with the
"light" the composition of the "heavy" output stream in practice is
composition of the phase,
"heavy" due to possible entraining phenomena from the "light"
not the same to that of phase
phase or erroneous assumption for phase equilibrium establishment between the two phases
in the flash vessel. To account for these phenomena an "entrainment factor" is
introducedto definethe compositionof the "heavy" output stream:
180
XoutH,
Kentr = (Ncomp- 1)
X ,i=1,2 .....
Hj
(7.66)
N -1
Xout, x
HN =I- outHi
omm i
Therefore, the composition of the "heavy" output stream is not equal to that of the "heavy"
phase, but it is enriched with "light" components at the expense of polymer. Note that this
factor is the same for all the "light" components.
The remaining tunable parameters refer to the FBR. The product removal stream from the
FBR conveys together with the polymer a significant amount of reactants and inert gases
either sorbed in polymer particles or entrained by polymer particles. In order to retrieve these
valuablecomponentsthe product streamin practicepassesthrougha flash unit operatingat
low pressureand the gaseousspeciesare recycled back to the FBR. Since an additional
dynamic model, for a flash separator unit located at the exit of the FBR, would
computationally overchargethe model it was "replaced" by a set of tunable parameters
(Kf1uh.
1)for the calculationof the compositionof the overall productoutput ignoring
stream,
the dynamicsof this additionalflash separator:
Xoutj
K flash, i - 9
i=1,2
x4i
N
(7.67)
-1
x =I- Xoutj
out.N p
Hence the composition (X.O,,

t,j) of the product output stream (F. t), with proper tuning of
Kflash,
i becomes
equal to the composition of the "heavy" output stream of the flash unit, while
calculation of the gaseousspeciesrecycled back to the FBR has been avoided.
The bed void fraction (Void) is a crucial parameter indicating the fluidization conditions in
the bed and therefore the dimension of the bed as well as the mixing and contacting pattern
betweenthe phasesexistingin the bed.Sincethe "light"-gas phaseandthe polymerphaseare
the only two phasesconsideredin this study (ignoring the existenceof other phases,i.e.
bubble phase)the bed void fraction is the volume fraction of the "light" phasein the bed.
Consideringthe well-mixed patternthat is assumedin the bed, the void fraction remainsthe
same along the bed while it is assumedthat during a dynamicchangeof the operatingprofile
of the FBR (i.e. during a gradetransition)the void fraction changesinstantaneously.Due to
the lack of analyticequations,or empiricalcorrelationsfor the calculationof the bed voidage
181
it is treatedas a tunableparameterto fit the bed volume(basedon industrial data)depending

on the operatingprofile of the reactor.
The current model for the Borstaroplant has beenbuilt to accountfor the last two process
units, that is the Flash Separatorand the FBR. It is well known though that the evolutionof
polymerization exclusively in the FBR dependson the molecular characteristicsof the
polymer feed from previousunits (Loop reactor).Therefore,polymerizationis possiblein the
FBR only if catalyst sites are conveyed to the FBR with the polymer stream from the Loop in
the form of potential, or vacant catalyst sites or "live" polymer chains. Due to the high
activity of Ziegler catalyst fed in the "pre-polymerization" rector unit of the plant it is
assumed that all the potential catalyst sites have been activated in the "prepolymerizee' and
no activation occurs in the subsequentunits. Besides this, for the polymer stream leaving the
Loop reactor it is assumed that the "live" polymer chains have been deactivated, by chain
transfer and spontaneousdeactivation reactions, and only vacant active sites remain available
and transferred to the FBR through the Flash Separator. Since the present model does not
contain dynamic models for the Loop reactors of the plant, the flow rate of the vacant catalyst
ff,)k type W becomes tunable The fresh catalystfeed in the "pre-

sites in
ac. of a parameter.
polymerizer" and the operatingconditionsin the Loop reactorfor every polymer gradeare
taken into considerationfor the propertuning of the overall vacantcatalystsitesinflow from
the Loop andthe relativeflow ratio of onesite to the other.
The list of the tunable parameters of the model is completed with the kinetic rate constants
for the polymerization kinetic mechanism. These constants obey to the Arrhenius kinetic
expression:
E
K =KO ex -.F- 7. T (7.68)
T)
g.
where K. and E is the term

pre-exponential and the activation energy and Rg., T is the
universalgasconstantand the that
temperature the reactiontakes place.The polymerization
mechanism (section 7.2.1) adoptedin this study consistsof 16 reactionsover eachcatalyst
site consideringthe existenceof two types of monomers.In the presentmodel a two-site
catalyst is consideredraising the number of reactionsover both sites to 32, and the total
numberof kinetic parametersto 64 (pre-exponentialconstantandactivationsenergies).
182
7.4 Model Input Parameters
There is an amountof information requiredby the mathematicalmodel in order to carry out

the dynamic simulationof the Borstaio plant. Thesemodel inputs rangefrom dimensionsof
processunits to parametersfor physicalpropertiesand can be classifiedin groupspreiented
in tabulatedformat. Discussionover thesemodel parametershelpsfor further comprehension
of processoperatingfeaturesandthe modeldevelopment.
In Appendix B the physical property parametersof the componentsappearedin different

units of the plant are presentedin Table B.3. Due to the sequentialstructureof processunits
in the Borstar plant, the interconnectingstreamstransferringpolymer and other compounds
successivelybetweenthe units influencethe operatingprofile and the molecularpropertiesof
the producedpolymerin eachunit. Thereis a setof variablesdescribingtheselinking streams
in ten-risof their flow rate, composition,pressure,temperatureand polymer properties.Table
7.2 describesthese data for the streamlinking the Flash separatorwith the Loop reactor
(previousunit) for the two different industrial polymergradesconsideredin this study.These
variables are consideredas model inputs and should be assigneda value in order to
the
mathematicallyrepresent "information stream"conveyedbetweenthe Loop and the Flash
separator.
Table 7.2: Linking-parametersof the FlashSeparatorwith previousunits (Loop Reactor).

Value
Parameter description Symbol Units
Grade A Grade B
Mass flow rate from previous unit Fi. 15795 13824.3 (kgth)
Mass fraction of ethylene Zinj 0.0200 0.01714 -
Zin, 0.02545 3.544410-4
Mass fraction of butene 2 -
Zin. 4.7166 10'4 6.322210'4
Mass fraction of hydrogen 3
Zin. 0.46255 0.407615
Mass fraction of propane 4 -
Zin, 0.491578 0.5742577
Mass fraction of polymer 5 -
Temperature of the stream from previous unit Ti,, 358.15 368.15 (K)
Pressureof the stream from previous unit Pi., 64.6 64.9 (bar)
DP., 192.588 115.8544
Degree of polymerization of polymer from P,,, -
previous unit DP,,, 486.61 292.7280 -
P,,
Molecular weight of polymer from previous m., 5459.8 3245.0 (gr/mol)
P,,
unit M 13795.4 8199.1 (gr/mol)
Density of polymer from previous unit Ppre 951.3 970.0 (k g/M3)
183
The final group of model inputs is the degreesof freedomof the model. This group consists
of a numberof variables,which are divided into two types;the variablesgiven by the userto
define the polymer gradethat should be producedundercertain operatingconditions,which
might havederivedeither heuristicallyor underoptimization.Thesevariablesor part of them
can be used as optimization variables in case of a dynamic optimization during a grade
transition.The other type of variablesrefer to structuralcharacteristicsof catalyst,in caseof
catalyst feed in the FBR, and to the molecular propertiesof deactivatedpolymer (dead
polymer') initially loadedin the reactoraccountingfor a possiblestudyof the plant behaviour
during a start-up.The valuesof thesedegreesof freedomfor the two polymer gradesstudied
in this work arepresentedin Table 7.3.
Table 7.3: Degreesof freedomandInitial conditions.

Value
Parameter description Symbol Units
Grade A Grade B
Product Quality - Operating Conditions
Pressure set point in the Flash unit PP 1.5 1.5 (bar)
Bed level set point in the FBR hsp 16.8 16.5 (M)
Pressureset point in the FBR PP 19.5 19.5 (bar)
Polymerization rate set point in the FBR R 11283.5 9697.8 (kg/h)
p,sp
Temperature set point in the FBR TP 353.15 353.25 (K)
Overall polymer density set point in the FBR PtSP 921.7 943.0 (kg/m3)
Overall polymer molecular weight set point M
7500 (gr/mol)
ntsp 11650
in the FBR
Flow rate of the recycle stream in the FBR Fr., 538 103 502103 (kg/h)
Flow rate of the bleed stream in the FBR FbIced 0-0 0.0 (kg/h)
Flow rate of the catalyst stream in the FBR F,at 0.0 0.0 (kgIh)
,
Initial polymer loading in the bed-Catalyst characteristics'
Metal concentration in the catalyst feed [Me] 0.0 0.0 (Mol/nI 3)
stream
ft 0.5 0.5
Molar fraction of active metal of type T site -
f2 0.5 0.5
site -
DP.,
Degree of polymerization of 'dead dead 192.588 192.588
polymer'
in the FBR DP,, &,d 486.61 486.61
Mim, 5459.8 (gr/mol)
Molecular weight of 'dead polymer' in the dead 5459.8
FBR Mw. 13795.4 (gr/mol)
dead 13795.4
Density of 'dead polymer' in the FBR Pdead 951.411 951.411 (kgIM3)
*Sk in
P, =[Me]fk site
184
7.5 Simulation Results
In order to illustrate the simulating capabilities of the model the model predictions are
compared with steady-state industrial data of two operating points corresponding to two
polymer grades. The polymer molecular specifications and the operating conditions of
process units for the two grades have been presented in the first part of Table 7.3. The first
grade corresponds to a high molecular weight, low-density final polymer product, while low
molecular weight and high density are the specifications of the second polymer grade. Note
that the molecular characteristics of the final polymer product are proportional to that of the
polymer coming from the Loop reactor in the sensethat the higher are the property values of
polymer from previous units, the higher are the property values of the final product and vise-
versa. The operating conditions in the FBR are the same for both grades despite the distinct
differences in polymer molecular properties. Hence, it seems like these operating conditions
are satisfactory from fluidization and phase equilibrium point of view. Accounting for the
different molecular properties of the polymer grades the kinetic rate constants of the two-site
catalyst were tuned so that one catalyst site to be in favour of low density and high molecular
weight polymer corresponding to the first grade. Therefore with proper tuning of the flow
k
(Fvac. ) from the Loop the
rates of the vacant catalyst sites in coming reactor molecular
specificationsfor the two polymer grades can be achieved. The tuning of theseparameters
should be in consistencyto the initial loading of the "pre-polymerizee'with fresh catalystfor
the two grades.The Arrhenius expressionsof the kinetic rate constantsfor the two sitesof
catalyst as well as the feed rates of vacant catalyst sites from the Loop in the FBR are
presentedin Table A. 3 of Appendix A. It should be noticed that the overall vacantcatalyst
site feed for the secondpolymer gradeis higher than that for the first gradecomplying with
the increaseof fresh catalystfeed rate in the "pre-polymerizer"from the first to the second
grade.
The numberof model predictionsthat can be comparedto availableindustrial valuesis large

enough to let a global assessment
of model capabilitiesfrom different In
perspectives. Figure
7.2 the time evolutionof cumulativepolymerdensityduring the transitionfrom gradeA to B
and back to A is presentedfor the overall polymer product and the polymer produced
exclusively in the FBR. Model predictionsagreeperfectly with the industrial valuesboth for
the total polymer massand the polymer producedin the FBR. This indicatesthat the model
predicts the
successfully ratio of massesof the two types of polymer existing in the FBR at
185
970
965
960
955
950 ....... a
945 Grade B Overall polymer

