friday 3/5/20021 metallocene catalyzed liquid-pool polymerization in a continuous hsr dpi # 114...
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Friday 3/5/2002 1
Metallocene Catalyzed Liquid-Pool Metallocene Catalyzed Liquid-Pool Polymerization in a Continuous HSRPolymerization in a Continuous HSR
DPI # 114DPI # 114
Mohammad Al-haj AliMohammad Al-haj Ali
DCP\IPP Groups
Chemical Engineering Department
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Quality Assurance of a Polypropylene Reactor Quality Assurance of a Polypropylene Reactor During Continuous Production and Product During Continuous Production and Product
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Presentation Outline:Presentation Outline: The mechanism of polypropylene polymerization.
1) The catalyst system.
2) Polymerization steps.
Development of expected MWD function.
1) Instantaneous MWD.
2) Derivation of instantaneous MWD function.
Factors affecting MWD.
1) Catalytic System.
2) Polymerization Parameters.
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Grade transition strategies.
1) Factors affecting grade transition policies.
2) Grade transition approaches.
3) Optimization problem formulation.
4) Objective function.
5) The method of solution.
What is next.
Friday 3/5/2002 4
Catalyst System:Catalyst System:The catalyst system used in this work is: rac-Me2Si[Ind]2ZrCl2/MAO/TIBA
1- Metallocene Catalyst:
rac-Me2Si[Ind]2ZrCl2
Me2Si ZrCl 2
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Catalyst System:Catalyst System:
2- Cocatalysts:
a- MAO
b- TIBAAl
R C
H
R
R
C
C
C
HH
H
HH
H
H
H
R=
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The Mechanism of Propylene Polymerization:The Mechanism of Propylene Polymerization:
1- Initiation
MCl2
Me
AlO+ MMe2
Me
AlO
Me
AlO
-
MMe2
Me
M
+
+ +
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The Mechanism of Propylene Polymerization:The Mechanism of Propylene Polymerization:
2- Propagation:
Me
M+
RMe
RM+
R +
M
nR
M+
R
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The Mechanism of Propylene Polymerization:The Mechanism of Propylene Polymerization:
2- Propagation:
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The Mechanism of Propylene Polymerization:The Mechanism of Propylene Polymerization:
2- Propagation:
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The Mechanism of Propylene Polymerization:The Mechanism of Propylene Polymerization:
3- Termination:
a-Transfer with Hydrogen:
H2
+
M
nR+
+
M H
nR+
b- Transfer with Monomer:
+
+
M
nR+
nR
+
M Me
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Development of Expected MWD Function:Development of Expected MWD Function:Instantaneous MWD:
The method of instantaneous MWD relies on the big difference in time scale for
the polymerization reactor and the polymers life time.
The instantaneous MWD of polyolefins with single-type catalyst:
)jqexp(jqy 2dj
Schulz-Flory distribution function assumptions:
1- All chain propagating species have the same kinetic parameters.
2- The probability of chain termination does not depend on chain length.
3- polymerization reactions are carried out at constant monomer concentrations.
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Development of Expected MWD Function:Development of Expected MWD Function:
Derivation of instantaneous MWD function:
1- Propagation reaction
MPkrPMP jpp1jj
2- Transfer reactionsa- transfer with hydrogen:
j2HtHt*
j2j P]H[krCMHP22
b- transfer with monomer
jMtMt*
jj MPkrCMMP 3- Deactivation
jddjj PkrDMP
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Development of Expected MWD Function:Development of Expected MWD Function:
Derivation of instantaneous MWD function
The production rate of active and dead polymers:
dMt2Ht
jdMt2HtMj
jdjMtj2Htj1jppj
N
1iik,ik
kMk]H[kT
P]kMk]H[k[R
PkMPkP]H[k)PP(MkR
rR
2
2
2
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Development of Expected MWD Function:Development of Expected MWD Function:
Derivation of instantaneous MWD function
By using QSSA for the active polymer
1qp
pPP
MkT
Mkp
MPkP]MkT[
1jj
p
p
1jpjp
MkkMk]H[k
kMk]H[kq
pdMt2Ht
dMt2Ht
2
2
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Development of Expected MWD Function:Development of Expected MWD Function:
Derivation of instantaneous MWD function
)jqexp(TqPR
P)jqexp(qP
pq
PP
P)jqexp(pP
PpP
tMj
tj
1t
11
j
11j
j
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Development of Expected MWD Function:Development of Expected MWD Function:
Derivation of instantaneous MWD function
21n
1j
n
1j1j
1jt
tdj
1jMjM
MjMdj
qq!ndj)jqexp(j
dj)jqexp(j)jqexp(j
)jqexp(TjqP
)jqexp(TjqPy
RjM
RjMy
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)jqexp(jqy 2dj
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Factors Affecting MWD:Factors Affecting MWD:
1- Catalytic System:
a- Catalyst type.
b- Cocatalyst.
c- Catalyst / Cocatalyst
2- Polymerization Parameters:
a- Hydrogen concentration.
b- Reaction temperature.
c- Reaction time.
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Factors Affecting MWD:Factors Affecting MWD:
1- Hydrogen concentration
Low H2
High H2
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Factors Affecting MWD:Factors Affecting MWD:
1- Reaction temperature
Low T
High T
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Factors Affecting MWD:Factors Affecting MWD:
1- Reaction time
No effect is found for time in MWD:
1- Naofumi & Mizunuma, 1998
2- Chien & Wang, 1990.
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Grade transition strategies:Grade transition strategies:
Desirable grade transition policy, takes the following points into account:
Time.
Plant safety.
Polymer instantaneous properties.
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D ynamic S imulations U isng D ynamicKinetic & P rocess M odel
u s in g co rro la tio n m o d els fo r p o lym er p ro p erties u s in g m o re co m p licated k in etic m o d els
S olving D ynamic M odel-B ased O ptimizationP rob lem
G rade T ransition A pproach es
Requires an extensive trial & error
Can not represent PDI Consider all polymer properties
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Grade transition strategies:Grade transition strategies:
Optimization problem formulation
uplow
uplow
oo
fo)t(u
x)t(xx
u)t(uu
x)t(x
)]t(x),t(u[fdt
dx
0)]t(x),t(u[c.t.s
]t,t[t)]t(x),t(u[Fmin
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dt))PDITPDI
PDIT)t(PDI(*t*w)
TMWMW
TMW)t(MW(*t*w(F
f
o
t
t
2
0t2
2
n0t,n
nn1
Grade transition strategies:Grade transition strategies:
Objective function
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Grade transition strategies:Grade transition strategies:
The method of solution
s
1jijiji )t(a)t(U
Control Vector ParameterizationControl Vector Parameterization
time
ij
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0)a(h
0)a(g.t.s
)a(Fmin
ij
ij
ija ij
Applying U(t) in the original optimization problemgives:
Grade transition strategies:Grade transition strategies:
The method of solution
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What is Next:What is Next:
1-1- Formulation of the second optimal strategy for grade transition of Formulation of the second optimal strategy for grade transition of
Polyolefins using Polyolefins using Barrier ApproachBarrier Approach . .
2- 2- Experimental model validation of the batch mode of the HSR model, Experimental model validation of the batch mode of the HSR model,
and producing bimodal PP theoretically and experimentally.and producing bimodal PP theoretically and experimentally.
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