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Univation Technologies
Exxon Chemical/Union Carbide Joint Venture
PO Box 670
Bound Brook, NJ 08805
USA
MANUFACTURING EFFICIENCIES FROM METALLOCENE
Reactants
Compounding PE
PE PE PE
Catalysis Production Resin End-Use
Fabrication Application
Process Product Processing
Additives
2
MANUFACTURING EFFICIENCIES FROM METALLOCENE
3
MANUFACTURING EFFICIENCIES FROM METALLOCENE
Metallocene ligand structure, metal center, and monomer, comonomer, hydrogen, nitrogen
activation chemistry define the electronic and and inert condensing agent such as hexane
steric environment of the catalyst system, which, or isopentane. The “cycle” gas flow provides
in turn, establish the catalyst’s regulation of the monomer and comonomer for polymerization,
stochastic processes of monomer/comonomer agitates the bed, and also removes the heat
insertion and chain transfer chemistries. of polymerization. The cycle gas exits the
“Electronics and sterics” also define catalyst top of the reactor and is then compressed and
kinetic profiles, e.g., activation and decay char- cooled before being fed into the bottom of the
acteristics which determine catalyst productiv- fluidized bed.
ity, and catalyst kinetic response to temperature
and reactant concentrations. Figure 2 shows the
differing copolymerization responses for a range Figure 3. CHAIN-TRANSFER-TO-HYDROGEN
of metallocenes. RESPONSE FOR SELECTED
METALLOCENE CATALYSTS
10
D
0.940
E
Melt Index (dg/min)
F
1
0.930
0.1
0.920
2 1
Density (g/cc)
3 0.01
0.910
4
0.900 0.001
5
1 10 100
H /C Ratio (Micromole/mole)
2 2
0.890 6
0.880
0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
Figure 4. GAS-PHASE POLYMERIZATION KINETIC
C /C Ratio (mole/mole)
6 2
PROFILES FOR SELECTED
METALLOCENE CATALYSTS
4
MANUFACTURING EFFICIENCIES FROM METALLOCENE
5
MANUFACTURING EFFICIENCIES FROM METALLOCENE
0.930 1000
Metallocene
0.925
100
Z/N LLDPE
10
Chrome 1
0.915 Z/N - Ti
Metallocene LLDPE 1
0.910
Chrome 2
0.1
-7 -6 -5
10 10 10 0.0001 0.001 0.01 0.1 1
0.905
4 6 8 10 12 14 16 18
H /C Ratio (mole/mole)
2 2
wt % C in Copolymer
6
The combination of less dissolved co- varied over a wide range with easy adjustments
monomer in the resin and more homogeneous in reactor hydrogen concentration. Transitions
incorporation (absence of low molecular weight from high to low MI resins with certain Z/N
extractable fraction) dramatically reduces resin catalysts require removal of high hydrogen con-
stickiness in the reaction and conveying proc- centrations. These transitions can require flaring
esses, allowing increased reactor operating cycle gas, resulting in lost monomer and co-
temperature. These factors also allow increased monomer. Reduced hydrogen levels in the re-
condensing level in the reactor, leading to fur- actor will reduce monomer/comonomer loss in
ther process efficiencies which will be discussed transition and recovery, resulting in improved
in a subsequent section. process efficiencies.
Reaction production rates can be in-
Benefits of Improved Hydrogen Chain creased with metallocene catalysts because hy-
Transfer drogen in the cycle gas is replaced with materi-
Chain transfer to hydrogen is extremely als with higher heat capacities. Hydrogen can
efficient with metallocene catalysts. Typical constitute approximately five molar percent of
film and molding LLDPEs can be produced with the cycle gas at typical Z/N conditions for a 1-
significantly less hydrogen in the reactor than is MI film product. Reduction of hydrogen from
used for certain Z/N catalysts, resulting in sev- five to 0.01 percent with certain metallocene
eral process and product benefits. Figure 7 catalysts allows addition of five percent isopen-
compares the hydrogen response in the gas tane while maintaining reactor pressure. The
phase of various catalysts in producing C2/C6 overall gas heat capacity increases 10%, which
LLDPE. can translate to a 10% increase in the maximum
High melt index mLLDPEs can be made production rate (assumes no dew point limita-
with improved efficiencies because of decreased tion). This does not include the more important
hydrogen requirements. With certain metallo- benefit of condensed mode operation, to be
cene catalysts, polymer molecular weight can be discussed below.
6
MANUFACTURING EFFICIENCIES FROM METALLOCENE
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MANUFACTURING EFFICIENCIES FROM METALLOCENE
Summary References
Metallocene catalysis brings important 1. Hemmer, J. L., MetCon ‘95, Houston, Texas,
process technology benefits to gas-phase May 17-19, 1995.
polyethylene production that can be utilized to 2. Hogan, J. P., Levett, C. T., and Werkman,
enhance manufacturing efficiencies with the R. T., SPE Journal 1967, 23, 87-90.
UNIPOL PE Process. With specific metallo- 3. European Patent Application 0659773
cene catalyst systems, high catalyst activities, (Priority Date 12/21/93) to Union Carbide
unique Corporation.
process response characteristics, and control of 4. Ohgizawa, M., Takahashi, M., and Kashiwa,
polymer molecular architecture can be com- N., MetCon ‘95, Houston, Texas,
bined May 17-19, 1995.
synergistically in the UNIPOL process for
improved manufacturing efficiencies.
Acknowledgments
Technology described in this paper rep-
resents he efforts of Univation Technologies’
scientists and engineers.
UC-UT005 P7-7578
10/97-2M 8 Printed in U.S.A.