945
Previous unit
940
940
935
935- ...... FBR polymer
do set-point
930
930
.j set-point
925
925-
920 -
GradeAs Grade A
915-
910-
905'
go0- CI
895
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.2: Time profile of polymerdensityduring the transitionfrom gradeA to B and

back to A.
steady state for both polymer grades, considering the mixing rule applied between the
propertiesof the severalpolymer typesin the FBR to derive the total polymer The
properties.
dynamicsof densitychangesof the total polymer massare very similar to thoseof polymer
producedin the FBR due to the instantaneousdensity changesconsideredfor the polymer
coming from the Loop reactor.
A similar graph for the secondproduct quality property, the number averagemolecular
is
weight, presented in Figure 7.3 for the two typesof polymer and the overall polymermass
existing in the FBR. Once again the simulation results at steady state are in good agreement
with the industrial values,which are used as set points for the product quality controllers.
Therefore,the model's reliability is illustratedby the comparisonof the controllers' actions,
namely the flow rates of the make-up streams, and the correspondingindustrial values.
Figures 7.4-7.8 demonstratethe flow rates of the make-upstreamsand the percentmolar
fraction of the light componentsin the light phase.Steady-stateindustrial dataarecontrasted
against model predictions. The successful comparison between simulation results and
industrial valuesdemonstratethe satisfactorytuning of model parametersfor both polymer
grades andthe capabilityof the selectedthermodynamicmodels to simulate the phase
186
17001
1600( Overall polymer
Previous unit .............
150o(
------ FBR polymer
1400(
set-point
130o(
"Grade A
1200( 0.
110o( Grade A
.......................
ioooc
900c
800c Grade B
" 10 0
700C
600C
500c
4000
--------------------
3000
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.3: Time profile of polymernumberaveragemolecularweight during the transition

from gradeA to B andback to A.
21.0
10500
20.5
10000
20.0
6.a
. 9500
19.5
19.0 9000
18.5 8500
18.0
8000
17.5
7500
17.0 11, IIIIIi
IIIIIII. ' ýO
0 10 20 30 40 50 70 80 90 160
Time (h)
Figure 7.4: Time profile of the molar compositionof the light phasein the FBR andthe
make-upstreamduring the transitionfrom gradeA to B andback to A-Ethylene.
187
2000
13- Butene light-phj ase
Industrial values 1800
12
1600
11-
.-AW 0-0 4)
-A
10- 1400
9- 1200
8- 1000
7- 800
6-
600
5- 1
Butene niake-up 400
4- Industrial values
r 200
0 10 20 30 40 50 60 70 80 90 100
Tinte (h)
Figure 7.5: Time profile of the molar compositi on of the light phasein the FBR and the
make-up stream during the transition from grade A to B and back to A-Butene.
3.5 12.5
-Hydrogen light-phase
h9 Industrial values
3.01
2.0
2.5- Hydrogen make-up
Industrial
rA
2.0- 1.5
1.0
1.0-
0.5- 0.5
10 0
0.0 Iv J-
0.0
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.6: Time profile of the molar composition of the light phasein the FBR and the
make-up stream during the transition from grade A to B and back to A-Hydrogen.
188
58
80
56
70
54 60
50
52
40 2
Ll
50
30
48 20
10
46
i. 10
I, I, I, I, -1 ___ -, III -r- ,1
0 10
20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.7: Time profile of the molar composition of the light phase in the FBR and the
make-up stream during the transition from grade A to B and back to A-Nitrogen.
22.0 * Propane light-phase

-Industrial values
21.5
21.0
20.5
9
e 20.0
19.5
19.0
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.8: Time profile of the molar composition of the light phasein the FBR and the
make-up stream during the transition from grade A to B and back to A-Propane.
189
equilibrium betweenthe phasesof polymer mixture. The make-upstreamsslightly deviate

form the real valuesaccountingfor the streamcoming from the Flash to the FBR. Summing
up the flow rates of thesestreams(make-upstreamand inflow streamfrom the Flash)for
eachcomponentresultsin the actual-industrialvaluesof componentinflow ratesin theFBR.
In Figures 7.9-7.12 the time change of the FBR operating conditions during the transition in
terms of the bed level, the bed mass and the production rate and the reactor pressure and
temperature, as well as the flash pressure are presented. PI feedback controllers are used to
drive these process variables to their set points. The bed void fraction (Void) was tuned to fit
the bed mass predicted by the model to its industrial value for the two grades. Slight change
of void fraction required between the two steady-state operating points
(VoidA VoidB and it is expected that dynamically the void fraction
=0.7027; ='0.7159)
wouldn't change significantly during the grade transition.
17.4 24000
---- Product ren]Oval
o Industrial values
17.2 22000
17.0
Grade A- 20000
Grade A
,R 16.8
%_o 9ý0-<> -0- -0- -0 - 0- -0- -c- <>-O« 18000
m 16.6- Grade B
m 16000
.2 16.4
14000
16.2
16.0- -Bed levýel

ýIevel 12000
110000
Bed set-point
15 8. --* ' ýO ' ' ' ' ' ' ' '
0 10 3'0 410 5'0 6'0 710 8'0 9'0 100
Time (h)
Figure 7.9: Time profile of the bedlevel andthe productremovalfrom the FBR during the
transitionfrom gradeA to B andbackto A.
190
12000
Bed Mass
55000-
o Industrial values
11500
Grade A
'4000 GradeA
11000
53000
10500
52000
10000
51000 Grade B jrate
Production rate
Set.poctlon
nt
int
50000 ...... --, --T' . 9500
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.10: Time profile of the total bed mass and the product rate in the FBR during the
transition from grade A to B and back to A.
356
Reactor Pressure I
20.5] Set-point
355
20.0 354
v Grade A 52
,ýa -0 2
Grade B - 353
353
19.5- i
Grade
radeAA« 1
352
19.0
351
IV \1
18.5 ---- Reactor temperature
350
0 Set-point
' ' ' ' ýO , ýO ,
0110210' 3'0 410 5'0 6'0 9,0 100
Time (h)
Figure 7.11: Time profile of pressureand temperature in the FBR. during the transition from
grade A to B and back to A.
191
2.0 65.0
Grade B
..............................
1.8 64.8
Grade A Grade A
01.6 *------------------- 64.6
Ll
1 000* 00*
1.4 64.4 1
Ak
2
1.2 64.24
-Flash Pressure
fo Pressure set-point
1.0 -164.0
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.12: Time profile of pressurein the Flashunit andthe previousprocessunit during
the transitionfrom gradeA to B andbackto A.
7.6 Optimal Plant Operation
After the identification of the capabilitiesof the comprehensivemodel developedin this

chapterand the assessment of its validity through comparisonof the model predictionwith
industrial data,this model is posedas a reliable tool for further processsystemengineering-
like researchorientationover the Borstareplant. Towardsthis direction the optimisationof
the plant dynamic operation during the switching between the two polymer grades, A and B,
is investigated at a preliminary stage, trying to apply the research outcomes of the case study
of Chapter 5 on this industrial plant.
Precisely,the control schemefound in Chapter5 as the "optimal" one for a similar grade
transition is slightly modified to comply with the plant designand is employedto optimally
conduct the transition from grade A to B and back to A. Revisiting the optimal control
structureof Chapter 5 (see Table 5.3) the control system has to be adjustedin termsof the
flow rate of the bleedstream,Fblýed, and the catalyststream,F,.,, which cannotbe enlistedin
the set of the control variables,at least for the part of the Borstaroplant studiedhere.The
remaining of the control system fully complies with the design of the Borstaro FBR and
thereforeis adoptedasit is resultingin the following control scheme(Table7.4):
192
Table 7A Control scheme applied for the optimal operation of the Borstaro plant.
tr P h Rp Pt m, 1
,F 1 0 0 0 0 0-
Fm 0 1 0 0 0 0
F.. 0 0 1 0 0 0
ý
Fm 0 0 0 1 0 0
,
Ratio 1 0 0 0 1 0
FM3 0 0 0 0 1
LO
,
Based on this control structure and the second optimisation policy presented in section 5.3.2,
where apart from the comonomer to monomer ratio in the make-up feed stream (Ratio) and
the hydrogen flow rate (Fm, ), the set point of the bed-level (h,p) and the polymer production
rate (Rp,sp)PI feedback controllers were used as feedforward control variables, the optimal
control trajectories are sought using the gPROMS/gOPT modeling tools of PSE (Process
Systems Enterprise Ltd, London). The tuning parameters of the PI feedback controllers are
also amended as additional optimization variables, while the optimization problem is

constructed using the objective function Eqn (5.11) and the set of constraints (see section 5.3)
definedin the casestudyof Chapter5.
In order to highlight the gain achieved for the process performance when operating under
optimal control instead of PI feedback control, the same operating scenario is considered, in
the sense that the plant initially produces polymer of grade A for 10 hours, then switches to
grade B and remains on-spec until the 58h hour from the instant we started to measure the
time and then switches again to grade A. Figures 7.13 and 7.14 display the process
performance in terms of polymer density and molecular weight profiles respectively, for the
two cases where the plant operates under simple feedback control and optimal control. The
plant switches to the new grades and gets into the on-spec region faster when operating under
optimal control. The impact of the optimal control trajectories is better illustrated in terms of
the polymer molecular weight profile (Figure 7.14), for both transition directions, either from
grade A to B or from grade B to A. Comparing the Ratio and the hydrogen flow rate
trajectories (see Figures 7.15,7.16) it seemsthat the PI feedback control trajectory for Ratio
is very close to the optimal one, while the differences of the respective F., trajectories justify
the improved profile of the polymer molecular weight under the optimal control.
193
Chapter 7 Plant-%%ide Issuc%
944 . t ......
........
..........
. 1 .....
...............................
;- ý": ........................
940- .
irade B
- ...0.05
936
Densi(y (Feedback Control
Desired Naltie
932 Densilv (Opfillial Coillrol)
928
± 0.050,'o
924 irade A
%
............. -------------------------
--------------- ...................... -------------------------------
920
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.13: Comparison of the density profiles derived under 1eedback and optimal control
during the transition from grade A to 13and back to A.
12000 - Gradc A
. ................... ........................................................
11600- 2% 0000
........... *------------- ------------
11200 (Pradc A
E 10800-
-M,,, (Fcedback Control)
10400
* Desired value
10000- M (Ol)flmaI Control)
-M,,,
9600-
9200-
8800-
8400-
8000-
7600 - ---------- -- ---------------------------------- -----------------------
7200 - ----------- ------ --- Gradc B
6800
64001
ýO
0 10 20 30 40 50 60 70 80 1ý0
Ti [Ile (h)
Figure 7.14: Comparison ofthe molccular "eight profilcs derlvcd undcr I'cedback and
optimal control during the transition from gradc A to 13and back to A.
194
Chapter 7 I'lant-" ide Issues
1600-
1400-
1200-
1000-
800-
6001
Butene feed (Feedback control)

400-
0 Industrial values
Butene feed (Optimal control)
200
,, I. IýIII.
0 10 20 30 40 50 60 70 80 90 100
Time(h)
Figure 7.15: Comparison of the butene feed trajectories derived undcr t'ccdbick and optimal
control during the transition from grade A to 13and back to A.
2.25-
Hýdrogen feed (Feedback Confrol)
2.00- 1t is",t rial values
--ilydrogen feed (Optimal Coitfrol)
1.75-
1.50-
1.25-
1.00-
Z 0.75 -
0.50-
Gradc 13
0.25-
0.00-ýjGradc A Grade A
-0.25
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.16: Comparison ofthe hydi-oien fccd It-a.1cctorles denved Lindei- Icedback and
optimal conti-ol during tllc ti-ansitlon firom gi-ade A to B and back to A.
195
However, the major improvement on the processperformanceresults mainly from the

optimal handlingof the hp andProduction,p ascontrol variables(seeFigures7.17,7.18).The
reductionof the bed level setpoint during the changeover,towardsboth directions,contribute
to the fasterrepletionof the reactorandthe settlementof the new phase-equilibrium,which is
in favour of the new polymer grade.What is really interestingto point out is the trajectoryof
the set point of the polymer productionrate controller. Note that in contrastto the optimal
trajectory found in the casestudy of Chapter5 (seeFigure 5.10), wherethe optimiserforced
towards the increaseof the productionrate, regardlessof the direction of the transition,in
to
order accelerate the switching from one grade to the other, now the trend is different.
Recalling the control schemefor the production rate, an increaseof the production rate
requiresan increaseon the monomermake-up feed stream and vice versa. In the casestudy
of Chapter 5 where a reactor
single-phase was considered,the increase of productionrate,
that is, the increaseof the monomermake up feed helped the transition through a faster
production of new polymer resulting in faster of

replacement the old-undesiredone. In the
modeling approach adopted here, with the two-phasereactor,with the compositionof the
polymer phase being very sensitiveto the composition of the "light" phase, the best way to
acceleratethe transition is by achieving the appropriatecomposition of the "heavy " phase
that allows the productionof polymer with the desiredspecifications, rather than by simply
producing larger amount of polymer. Therefore, the monomer make-up feed is properly
handledto contributeprimarily to the desiredcompositionof the "heavy" phaseand then to
the required production rate, resulting like that to the optimal trajectory of the polymer
productionrate setpoint shown in Figure 7.18.
Finally, the direct influenceof the optimal control comparedto the PI feedbackcontrol on the
processperformance is demonstrated with respect to the production of off-spec polymer
throughout both transitions between the two grades. In Figure 7.19 this comparison is
When
presented. the under
plant operates the optimal control the transitiontime is reducedby
5.5 hours for the A to B transitionand by 4 hoursfor the reversetransitionin termsof how
fasterthe plant entersthe on-specregion,while the profitability of the plant is tremendously
increasedby the overall reductionof the amountof the off-specproductby 150tones.
196
7 Plant-Wide Issues
17.4
17.2
17.0
Grade A
16.8
16.6 Grade B Grade A
16.4
16.2
16.0
15.8
15.6 -Bed level (Feedback Contro]l)

Industrial Values
15.4 ------- h, (Optimal I con
Control)
01)
P
15.2 -Bed level (Ophimal Control)
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.17: Comparison of the bed-level profiles derived under feedback and optimal
control during the transition from grade A to B and back to A.
12000-
11600-
Grade A
11200 Grade A
10800
10400
010000
m Grade B
9600
-Production rate (Feedback Control
e Industrial values
9200
------- Production (Optimal Control)
-W
Production rate (Optimal Control)
8800
Time (h)
Figure 7.18: Comparison of the production rate profiles derived under feedback and optimal
control during the transition from grade A to B and back to A.
197
550
500
................................................................ f,
450
400 150tn
350
. ........................... ........................... .... --
300
250
.............
200
105 tn 4 hr
150
100
--Offspec Product (Feedback Contro
50
5.4 hr ----Offspec Product (Optinial Control)
0
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 7.19: Comparison of the off-spec polymer amount produced under feedback and
optimal control during the transition from grade A to B and back to A.
In this chapter a comprehensive mathematical model for the dynamic simulation of' the
Borstar@olefin polymerization plant has been presented. Although the plant operation was
studied with respect to only two different polymer grades, simulation of several other
operating points of the plant is feasible while it might require a re-evaluation of the tunable
parameters (see section 7.3). However, with the current tuning of the model's parameters,the
agreement of model predictions with steady-state plant data was satisfactory, while very
realistic were also the dynamics of the plant, as simulated by the model, compared to the real
industrial practice. However, verification of dynamic profiles predicted by the model with
real dynamic data will render this model a potential tool for the optimisation of the process
operation. Towards this direction the conceptual framework presented in the case study of
Chapter 5 for a simultaneous control structure selection and dynamic optimisation of process
operation perfectly applies to the whole Borstar& plant. The problem of the optimal control
system architecture during a grade transition emerges more complicated, since the number of
the controlled and manipulated variables and their possible pairings under a multivarlable
control scheme rises significantly when the overall plant is considered. A preliminary
application of this framework on this current state of the model was presented with some
very encouraging results.
198
7.8 Literature
Ferrero, M., Chiovetta, M. G. (1987). Catalyst fragmentation during propylene

polymerization:Part 1. The effects of grain size and structure.Polymer Engng.Sci. 27,
1436.
Hutchinson, R.A. (1990) Modelling of particle growth in heterogeneous catalyzed

olefin
polymerization. PhD Thesis, University of Wisconsin Madison.
Kirby, C.F.; McHugh, M. A. (1999). Phase behavior of polymers in supercritical fluid
solvents. Chem. Rev., 99, p. 565.
Kreituss,A.; Frisch, H.L. (1981).Free-volumeestimatesin heterogeneous polymersystems.

I. Diffusion in crystalline ethylene-propylenecopolymers.J. Polym. Sci. Polynz.Phys.
Ed. 19,p. 889.
McHugh, M. A.; Krukonis, V. J. (1994) Supercritical Fluid Extraction. 2"d Ed., Butterworth-
Heinemann.
Moore, S.J.; Wanke, S.E. (2001) Solubility of ethylene, I-butene and I-hexcne in
polyethylenes. Chem. Eng. Sci., 56, p. 4121.
Orbey, H.; Bokis, C.P.; Chen,C.C. (1998) Equationof statemodelingof phaseequilibrium

in the low-density polyethyleneprocess:The sanchez-lacombe, statistical association
fluid theory,and polymer-soave-redlich-kwong
equationsof state.Ind. Eng. Chem.Res.,
37, p. 4481.
Pater, Jochern T. M. (2001) Polymerization and morphology. Study on the factors

determining powder morphology in propylene polymerization. AD 77iesis, Twente
University, Enschede,The Netherlands.
Sanchez, I. C.; Lacombe, R.H. (1978) Statistical thermodynamics of polymer solutions.

Macromolecules,11,1145.
Zacca,J.J., Debling, J.A., Ray, W.H, (1996) Reactorresidencetime distribution effects on

the multistage polymerization of olefins-I. Basic principles and illustrative examples,
polypropylene. Chem. Eng. Science,51, p. 4859.
199
CHAPTER 8
Conclusions & Recommendations

for Future Research
In this chapterthe key resultsof this work are summarised.A global revision and discussion
over the targetsof the thesisis attemptedand the main conclusionsare drawn.Finally, areas
for future work are also identified.
8.1 Thesis Contribution
The main scopesatisfiedby this thesiswas a thoroughanalysisand investigationof various

designand operationalindustrial scaleproblems,which appearas everydayproblemsin the
lifetime of polymer industry in generaland the gas-phasepolyolefin industry in particular.
The results of this researchwork were based on detailed dynamic models that were
developed within this thesis for the accuratemathematical representationof these problems.
Under this conceptual framework, this thesis was properly constructed to provide the reader
at a first level, with the essential background information necessaryto identify the source of
this kind of problems. Additionally, it helps someone to realize the dimensions of these
problems, which are broadened to the majority of the polymer industry, and the economic
influences where these problems are extended to; while finally, it relates these issues with a
gas-phase polyolefin process, as a representative case study, in order to make the design
problem more specific and to elaborate deeper on its details.
The first two chapterscontributed towards this direction discussingin detail the market
orientations of the polymer industry. Financial indexes and statistical data were also
200
Chapter 8 Conclusions & Recommendations for Future Research
presentedto demonstratethe growing trend of the polyolefin industry, as a resultof the wide
range of polyolefin applications,predisposingthe reader for the context of the problems
addressedthrough the researchactivities of this work. Furthermore,some basic technical
characteristicsof variouspolyolefin processeswerepresentedand linking of the financialand
administrative nature of these issues with more engineering-likeaspectswas attempted
denoting the involvement of the process systems engineer. Through this analysis,the
dimension of the process design problem was revealed pointing out that such critical
questions are confronted by the majority of polyolefin processes,with the gas-phase
processesexhibiting moreintenseactivity over the management
of theseproblems.
At a second level, the necessary mathematical tools and solution algorithms were developed
in this thesis. Precisely, the theoretical principles over the mathematical model development
of a catalytic gas-phase fluidized bed polyolefin reactor were built up. The derived model
captured successfully a wide range of microscale and macroscale phenomena occurring in a
catalytic ethylene polymerization FBR, as a special case of the gas-phase olefin
polymerization processes.At the microscale level, a detailed polymerization mechanism and

the mathernatic description of the polymer molecular development, based on the method of
moments of the chain length distribution, were thoroughly discussed. At the macroscale
level, the fast dynamics of the polymerization scheme were combined with the slower reactor
dynamics composing the dynamic operation of the polymerization system on the basis of a
perfect mixing pattern in the reactor. Then, the generic process design and operational
problems were revisited in relation to the catalytic ethylene copolymerization FBR processin
a more specific way. The problems of process control synthesis, in terms of the identification
of the control structure and the control objectives, and the optimal process operation were
raised during a grade transition operating profile of the process. The linking of the polymer
grade specifications-molecular properties with the operating framework of the process and
the policies applied for the switching of the process from one operating framework to another
were contributive to realize the relation between the processprofitability and financial issues,
posed in the first chapter, with the optimality of process operation. The theoretical base over
the process controllability, switchability and dynamic optimisation together with the
formulation of a process performance criterion, for the assessmentof process operation
during a grade transition, were fully analysed, accomplishing the tools required for an
integrated approach of the problems mentioned above.
201
Chapter 8 Conclusions& Recommendationsfor Future Research
The major conclusions derived from this work were drawn in the last part of the thesis.Some
important design problems, motivated from the industrial practice, with serious impact on
polymerization process economics, were confronted through a model-based approachof two

case studies. The theoretical background that was built up and the dynamic model of the
catalytic gas-phase ethylene polymerization FBR were of great value for the extraction of
these conclusions. In both these case studies the identification of the time optimal operating
profile of a polymerization process during a grade transition, the selection of the appropriate
control scheme and the production campaign scheduling problem were presented as an
ordinary multidimensional process design problem, where both continuous dynamically
changed and discrete decisions were necessary. Despite the confessed interactive nature of
the above problems they have never been handled simultaneously. Within this thesis though
an advanced optimisation algorithm decomposing the problems to account for discrete and
continuous decisions (MIDO algorithm) was employed for an integrated approach of the time
optimal process operation and control structure selection firstly and next the time optimal
process operation and production campaign scheduling problem. The inference educed from
this analysis was the importance of an integrated approach to various process design
problems using advanced techniques. The latter significantly outperforms the conventional
sequential approaches,which treat each step of the composite process synthesis problem as
individual sub-problem, and guarantees a great benefit for the process under such strategic
manipulations.
Recognising the importance of the process model development step on the accuracy, the
validity and credibility of this research work, an attempt for the development of a composite
mathematical model, that will allow the investigation of similar problems from a plant-wide
point of view, was amended as final contribution of this thesis. The Borstare industrial plant
was selected to demonstrate the concept applying for the modelling of a multistage
polymerization process, raising the problem of simulating absorption and diffusion

in
phenomena a polymerization system, and the impact of polymer particle morphology on
the polymer molecular development. Despite the preliminary work, carried out so far within
this thesis as far as the modelling of the Borstaro plant is concerned, the major issues
Moreover, the basis for further

conditioning the plant operation were successfully considered.
improvement and better theoretically equipment of the model were posed, while the results
obtained so far were encouraging enough to force the completion of the model in order to
offer additional functionalities apart from process simulation. Towards this direction, a first
202
step was made through the investigation of the optimal plant operation under a predefined
control system architecture.
Summarisingthe researchinputs providedby this work from severalpoints of view it canbe

said that:
This thesis contributed at a first level to identify various process systemsengineering-

like problems in polymerization reaction processes,to assign to these problems their
actual dimension and importance and to relate the engineering with the economic
nature of these problems as far as their settlement is concemed recognizing the
processengineer as the most qualified person for such an intractable task.
The major impact and novelty of this study is the conceptual framework developed in
order to deal with such multilevel problems, spotting the operational and economic
benefitachievedthroughan integratedapproach,wherevariousinteractedbranchesof
the problem are confronted under a simultaneousarrangementaccountingfor the
influenceof the oneto the other.
9 The mixed integer dynamic optimisation (MIDO) mathematical algorithm, which
supports the above solution philosophy of various process system engineering

problems, was applied and found to be the most potential and efficient method. The
algorithm's capabilities were demonstrated with respect to two different case studies
representingreal industrial operatingscenarioswhere the dynamicoperatingprofile
with the processcontrol system architectureat the first case, and the dynamic
operating profile with the processproduction scheduleat the secondcase were
optimizedsimultaneously.The algorithmdominanceover otherconventionalmethods
was illustratedin termsof someengineeringaspects,which can be easily interpreted
into pureeconomicterms.
0 The basement of all the research activities carried out throughout this work was the
development of two detailed and comprehensive mathematical models on the
gPROMSmodelingenvironment,for the dynamicsimulationcontrol andoptimisation

on a single polymerizationprocessunit and on a plant wide base,respectively.Both
these models provide powerful tools for a deeper and wider investigation of process
system engineering problems in catalytic polymerization processes,utilizing various
advancedsolution algorithms such as the MIDO method.
203
8.2 A Challenge for Future Research
Recalling the work that has been done so far and thinking ahead of the future objectives, it
becomes obvious that this report serves as a precursor for further research activities specially
localized in the industrial practice. In particular this work builds up the required background
for a more comprehensive and integrated approach of the multistage problem of optimal
process design and operation of polyolefin processesin relation to the economic profitability
and competitiveness of these processes.The plans for any future research activities are drawn
on the basis of this concept and thinking of the industrial interest over the research area
explored by this thesis. Therefore, what is principally recommended for future work is to
extend this investigation over an industrial plant using the advanced MIDO algorithm,
presented in this thesis, and based on a detailed mathematical model that will amplify
considerably the importance, the worth and the applicability of the results of this thesis.
Precisely, it is proposed an integrated analysis over the design of the total Borstaro industrial
plant accounting for:
0 The selection of the optimal control system architecture based either on a

conventionalPID control configuration or on an advancedcontrol system,such as model
predictivecontrol (MPC). This control system shouldbe capable of providing both regulatory
control in the of
presence variousprocess disturbancesduring the processoperation,as well
as servocontrol driving the processsuccessfullyfrom one operatingpoint to a new one,that
is, from one polymer grade to another.The identification of the appropriateplant-wide
control scheme is a very complex task both because of the large set of controlled and
manipulatedvariablesand particularly because of the highly interactivenatureof the process
unit operatingprofiles. This is due to the topology
sequential of the units from one point of
view, and from the other, due to the recycle streamslinking reverselythe units with each
other.
0 The dynamic and steady-stateoptimisationof the processoperatingprofile and the

static operatingpoints The
respectively. optimisationof the processoperatingprofile over a
period of the processlifetime is a two-branchproblem.The first branch refersto a switching
periodof the from
process to
onepolymergrade another where a feedforward optimal control
The secondbranchon the other side,refersto a productionperiodof the process
is necessary.
is
where a supervisoryoptimal control required for the rejection of processdisturbances,
which bring about a processdeviation from the desired operating points found by static
204
maximisationof processyield or basedon other pure economicindexes.This problem,when

addressedin terins of the overall Borstaroplant, is a very demandingand challengingtask.
The only criterion for the assessmentof the processperformanceis the satisfactionof
polymer property specificationsin terms of the final product exclusively, coming out from
the last reactor. At this stage, the polymer molecular weight distribution (MWD) or
copolymer composition distribution (CCD) can be also consideredas additional product
molecular specificationsof higher industrial practice than the averagevalues, requiring
though further modeling effort. Thinking then that the propertiesof the final product are
reliant to the operatingframeworkof a seriesof reactors,and not of the final one only. it is
obvious that any heuristicapproachto this problemwill be inferior comparedto an approach
basedon advancedmathematicaloptimisation techniques.The latter will result in optimal
trajectories of the decision variables accounting for the operating framework of all the
processunits andthe impact of eachof themon the total polymerproduct.
9 The production-scheduling problem incorporating further economic criteria apart

from the polymer property specifications, for the assessmentof the proposed production
campaign. In order to addressthis problem in relation to the industrial Borstaro plant, a more
realistic scenario should be considered. The problem should be properly formulated so as to
account for a variable market demand and different prices of the various polymer grades as
well as for a reduced price of the off-spec product. Then, allowing for intermediate storageof
the product with the design of the storage vessels, the storage time and the inventory levels
incorporated within this scheduling problem, each polymer grade would be produced during
several periods of the process cycle time and the problem will reflect closer tile industrial
reality.
It should be noticed at this point that a model-based approach of the three problems stated
above, appeal for a dynamic model of the overall plant that should be developed basedon the
same modeling principles, encompassingequal degree of detail with the model presentedin
the previous chapter. Therefore, the modeling activities through out this thesis will set the
basis for the development of a complete and further improved dynamic model of the total
industrial plant. This model will serve as a powerful tool that will allow the simulation, under
high fidelity levels, of real scale problems discussed above, and the investigation of these
problems that will result in valuable and credible outcomes applying advanced mathematical
solution algorithms.
205
Related Publications Arising from this Work
1. C. Chatzidoukas, J.D. Perkins, E.N. Pistikopoulos, C. Kiparissides (2003) Optimal

Grade Transition and Selection of Closed-Loop Controllers in a Gas-PhaseOlefin
Polymerization Fluidization Bed Reactor. Chemical Engineering Science, 40, p.
3643.
2. C. Chatzidoukas, J.D. Perkins, E.N. Pistikopoulos, C. Kiparissides, Optimal Production

Scheduling in an Industrial Gas-Phase Polyolefin FBR using a Mixed Integer
Dynamic Optimization Approach (under submission in Chemical Engineering
Science).
3. C. Chatzidoukas,C. KiparissidesJ.D. Perkins, E.N. Pistikopoulos(2001) Dynamic

Simulation and Optimizationsof an Industrial Olefin PolymerizationFBR using the
gPROMS9/gOPT8ComputationalTools. DYCOPS 6"' IFAC Symposium,Jejudo
Island, Korea.
4. C. Chatzidoukas, C. Kiparissides J.D. Perkins, E.N. Pistikopoulos (2001) Optimal

Grade Transition in a Polyolefin FBR using Mixed Integer Dynamic Optimization,
AlChE Annual Meeting, Reno Nevada November 4.
5. C. Chatzicloukas, J.D. Perkins, E.N. Pistikopoulos, C. Kiparissides (2002) Optimal

Grade Transition in a Polyolefin FBR using Mixed Integer Dynamic Optimization,
2nd European Conference on the Reaction Engineering of Polyolefins (ECOREP),
Lyon France, July 1.
6. C. Chatzidoukas, J.D. Perkins, E.N. Pistikopoulos, C. Kiparissides (2002) Dynamic

Simulation of the Borstar Multistage Olefin Polymerization Process,AlChE Annual
Meeting, Indianapolis, Indiana, November 3.
7. C. Chatzicloukas, C. Kiparissides J.D. Perkins, E.N. Pistikopoulos (2003) Optimal

Grade Transition Campaign Scheduling in a Gas-PhasePolyolefin FBR using Mixed
Integer Dynamic Optimization, 13'h European Symposium on Computer Aided
Process Engineering (ESCAPE), Lappeenranta,Finland, June 1.
S. C. Chatzidoukas, J.D. Perkins, E.N. Pistikopoulos, C. Kiparissides (2003) Dynamic

Simulation of the Borstar Multistage Olefin Polymerization Process, 13"' European
206
Symposium on Computer Aided Process Engineering (ESCAPE), Lappeenranta,
Finland,June1.
9. C. Chatzidoukas,C. KiparissidesJ.D. Perkins, E.N. Pistikopoulos (2003) Optimal

GradeTransition CampaignSchedulingin a Gas-PhasePolyolefin FBR usingMixed
Integer Dynamic Optimization, 81hInternational Symposiumon ProcessSystems
Engineering(PSE),YunnanProvince,P.R.China,June22.
10. W. V. Brempt, P.V. Overschee, T. Backx, 0. Moen, C. Kiparissides, C. Chatzidoukas

(2004) Plantwide Economical Dynamic Optimisation: Application on a Borealis
Borstar Process Model, Intenzational Symposium on Advanced Control of Chemical
Processes(ADCHEM). Hong Kong, China, January 11.
207
APPENDIX A
Pseudokinetic Rate Constants -

Rate Functions for Olefin Copolymerization
A. 1 Introduction
For multicomponent polymerization (copolymerization with two or more monomer types),

the introduction of pseudokinetic rate constants in the group rate functions simplifies
considerably the kinetic rate expressions and reduces the complexity of the mathematical
description of the polymerization mechanism. This reflects to a respective reduction of the
computational effort needed to solve the already overcharged system of equations of the
kinetic model. Furthermore, through the definition of the pseudokinetic rate constants, an
elegant and effective solution method is attained, which relies on a thorough understandingof
the chemical and physical microscopic phenomena that control chain microstructure.
Hamielec and MacGregor (1983) were the first who used the pseudokinetic rate constant
method for molecular weight calculations. Subsequently, Achilias and Kiparissides (1992)
applied this method to study the molecular weight and compositional changes in free-radical
copolymerization reactions, while a detailed analysis and evaluation of this method was
presentedby Xie and Hamielec (1993) and Baltsas et a]. (1998) .
In this appendix the pseudokinetic rate constants based on the generalized mechanism
presented in Chapter 3, (see Table 3.1) are presented for all the reaction steps of the
polymerization scheme. For the definition of these constants the instantaneouscomposition,
$jk, of the "live" polymer chains fon-ned over the W catalyst site
needs to be calculated.
Assuming that this composition is independent of the chain length, then is given by the
following expression:
208
Appendix A PseudokineticRateConstants- RateFunctionsfor Olefin Copolymerization
Pn'.
i
n=I
N (Al)
y
pnk,
i=l n=l
Applying the steady-state hypothesis for the "live" polymer chains and the long-chain
approximation according which the monomer consumption due to all but the propagation
reactions can be neglected, then following the analysis of Carvalho de et al. (1989) the
instantaneouscomposition of the "live" polymer chains for a binary copolymerization system
are:
kk f, kk f2
k P21 4)k p12
2 = 'jk (A2)
kk f2 f2
P21 f, +kkP12
f, +kkP12
p21
wherefi is the molar fraction of monomerT in the reactionphase.
fi (A3)
The generalized pseudokinetic rate constants for the basic reactions of the mechanism shown
in Table 3.1 are defined accordingly in Table A. 1.
Table AJ: Basic reaction pseudokinetic rate constants.
Reaction Step Pseudokinetic rate constant Reaction Step Pseudokinetic rate constant
ý(kk N
Activation by kk
Deactivation by kk Y (kk fl)
aMT aM i
fi dM TW , dM
monomer i=l monomer i
N ) ý(kk
kk
Y(kk
f, Chain transfer kk
Initiation OT = Oj 10 H2 T LH I
i=l
ý (kk
kk f kk f
PiT Pu J) LM,T =ý(kk N O j)
j=l j=l
Chaintransfer ý(kk
Propagation kkPir,
ý( Ikk ýDý
PIij
kk
tmn 4
(Dk
kkPTr =
ýý(kk
ýDkf
toA kk =
ýý(kk tm1 (Dýf J)
PO I j) tm IT IM O I
i=l i=l i-I i-I
209
Appendix A PseudokineticRateConstants- RateFunctionsfor Olefin Copolymerizatio
Spontaneous (k N
kk k CDý kk kk fj
Chain transfer ,
tSPT tSP, 1 nS'MsT ýy nstmq
i=l J=j
Transformation ý(kk
kk 4bý
without nstM,, nstmd I
i-I
termination by M,
NN
Transformation kN $ý)
(kk
kk kk
k nstHT "ýYY
without nstHi nstMrr ns
tMo$ýfj
termination by H,
Using these expressions of the pseudokinetic rate constants the grouping rate functions are
modified accordingly:
Activation:
Pk =kk [E]+kk IMT I (M)
a asp +kkA[A]+kk allIH2]+kk aE aMT
Deactivation:
[A]+kk [Z]+kk IMT I (M)
Pk =kkdSP+kkdA d
dH[H2]+kkS[E]+kk dZ dMT
d
Chain Transfer.
[A]+kk [E]+kk IH2]+ktmrr
k IMT1
pktT =kktSPT +kktAT (A6)
tET tHT
Transformation with termination:

[A]+kkl [El+kkl [Z]+kkl IH2 ]+ kkl IMT I (A7)
pkl=kkl
st +kkl
stsp stA stE stz stH StMT
Transformation without temination:

[Z]+ IH2]+kktMlr IMT I
p,kltT = k.ki, + kklnstA [A]+ kklnstE [E]+ kkItZ, kki (A8)
's ssp, TTT ns nstH ns
A. 2 Kinetic Model
Revisiting the generalized kinetic model developed in Chapter 3 the pseudokinetic rate
constants are introduced in the expressions of the net rate functions. The kinetic model is
rewritten here and is adopted to the considerably simplified kinetic mechanism shown in
Table 3.2, which contains a set of elementary reactions that apply throughout this thesis, both
210
for the two case studies presentedin Chapters 5 and 6 and for the plant-wide dynamic model
of the Borstare process. Setting equal to zero the kinetic constants of the reaction steps that
are not considered in the polymerization mechanism, the net production rates of "live" and
"dead" copolymer chains as well as the net production rates of potential and vacant catalyst
sites are derived:
Net production rate of "live" copolymer chains pk i*

,
[pk. ]-ßk[pk, ]+8(n)(1 - [pýk,
j+ [p
Rk =-kk kk Z kk k
pýo sp nj t' n, tmji 01 0X1
j=I n=I (A9)
[Pný1, lpnkiIM
+ (1-8(n»lkk. pj, j][Mi]-kk TI ; n=I ... N- andi=1,2
p
j=I
where, 5(n) is the Kronecker's delta function and pk is a Jumpedrate function for chain
U
transfer to hydrogen, to monomer and spontaneouschain transfer reactions:
Net production rate of "dead" copolymer chains D,,:
)N [pnk
Rk
=(kkdsp +pk (AIO)
D tT
Net consumption rate ofpotential catalyst sites of type T:

kkj
Rkk -kaAa [A] (A 11)
SP= p
Net production rate of vacant catalyst sites of type T:

[pk k+kk (k [H21) kk"0 (A12)
RkPO =-kkp[pk]-kk
ds 0 OT OIIMTI-Rsr tSPT +k tHT
Accordingly, the monomerconsumptionratewith respectto the T activecatalystsitecan be

written as:
[M, ]ýk [pok ]+ (kk k )), k
Rk
m i= oi tmT,
+k
PT, 0 (A13)
Finally, the overall copolymerization rate in mass units, will be given by the sum of the
individual monomer incorporation rates into the copolymer chains formed over all the
211
catalyst active sites, which coincides, for the mechanism considered here, with the
summation of all the monomer consumption rates:
N,,, N, )= N., (kk
[M [pk ]+ (kk )Xk
R, =JE( Rk MW, MW, E +kk (AW)
M, 0i 0I tmr, Pri 0
i=l k=l k=l
The corresponding rate functions for the moments X' and ýtk can be obtained from Eqns
vv
(A9) and (A.10) by multiplying each term by n' and summing up the resulting expressions
over the total variation of W. The final expressions for the corresponding moment rate
functionsare:
kp-pk kk [MTI)+ [p IIMT1

Rk kds (A15)
tT + ktmrr k OT ok
=Xk
)LO o
[- J+ (ktmrr [MTI+ k ýOfl ý4d

Rk =Xk kdksp kkk)
+k Xk0 kOT (A 16)
;L, i tT PTr
k[-, ý J+kk Ml+kk Q+2%jk)[MT1+lý, V01M]

RkX2 = X2
Kp (A 17)
s -pk IT OýIIT P17
[kdsp
RkPo =k4 +pktT (A 18)
[kdsp
k +pk I (A19)
RkI =Xk
pI tT
[kdsp j
k2 k+ pk
R = Xk
tT
(A20)
p2
Finally, the values of the kinetic parametersfor the kinetic rate functions used to describe the
polymerization mechanism, are reported separately for the FBR model, employed in the two
dynamic optimisation case studies (see Chapters 5& 6), and the dynamic model for the
Borstare plant in Tables A. 2 and A. 3 respectively. Although there are few papers in the
literature where someonecan find valuesfor some of the kinetic parameters,thesevalues

differ for various systemsand in generalthere is only a range of valuesthat thesekinetic
lie
parameters within. Therefore,tuning of these particularly
parameters, for the Borstaro
model, is necessary and it is a very hard task, which requires exceptional insight of the
process operation and the various phenomenaoccurring in the reaction area. Considering the
highly interactive nature of these phenomena an iterative procedure between the following
212
tuning actionsof the model parameters,properly constrainedwithin acceptableranges,was

appliedto comeup with the resultedvaluespresentedin Table A-3:
0 Tuning of the binary parametersof the Sanchez-Lacombe EoS using experimental

dataof binary mixturesof polyethylenewith any of the gaseouscomponents.
Tuning of model parameters(i. e., Kfiash,

i, Void) to fit the industrial data with respectto
the composition of the "light" phase and the inventory of the reactor.
0 Tuning of the kinetic constants to fit the molecular polymer properties together with
the composition of the "light" phasein the reactor.
213
Appendix A PseudokineticRateConstants- RateFunctionsfor Olcfin Copolymerization
Table A. 2: Numerical values of the kinetic rate constants of the ethylene-I-butene
copolymerization over Ziegler-Natta catalyst of two active sites-FBR model.

Kinetic Constant k=k0 exp (-E/RT)
Reaction step Units
Sitetype 1 Sitetype2
Activation-by cocatalyst (Al): k' =102 exp(-9/RT) k2 =102exp(-9/RT) CM3/MOI/S
A aA
Initiation-with monomer(1): k' =103 exp(-9/RT) k2 =103 exp(-9/RT) CM3/MOI/S

01 01
Q
ko' =0.14103exp(-9/RT) CM3/Mol/S
withmonomer(2): 2 =0.14103exp(-9/RT) 02
Propa2ation-
k IP,. 85 103 exp(-9/RT) k211
'live' chain with end unit of P = 85103 exp(-9/RT) cm3/mol/s
type (1) with monomer (1):
'live' chain with end unit of kI 2103 k2= 15103

P12 exp(-9/RT) P12 exp(-9/RT) Cm3/mOI/S
'live' chain with end unit of kI= 64 103 exp(-9/RT) k2 = 64103 exp(-9/RT) cm3/mol/s
type (2) with monomer(1): P21 P21
'live' chain with end unit of k' =1.5103 exp(-9/RT) k2 =6.2103 exp(-9/RT) =3/mol/s
type (2) with monomer(2): P22 P22
Deactivation-Spontaneous: kd', 10-4 k2 10-4 I/S

P exp(-8/RT) dsp exp(-8/RT)
Chain Transfer-
'live' chain with end unit of kitsp, 10-4 k2Pj 10-4

exp(-8/RT) ts exp(-S/RT) I/S
type (1), spontaneous:
'live' chain with end unit of 10-4 k2P2 10-4

k ItSP2 exp(-8/RT) ts exp(-8/RT) I/S
k2j
'live' chain with end unit of ktH = 88 exp(-8/RT) aI = 370exp(-8[RT) CM3/MO, /S
type (1) with hydrogen: I
k2
'live' chain with end unit of k1H = 88 exp(-8/RT)
t 2 W2 = 370exp(-8/RT) CM3/MOj/S
type (2) with hydrogen:
'live' chain with end unit of k'tM 2.1 exp(-8/RT) k22.1 = exp(-8/RT) CM3/MOI/S
tMIJ
type (1) with monomer (1): 1
'live' chain with end unit of k'tMI2 6 exp(-8/RT) k2tM12 110exp(-8/RT) CM3/MOI/S
type (1) with monomer(2):
'live' chain with end unit of k'tM2,2. lexp(-8/RT) k2-I : exp(-8/RT) CM3/MOj/S
tM21 -
'live' chain with end unit of 3/MOI/S

k tM22 6 exp(-8/RT) k2tM22 110exp(-8/RT) CM
214
Table A. 3: Numerical values of the kinetic rate constants of the ethylene-I -butene
copolymerization over Ziegler-Natta catalyst of two active sites-Borstare plant model.

Kinetic Constant (k= ko exp (-E/RT) ]
Reaction step Units
Site tvpe I
Activation-by cocatalyst (Al): k' =0.36exp(-5/RT) k2 =0.36exp(-5/RT) m/mol/h
aA A
ki exp(-4/RT) k2 =100 exp(-4/RT)
Initiation-with monomer (1): =100
0,0, m3ftol/h
kolý =40 exp(-4/RT) Q exp(-4/RT)
with monomer (2): 02 =40 M3/rnOI/h
Provaeation-
'live' chain with end unit of kIP11=789.7exp(-9.25/RT) k2= 450.9 exp(- I 2.03/RT) m3ftol/h
P11
'live' chain with end unit of kiP12=5.154exp(-14.4/RT) k2 = 0.06exp(-31.03/RT) m3ftol/h

type (1) with monomer (2): P12
'live' chain with end unit of kI k2 = 15.36 exp(-8.75/RT)

=25.17exp(-15.1/RT) m3/mol/h
type (2) with monomer (1): P21 P21
'live' chain with end unit of kI k2 =0.033exp(-12.6/RT)

=0.401exp(-12.6/RT) m3/mol/h
type (2) with monomer (2): P22 P22
kldp 2=0.00144exp(-4/RT)
Deactivation-Spontaneous: :--0.00144exp(-4/RT) k dsp J/h
Chain Transfer-
k' 0.36 exp(-4/RT) k20.36 exp(-4/RT) I/h
'live' chain with end unit of tsp, tsp,
'live' chain with end unit of k'tSP2 0.36 exp(4/RT) k20.36 exp(-4/RT) I/h
tSP2
'live' chain with end unit of kI ": 3.667exp(-20.3/RT) k2 ý 3.230exp(-16.2/RT) m3/mol/h

type (1) with hydrogen: tH, (HI
'live' chain with end unit of kItH2= 3.65cxp(-21.5/RT) Q=3.62cxp(-16.2/RT)

tH2 M3/mOI/h
type (2) with hydrogen:
'live' chain with end unit of k1, :: 2.83 exp(-5.4/RT) k2 ý-6.29 exp(-5-4/RT)
M11 tmll m3/mol/h
'live' chain with end unit of k 1tM 0.06 exp(- 12.5/RT) k2

12 = -0.072exp(-12.4/RT)
2,,
tm, m3/mol/h
'live' chain with end unit of k' k2 0.41exp(-5.4/RT) m3/mol/h

tM , =0.411exp(-5.4/RT) tm 21,,:
'live' chain with end unit of kI ,=0.026exp(-12.5/RT,

' k2
22 =0.004exp(-12.4/RT)m3/moVh
type (2) with monomer (2): LM2 LM
(F k
Vacant catalyst siteflow rate Vac
Grade Catalystsite I Catalystsite 2 Units
A 0.255455 0.0255956 (mol/h)
B 0.082 0.2883 (moVh)
215
A. 3 Literature
Achilias, D. S.; Kiparissides, C. (1992) Toward the development of a general framework for
modelling molecularweight and changes

compositional in free-radicalcopolymerization
reactions. J.M. S.-Rev. Macromol. Chem. Phys., C32, p. 183.
Baltsas, A.; Papadopoulos, E.; Kiparissides, C (1998) Application and validation of the
pseudo-kinetic rate constant method to high pressure LDPE tubular reactors. Computers
Chem. Eng., 22 Suppl., p. S95.
Carvalho de, A. B.; Gloor, P.E.; Hamielec, A. E. (1989) A kinetic mathematical model for
heterogeneousZiegler-Natta copolymerization. Polymer, 30, p. 280.
Harnielec, A. E.; MacGregor, J.F. (1983) Polymer Reaction Engineering. K. 11. Reichert, W.
Geiseler, Eds., Hanser Publishers, New York, p. 2 1.
Xie, T.; Hamielec, A. E. (1993) Modelling free-radical copolymerization kinetics-evaluation
of the pseudo-kinetic rate constant method, 1. Macromol. Chem. Theory SinzuL,2, p.421.
216
APPENDIX B
Physical Properties - Process Unit Design Parameters
Throughout this thesis a number of parameters are required for the calculation of various
physical properties of single components or mixtures of components, which appear in the

polymerization systems, necessary for the development of a complete mathematical model.
In this appendix these parameters are reported together with some design parametersof the
process units both with respect to the complex Borstaro plant model (Table B. 1) and the
simpler FBR model (Table B. 2).
Table BA: Processunit design and operational parameters-Borstaroplant model.
Parameter description Value

Flash Separator
Volume of the flash vessel Vvcsse, 96 rn3
=
HeatinE-Cooliný rate of the flash vessel Q=0.0 cal/h
FBR
Dbcd
Diameter of the bed = 3.8 m
Number of well-stirred zones in the heat exchanger N;,. 4
Overall heat exchanger area A 257.25 rn2

tw,
Maq 5 103 kg
Accumulated water mass in the tank of heat exchanger
Total accumulated gas mass in the tubes of heat Mgas = 0.8 103 kg
, total
exchanger
Input temperature of water in the heat exchanger T,,,i,, = 283.15 K
Make-up streamstemperature T. = 303.15 K

k
Overall heat transfer coefficient of the heat exchanger Ue = 3.6 106J/h/m2/ K
217
Appendix B PhysicalProperties- ProcessUnit DesignParameter
Table B. 2: Reactor and heat exchanger design parameters-FBR model.
Parameter description Value

Bed diameter Dbcd= 2.5 m
Active metalconcentrationin the [Me] =2 mol Me/lLcat
catalystfeedstream
Fractionof metalthat can form catalyst ft=0.6; f; Me
site site =0.4 mol/mol
active site of type V
Bed voidage P-bed 0.5
-=
Heat transferareaof eachcompartment Aj 64
= m
of the heatexchanger
Overall heattransfercoefficient Uj = 1000J/K/m'/s
Coolantinlet temperature Tw,in 288.15 K
Accumulatedwatermassin the tank of Maq 5 103 k9
the heatexchanger
Accumulatedgasmassin eachwell- Mj, 1= 0.2 103 kg
t.t.,
stirredzoneof the heatexchanger
The necessaryparametersof the componentsphysicalpropertiesare presentedin Table B.3

Theseparametersare usedeither in the Borstaro-plantdynamicmodel and/orin the simpler
FBR model.
Table B.3%Components'physicalpropertyparameters.
Parameter description Symbol Value Units
Heat of evaporation of ethylene AHvap,i 114.28 10' cal/kg
Heat of evaporation of butene AHvap'l 94.6410 cal/kg
125 103
Heat of evaporation of hydrogen AH cal/kg
i
vap,
Heat of evaporation of propane AHvap,i 100.56 10' caUkg
Heat of evaporation of polymer AH 0.0 cal/kg
vap,j
Enthalpy of polymerization 103
AHreac -916 cal/kg
Catalyst density NO 2.84 103 kg/m 3
Density of the crystalline polymer PCrYS 997 kg/M3
Density of the amorphous polymer Pam 854 kg/M3
Critical temperature of ethylene To 283.05 K
Critical temperature of butene To 417.88 K
Critical temperature of hydrogen To 33.16 K
* Perry,R.H.; Green,D.W. (1998)Perry's ChemicalEngineers'Handbook.Vh Ed., McGraw-Hill.
218
Appendix B PhysicalProperties- ProcessUnit DesignParameters
Critical temperature of nitrogen To 126.28 K

Critical temperature of propane T"i 369.94 K
Molecular weight of ethylene Mwj 0.028 kg/mol
Molecular weight of butene Mwj 0.056 kg/mol
Molecular weight of hydrogen Mwj 0.002 kg/mol
Molecular weight of nitrogen Mwj 0.044 kg/mol.
Molecular weight of propane Mwj 0.044 kg/mol
Molecular weight of water MwW 0.018 kg/mol
Coefficients for the isobaric heat capacity Cpj
Ethylene CPAJ 9.326018 cal/mol/K
CP 0.1393934 10" cal/mol/K2
13,1
Cpcj 0.1010831 10'5 cal/mol/K3
CPD,I -7.516552 10-9 cal/mol/K4
Butene CPAJ 17.96141 cal/mol/K
CP 0.3297022 10" cal/mol/K2
Bj
CpCj -0.605339 10'5 cal/mol/K3
CPW -5.69809 10-9 cal/mol/K4
Hydrogen CPAJ 6.647816 cal/mol/K
Cp 0.2472647 10-2 cal/mol/K2
Bj
Cpcj 10-6 cal/mol/K3
-4.557635
CPDJ 0.311770110'8 cal/mol/K 4
Nitrogen CPAJ 6.947158 cal/mol/K

CP 0.6609477 10'4 2
BJ cal/mol/K
Cpc'i 0.5693395 10-6 cal/mol/K3
CPW 3.226862 10"' cal/mol/K 4
Propane CPAJ -4.224 cal/mol/K
Cp B,I 3.063 10" cal/mol/K2
10-4 3
CpC'I -1.586 cal/mol/K
CPDJ 3.215 10,8 cal/mol/K 4
0.96 103
Polymer CPAJ cal/Kg/K
Cp 13,1 0.0 cal/kg/K 2
CpCj 0.0 cal/kg/K3
CPD,i 0.0 cal/kg/K4
Water CPA. 17.3 1U744
w cal/mol/K
10'3 2
CP
B,w
2.48375 cal/mol/K
cpc, 10'6 3
w -0.35766 cal/mol/K
4
CPD, 0.0 cal/mol/K
w
219
Appendix B PhysicalProperties- ProcessUnit DesignParameter
The molecular heat capacity of each componentis calculatedaccordingto the following

expression as a function of temperature:
CPi +Cp, +CPD, 1)

-ýCPAJ 3,iT+Cpc, iT2 jT3
while, in order to calculate the corresponding property for a mixture of components, the
molar composition (xi) of each component in the mixture is required:
p
E(Xicpi) (B2)
cpmix ,4
,
i=l
220
APPENDIX C
Detailed Analysis of the MIDO Algorithm
C.1 Novel Solution Method of MIDO Problems
In this appendix an advanced modification of the MIDO approach is presented basedon the
developments of Bansal (2000) and Bansal et a]. (2003) where a more detailed and analytic
description, compared to that presentedin Chapter 5, can be found. This alternative approach
is based on v2-GBD principles (Floudas, 1995) but is less computational expensive in terms
of the derivation of the dual variables and the construction of the "master" sub-problem.
Then follows the decomposition of problem (5.1) into a "primal" and a "master" sub-
problem illustrating the advantageof this method.
Primal Problem Construction

At the kthstep of the iterative GBD algorithm the following dynamic optimisation problem is
solved:
Min J=G(x(tf), y(tf), d, b, tf)+ffF(x(t),

to
y(t), u(t), d, b, t)dt
u(t), d, b, tf
S.t. f (i(t), x(t), y(t), u(t), d, b, t) = 0, VtE [tot t(
I1(X(t), y(t), u(t), d, b, t) = 0, VtE [to, tf
ho(i(to), x(to), y(to), u(to), d, b, to) =0
h,(t(t), x(ti), y(Q, u(Q, d, b, tj =0V ti G [to,tf
gi (i(t), x(t), y(t), u(ti), d, b, tj :50, V [to

tj 6 vtf
h, (b, d) =
9b (b, d) :5
-(k-1)
ha =b-b =0
221
Appendix C DetailedAnalysisof the MIDO Algorithm
where b is now a vector of continuous time invariant search variables and ý(k-l),
S the set of
complicating binary variables derived from the solution of the (k- I )Ih "master" sub-problem.
Then, if the solution of the "primal" problem is denoted as fik (t) and jk, with resulting state
and algebraic variables jk (t) and ýk (t) respectively, and the vector b at the optimal solution
(C. 1) fik, the "master" sub-problems is formulated

of as accordingly.
Master Problem Construction

The "master" problem is formulated using dual information and the solution of the "primal"
problem. The dual variables are derived directly when the gradient evaluation method is used
for the "primal" sub-problem (Mohideen et al., 1997), or through the solution of the final
value problem (Bryson and Ho, 1975; Schweiger and Floudas, 1997). Therefore, for a
feasible "primal" problem (C. 1), the Lagrange function, Ek is given by:
,
1: k (fik akb (tf ), ýk (tf ), a k )+ ft"F(i kk (t), fi k (t), dk
G(jk bk, tf bk, t)dt
0
'fVkT(t) (jk(t), 6k
+f f jk (t), ýk (t), fik (t), ak
f , t)dt
to
t(VkT
+f (t)h(ik(t), yk(t), Ü k(t), dk, bk, t)dt
h
to
ik(to), ýk(to), Ük(t ^^ bk

dk, (C2)
+ýkT ho(ik(to), 0),
to)
(jk(t,
" kik'hi ), ýk (t, ), fik (t, ), a k, 6k, t,
Ib
(i
" Itjgi k (t, k (t, ), fik (t, kk,b t,
I
ak T
" kkT hb(bk, +Itk gb(bk, d k)
b b
+CokT(fik -E)
where Vf.Vh,4 are the dual multipliers associatedwith the differential and algebraic equations
and the set of initial conditions respectively, 4, Itit 49 l1b are dual multipliers associatedwith
the point equality and inequality constraints, and the time invariant equality and inequality
constraintsrespectively,
and finally cois the set of the dual multipliers for the 11,,
equations.
Since the Lagrangefunction is defined at the solution of the "primal" problem and all the
equations of the "primal" problem f, h, ho, hi and 11bare not functionsof the complicating
ý, then they are all equalto 0
variables and their associatedtermscan be removedfrom the
Lagrange function. Besides this, the complementarity optimality conditions for the NLP in
222
the "primal" sub-problem ensure that tti kTgi : -- ItbkT9b

= 0, and since neither gi, nor 9b is
function of b, their associatedterms can be removedfrom the Lagrangefunction as well.

Thereforethe resultedform of the simplified Lagrangefunction is:
a k, ý) )+ f
Lk (fik, = G(ik (tf )jk (tf ), a k, fik, tf
'F(jk (t), ^k (t), fik (t), ak
ybk, t)dt
to
+(OkT(fik
while the "master" sub-problem is stated accordingly:
Min ii,
b, tl
(C4)
Lk (fik, ak, ý), kE Kfeas
S.t.
where Kf,. is the set of all feasible "primal" problems solved up to the iteration under
consideration. Note that the "master" sub-problem might also contain some binary
(imposed integer ý)
constraints on the variables and if these constraints are linear
expressions then the "master" sub-problem is an MILP and can be solved via conventional
branch-and-bound methods. It should be pointed out that integer cuts (Floudas, 1995) of the
form:
Y,; Z-bi: 5lBkl-l,

i-
ieBk ieNBk
Bk ýj
: = 11 (C5)
NBk ýj
=I: = ol
where jBkIiS the cardinality B k, are additional constraints introduced into the sub-problem
(C4) in order to avoid repetition of previous integer solutions.
The MIDO algorithm terminates when the difference between the least upper bound from the
"primal" problems and the lower bound from the "master" problem is less than a specified
tolerance, or if there is an infeasible "master" problem, in which case, all feasible integer
combinations have been already considered. The solution of the MIDO problem then
correspondsto the solution of the "primal" problem with the least upper bound.
From the preceding analysis of the solution algorithm for MIDO problems two major
advantagesrelated to the generic character of the algorithm are easily recognized. The first
one is deemed from the prospect of algorithm capability of addressing MIDO problems even
223
if the binary variablesappearexplicitly and non-linearly in the DAE system,and then the
"master" sub-problemis constructedwithout any dual information with respectto the DAE
systembeing necessary.This comesat the expenseof adding the set of equations11,= 0,

howeverthe simplicity gainedin the formulation of the '6mastee'sub-problemis muchmore
momentous compared to the complexity added in the "primal" sub-problem by the
ý.
introduction of theseequationsand the searchvariables The secondimportant benefit
gained by this MIDO algorithm is that it is independentof the type of method usedfor
solving the dynamic optimisation "primal" problem. In other words, any existing dynamic
optimisationsolvercan be usedto solveMIDO problemssinceit is a trivial taskevenfor the
most elementaryNLP codesto supply the simple Lagrangemultiplier information required
for the "master" sub-problem.However, despitethe above advantages,the current GBD
basedMIDO solution algorithm exhibits somerestrictionsin the identification of the global
it
optimality, nevertheless,as was statedby Barisalet a]. (2003),it will alwaysconvergeto at
leasta local optimum.
A step-by-stepanalysis of the solution techniquediscussedso far is presentedbelow for

deepercomprehensionof the algorithmfunctionality.
C.2 Algorithmic Procedure of the MIDO Method
The sequenceof steps that describe the iterative solution algorithm from MIDO problems is
summarised as follows (Bansal 2000), while it schematically representedin Figure C. I:
Ste7zI
Set the termination tolerance, e. Initialise the iteration counter, k=1; lower bound, LB
and upper bound UB = oo.
Stfp 2
Fix the values of the "continuous" variables b to the optimal values of the integer variables
found in the (k- I)Ih "master" problem (if k=1 then an initial guess of the binary variables,
is required to initiate the algorithm). Then solve the kth "primal" problem (5.1) to obtain a
solution jk . For computational speed, omit the search variables and their associated
in formulation (C. 1) of the "primal" Set UB jk )
constraints resulted the problem. = min(UB,
224
Appendix C Detailed Analysis of the MIDO Algorithm
and store the continuous and integer variables corresponding the to the best "primal" solution
so far.
Stfp 3
Solve the "primal" problem (C. 1) at the solution found in Step 2 with the full set of search
variables and constraints included. Convergence will be achieved in one iteration. Obtain the
k
multipliers co neededto construct the kýh"master" problem (CA).
StCp4
Solve the k th relaxed "master" sub-problem (CA) with integer cuts (C. 5) to obtain a solution
k. Reset the
TI new lower bound, LB =Ilk.
Stgp 5
If UB - LB: 5 c, or the "master" sub-problem is infeasible, then stop. The optimal solution
b(k+l) = ýk
corresponds to the values stored in Step 2. Otherwise set k=k+1, and return to
Step 2.
In the case that an infeasible "primal" problem (5.1) is resulted for a particular set of values
bk, then in Step 3 the following infeasible minimisation problem is solved instead of (C. 1):
Min a,
a, u (t), d,b, tf
S.t. f (i(t), x(t), y(t), u(t), d, b, t) = 0, Vt EE[to, tf ]
h(x(t), y(t), u(t), d, b, t) = 0, Vt EE[to, tf ]
ho(i(to), x(to), y(to), u(to), d, b, to) =0
hj(x(tj), y(tj), u(tj), d, b, tj) =0 Vtj r=ItOotf I i=1 N

...... (C6)
(x(ti), d, b, )
ti :5a-e, V [to,
ti EE tf Ii=I...... N
gi y(ti), u(ti),
hb(b, d) =0
gb(b, d) :50
ha =b 0
a>O
where a is a positive scalar quantity and e is a vector whose elements are all equal to one. In
Step 4, the "master" sub-problem then is modified accordingly:
225
Appendix C Detailed Analysis of the MIDO Algorith
Min il,
b, Tj
jk U):g
S.t. +CokT(Gk
- 11,kEKf., (C7)
WkT(fik-U): 50, k(z-Kinfeas
where Kfea,denotes the set of iteration numbers for which feasible "primal" problems are
found, while Kjý,f,,,, the set for which infeasible "primal" problems are found.
Initial Guess
do, tf, ýo
uo(t),
Fix b=b
Prinial problem (5.1)

I NLP-
solution algorithm inDAE-0 r
------
_____tegrit _j
Fix u (t), d, tf
Printalproblent (C.1)
Convergence in ONE iteration

b are treated as decision variable!
Dual information w
Solution qfthe primal problem J
Master Problem (C. 4)

Introduction of integer cuts (C. 5)
MILP Problem
NO
Check for convergence
I Yes
Optimal Solution
the solution of Primal (5.1)
Figure CA: Algorithmic steps of the MIDO problems solution method.
226
Appendix C Detailed Analysis of the MIDO Algorith
C.3 Literature
Bansal, V. (2000). Analysis, design and control optimization of processsystemsunder

uncertainty. PhD Thesis, Imperial College, University of London.
Bansal, V.; Sakizlis, V.; Ross, R.; Pcrkins, J.D.; Pistikopoulos, E.N. (2003) Ncw algorithms
for mixed-integer dynamic optimization. Computers Chem. Eng., 27, p. 647.
Bryson, A. E.; Ho, Y. (1975) Applied Optimal Control. New York: Taylor & Francis.
Floudas, C.A. (1995) Nonlinear and mixed-integer optimization. Oxford University Press,
New York.
Mohideen,M.J.; Perkins,J.D.; Pistikopoulos,E.N. (1997) Towards an efficient numerical

for
procedure mixed integeroptimal control. Eng.,
Chem.
Computers 21 Suppl.,p. S457.
Schweiger, C.A.; Floudas, C.A. (1997). Interaction of design and control: Optimization with
dynamic models. In: Optimal Control: Theory, Algorithms and Applications, W. W.
Hager and P.M. Pardalos, Eds., Kluwer Academic Publisherts B. V., p. 388.
227
APPENDIX D
The Sanchez-Lacombe EoS as a Tool

for Thermodynamic Calculations
From the analysis over the polymerization kinetic mechanism it is well understood that the
polymer molecular development is dependent on the monomer concentration at the active

sites of catalyst, and this concentration is in turn dependenton the solubility of the monomers
in polyethylene at the temperature and pressure at which the polymerization occurs.
Therefore, in order to study or model a polymerization process, accurate calculations on
monomer solubility are necessary. This is a challenging task particularly when polymer
production processesare concernedwhere one encounterscomplex polymer-monomer-
solvent mixtures, that is, mixtures of small conventional molecules with long-chain
polymers.Equationsof State(EoS), appropriatefor such mixtures,are very attractivetools
that can simultaneous accomplish various modelling tasks in terms of volumetric,
calorimetric and phaseequilibrium properties of the mixture.
For the needs of this thesis, (i. e., phase equilibrium calculations in the Flash unit of the
Borstars process, volumetric and pressurecalculations in the proccss units, ctc.) the Sanchez-
LacombeEoS was used, which is appropriatefor polymer mixtures and is basedon the
Lattice-Fluid theory on polymer solutions.A reducedform of the Sanchez-Lacombe
EoS for
a pure component T is given by the following expression:
)( 1)-ij=o
-2 -
pi +Pi +Tj In I-pi + I-- p
ri
228
AppendixD The Sanchez-Lacombe
EoS as a Tool for ThermodynamicCalculations
where r is the number of lattice occupied by a molecule:
MwiPi*
(D2)
R Ti* pi*-
and Pj, Tj and pi are the reduced pressure, temperature and density of a pure component
defined in terms of the respective characteristic values (Ti*, Pj* and pi* or ui*,) of the
component:
Ti = T/Ti*,
Pi = P/Pi*, (D3)
pi =p/pi* where pi* =Mwi/(ri ui*)
From the characteristic values of component T, the interaction energy (ci*i) between two
mers of this component and the close-packed molar volume (uj*j) of a mer are defined
accordingly:
c*ii =RTi* U!11=e!11/P*i (D4)
The three characteristic parameters,(i. e., Ti*, Pi*,p! ) for every component 'i' are obtained by
fitting the Sanchez-Lacombeequation to pure component PVT data. Table DA summafizes
the characteristic values of all the components appear in the polymerization system of the
Borstare process.
When the Sanchez-Lacombeequation applies for a binary or a multicomponcrit mixture, then

both the reduced and the characteristic variables are defined for the mixture based on the
molar-volumecomposition(9) of the mixture asshownbelow:
Tmix = T/Tm*j where, Tm*ilx /R

=c*mix
mix
P. i,, = P/P*. where, P*- =e* /u* (D5)

nux frux -
mix mix
p. j., =plp*. i., where, p*.i,, =Mw /(r. u *.

j., i,, j.,
229
Table D. 1*: Characteristic parameters of the Sanchez-Lacombe EoS for the components of
the polymerization mixture.
Polymer
Component i: Ethylene Butene Hydrogen Nitrogen Propane
(PE)
Ti* (K) 278.0 403.0 51.45 129.0 371.0 649.0
(bar) 3400.0 3220.0 313.8 1960.0 3130.0 4250.0

i
P*(g / M)
rc 0.668 0.736 0.1128 0.945 0.690 0.904
i
The mixing rule for the characteristic close-packed molar volume of the mixture (u*,,,i.,) is:
NE Nwinp
u *Mi.=ýýi9iu1; whereui*j =0.5(ui*i +ul)(1-nij) (D6)

i=l j=l
where the binary interaction parameters nij between the components T and 'j' are used to
correct deviations from the arithmetic mean, while the volume fraction of the component T
is defined as:
mi /II Ný
p Mi I
Ti ,-:
u -, j=l P! U!
where mi is the mass fraction of component T in the mixture.
Similarly, the mixing rule for the characteristic interaction energy per mer of the mixture
(C*.i,,) is:
Nýjp Nxmnp
cij (cjjcbý)0-5(l kij) (D8)

mix u iyjci*juijl ; where = -
mix i=l j=l
1. McHugh, M. A.; Krukonis, V. J. (1994) Supercritical Fluld F-wraction-2ndEd., Butterworth-11einemann.

2. Sanchez,I. C.; Lacombe, R. H. (1978) Statistical thermodynamics of polymer solutions. Macromolecules,
11,1145
230
where the binary interaction parameterskij between the components T and 'j' are employed
to correct the interaction energy of a mer of mixture. Both the nij and kij interaction
parameters,are adjustable parameters used to fit experimental thermodynamic data and they
used to be functions of temperature in order to obtain a good representation of the
thermodynamic behaviour of a mixture. However in this study the values of these parameters
were constant despite the extremely different operating conditions of temperature and
pressure between the process units of the Borstar@ plant operating under. Table D. 2
summarizes the values of these binary interaction parameters for the set of components
existing in the processunits of the Borstare plant.
The mixing rule for the number of sites occupied by a mer of mixture is given by:
N Tj
(D9)
rmix j=l rj
Therefore the Sanchez-Lacombe equation is properly adapted to account for the mixture
properties:
-2 )(r. I )pmixl=o
pmix+P, ix +Tmix In I-pmix + I- (DIO)
ix
The equation above for given p. i,, andTmix can be solved for Pmix in consistency to the
Eqns. (7.3) and (7.36) or alternatively can be solved for pmi.,, when Prix andTmix are
known in consistency to the Eqn (7.37). In the latter case, there are three solutions of the
Eqn. (DIO) and selection of the appropriate solution is required in terms of the
thermodynamic state of the mixture (e.g., liquid-, gas-phase, etc.). Therefore, in case of a
two-phase mixture, the lower value of density derived from the solution of Eqn. (DIO)
correspond to the density of the "light" phase, while the respective higher value of density
depicts the density of the "heavy" phaseof the mixture.
The Eqn. (DIO) can be usedto calculatethe volume changeof a mixture with temperature
variationsat constantpressure:
dV V*- dVmix V*.

nux
I dp. ix
nux (DII)
-IP
dT
=
T; ýx p =-- Tm*ix 2
dTmix Ti mix
pd
231
EoS asa Tool for ThermodynamicCalculations
Table D. 2: Binary interaction parametersfor the mixing rule of the Sanchez-LacombeEoS

Ethylene Butene Hydrogen Nitrogen Propane Polymer PE
i kij nij kij nij ký nq kU nij kij nq kij nij
Ethylene 00 0 0 0 0 0 0 0 0 -5.65E"' 0
Butene 00 0 0 0 0 0 0 0 0 -2
-1.813 -5.67E "2
Hydrogen 00 0 0 0 0 0 0 0 -0.3515 0
Nitrogen 00 0 0 0 0 0 0 0 0 0.037 0
Propane 00 0 0 0 0 0 0 0 0 2
-0.015 -3.67E
Polymer -5.65E-2 0 -2 -2 0 0.037 0 15 3.67E -2 0 0
-1.8E -5.67E -0.3515 -0.0 -
drrix
Considering negligible the change of r. ix with the variation of T. ix (i. e., 0) then
, -=
dTrnix
differentiating the Eqn. (DlO) with respect to T ix we obtain:

..
In (I -p. ) +(I--) p. j.
dpmix j.
rmix (D 12)
dTmix
2p. +Tmix (I -
ix rmix
Prnix
therefore,
I
In (I - p,, + -) p,,,ix
dV " I ý
rmix (D 13)
-IP=V.
dT Tm* 2
i. ýI
Pnlix 2
p- +T
rmix I-Pmix
When the Sanchez-Lacombe equationis employedfor phaseequilibrium calculation in a

multiphase system then appropriatemanipulationsare necessaryin order to obtain the
chemicalpotential of every component T in eachphase from the Gibbs free energyof the
mixture accordingto the following thermodynamicrelationship:
DieL.
232
aG ri
RT[In (pi +(I -
aNi rmix
T, P,N,, j
1-( z(pi C(C

-p. ü.
(D14)
+ri +RTu, i, [(I-pmix)ln(I-pmix)+Lm-ix Inpmixl

ri
N
......p
+Pumi, (2 jyjuýlj -u*mi. )
j=l
where Ni is the number of moles of component T in the mixture.
Therefore,in caseof a biphasialmixture, all the abovecalculationare carriedout separately

for every phaseand the mathematicalexpressionof the thermodynamicequilibrium between
these phasesis:
gi2 ;i=1,2 N (D15)

I ..... comp
From the above equilibrium statement the molar composition of the two phases of the
mixture can be derived.
233

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CONTROL AND DYNAMIC

NIZ CENTRE FOR PROCESSSYSTEMSENGINEERING

The commercial technology development related to the olefin polymerization processesresults

polyethylene in particular, as well as from a considerable economic importance of this

1. Polyolefin Market Status I

2. Polyolefin Technology Developments: Polymerization Processes&

2.5.1 Catalyst for Gas-PhasePolymerization 30

3. Catalytic Gas-Phase Olefin Polymerization Fluidized Bed Reactor

3.2.2 Kinetic Rate Expressions 48

3.3.2 Dynamic Mathematical Model 61

4. Process Design and Control Optimisation 69

4.1 Problem Statement 69

4.2.1 Five-StepProcessControl Synthesis 71

4.3.1 ControlObjectives............................................ o....................

4.4 Dynamic Process Optimisation 80

5. Optimal Control and Grade Transition Operation of a PE FBR 102

5.1 IntegratedSolutionof the GradeTransitionProblem-MIDO.................. 103

5.1.1 TbeMIDOProblemFormulation 103

5.3 MathematicalProblemFormulation......................... 0...................... 108

5.5 ConcludingRemarks................................................................... 130

5.6 Literature................................................................................. 131

6. Optimal Production Campaign Scheduling in a PE FBR 133

6.1 Problem Statement-Motivation ...................................................... 134

6.2 Current Research Orientation ....................................................... 135

6.3 Construction of the Multilevel Problem ............................................ 137

6.3.1 Definitions .......................................................................... 138

6.3.2 Clarification Remarks 139

6.5 Mathematical Model Formulation 141

6.5.3 Known Initial Operating Point 147

6.5.5 Sequential Transition Mode 147

6.6 Solu tion Procedure 148

6.7 Results 149

6.9 Concluding Remarks................................................................... 156

7. Plant-Wide Issues 160

7.1 Introduction-The Borstaro Process.................................................. 160

7.1.1 Catalyst System - Pre-polymerization Section................................. 162

7.1.2 Plant Units - Model Consideration............................................... 163

7.2 Mathematical Model 164

7.2.1 Polymerization Kinetics 164

7.2.2 Reactor Model 166

7.2.3 Flash Separator Model 171

7.2.4 Thermodynamic Model 173

7.2.5 Process Control Configuration 177

7.3 Modelling Limitations .................................................................. 180

7.4 Model Input Parameters ............................................................... 183

7.5 Simulation Results 185

7.8 Literature ................................................................................. 199

8. Conclusions & Recommendations for Future Research 200

8.1 Thesis Contribution ..................................................................... 200

8.2 A Challenge for Future Research .................................................... 204

Related Publications Arising from this Work 206

A Pseudokinctic Rate Constants -Rate Functions for Olefin

B Physical Properties - Process Unit Design Parameters 217

C Detailed Analysis of the MIDO Algorithm 221

C. 1 Novel Solution Method of MIDO Problems ....................................... 221

C. 2 Algorithmic Procedure of the MIDO Method .................................... 224

C.3 Literature ................................................................................. 227