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29 Polyethylene 25
producers of these copolymers have constructed catalysts give their highest yields at temperatures
plants especially for their manufacture, using at which polyethylene is insoluble. The Phillips
corrosion-resistant steels. process on the other hand originated in the labo-
ratory as a solution process that uses a fixed bed
of catalyst [111] and was commercialized in
5.1.4. Linear Low-Density Polyethylene 1956 as a solution process using a powdered
(LLDPE) catalyst which had to be removed by filtration.
Laboratory developments led to the discovery of
CdF Chimie converted high-pressure process high-activity catalysts which fragment at tem-
equipment to use Ziegler catalysts to make peratures below 105 C to enable the low con-
HDPE. These plants were later used to copoly- centration of finely divided catalyst residues to be
merize ethylene with butene and other comono- left in the product. Since 1961 all Phillips plants
mers to make LLDPE. The catalysts used are have been of this type using novel process tech-
generally of the Ziegler type but have been nology to implement their Particle Form suspen-
specially developed for the high temperatures of sion process.
the high-pressure process [107]. Several other Many companies have built plants to make
manufacturers have modified existing high-pres- polyethylene by using Ziegler catalysts, but be-
sure plants to enable them to make a rapid, but cause the license was only for the use of the
limited entry into the LLDPE market, but this catalyst, there has been a diversity of process
route is not seen as suitable for a large new designs, even amongst the suspension processes.
investment. The required modifications (gener- The Phillips process was licensed as a package
ally similar to those for free-radical co-polymers and the plants themselves tended to be very
together with some additional ones associated similar. More recently the picture has become
with the different type of catalyst) are as follows: blurred as chromium-based catalysts have been
used in fluidized-bed reactors and Ziegler cata-
1. Purification columns to remove polar impuri- lysts are being employed in loop reactors. Early
ties from the ethylene and olefin comonomer. Ziegler plants included a catalyst residue remov-
2. Hydrogen injection for MFI control. al stage which added considerably to the com-
3. Compressor modifications to take account of plexity and cost. Since the late 1960s it has been
the lower compressibility and poorer lubricat- possible to eliminate this step. Other variations
ing properties of the monomer mixture [108]. arise from the selection of the diluent. A high-
The concentrations of butene or other olefin of boiling diluent generally requires more energy to
ca. 50 % are much higher than in the free- remove the final traces from the polymer, and
radical copolymer case. stripping with steam is frequently employed.
4. Catalyst handling equipment to produce Because of the low flash point, the use of a
pumpable dispersions, and to maintain the low-boiling diluent such as hexane requires more
catalyst under a nitrogen atmosphere. care in the design and operation of the plant, but
5. A system for injecting a catalyst deactivator this seems to be the preferred route for modern
such as a suspension of calcium stearate [109], plants.
after the reactor and before the separator. The suspension process has been used exten-
6. Usually some modifications to the pelletizing sively for the production of HDPE, and in many
extruder to take account of the higher torque cases these polymers incorporate a small amount
generated by LLDPE. of comonomer to increase the toughness or resis-
tance to stress cracking. The use of higher con-
centrations of comonomer to produce LLDPE
5.2. Suspension (Slurry) Process presents problems however, as a significant frac-
tion of the product dissolves in the diluent.
The formation of polyethylene suspended in a Because of the poorer solvent properties of iso-
hydrocarbon diluent was envisaged as a conve- butane, the Phillips process is best suited to
nient form of production process from the earliest making lower density materials. With the origi-
patenting by ZIEGLER [110]. This was reinforced nal Phillips catalysts the lower density limit was
by the fact that, for a given pressure, most Ziegler considered to be about 930 kg/m3, but with more
26 Polyethylene Vol. 29
recent catalysts, particularly supported single- on a number of factors, including solvent type,
site catalysts, the limit is reduced to around particle size and shape, but principally on the
920 kg/m3. bulk density of the polymer particles. Slurry
concentrations vary from 15 to 45 wt % [115],
with many patents reporting values in the range
5.2.1. Autoclave Process 30 –35 % in a heavy diluent.
The slurry from the run-down reactor then
Figure 17 shows a flowsheet for a suspension passes to a centrifuge to remove the bulk of the
(slurry) process based on various descriptions of diluent, which is recycled directly to the reactor.
the Hoechst process [8, 74, 112, 113]. The pres- This diluent contains aluminum alkyl and como-
sure employed is between 0.5 and 1.0 MPa, nomer, if used, and the injection rates of these
allowing the use of large reactors (ca. 100 m3). raw materials are adjusted to take into account
The reaction temperature is 80 – 90 C. The the amounts reintroduced by the diluent recycle.
diluent is a low-boiling hydrocarbon such as The polymer is dried in a continuous fluidized-
hexane. The catalyst compounds and aluminum bed drier in a stream of hot nitrogen to remove
alkyl are slurried with diluent in the catalyst residual diluent. Further quantities of diluent are
mixing vessel before being fed to the reactor at condensed from the circulating nitrogen stream
a rate sufficient to maintain the required poly- and recycled. Before extrusion into pellets, sta-
merization rate. Only one main reactor is shown bilizers are added to neutralize the catalyst re-
but, at least in the case of bimodal MMD high sidues, and other additives such as antioxidants
molecular mass polymers [114], two or more may be added at this point.
reactors in cascade may be used. The reaction The powder-fed extruder has a longer barrel
mixture is then passed to a run-down reactor than is the case for the high-pressure process
where the dissolved ethylene is consumed almost because in addition to generating sufficient pres-
completely, avoiding the need for an ethylene sure for the pelletizing head, it must also melt the
recycle. The slurry concentration is an important polymer powder. Although a single long barreled
parameter in the process. A high concentration extruder is shown, new installations increasingly
allows higher outputs from a given reactor vol- make use of a combination of a short extruder to
ume, but the heat transfer to the cooling jacket is melt the polymer followed by a gear pump to
worse and stirring becomes more difficult. The generate the pelletizing pressure. This combina-
maximum usable slurry concentration depends tion has a lower energy requirement.
A simplified flowsheet for the Phillips Particle Fluidized-bed processes for the production of
Form process is shown in Figure 18. The novel HDPE were developed in the late 1960s by Union
double loop reactor constructed from wide-bore Carbide and somewhat later by Naftachemie
jacketted pipe was developed by Phillips engi- (now BP). Although an innovative technology,
neers to avoid deposits, which had been trou- the process did not offer clear economic advan-
blesome in a stirred autoclave [111, 116]. It also tages over the established slurry processes (see
has a high surface-to-volume ratio, facilitating Table 10). A rapid increase in the building of
heat removal and allowing short residence fluidized-bed plants followed Union Carbide’s
times. The impeller forces the reaction mixture announcement of their Unipol process for
through the pipework in a turbulent regime with LLDPE in 1977. In this case the fluidized-bed
a velocity of 5 – 10 m/s. The reaction condi- process is competing with solution and high-
tions of 100 C and 3 – 4 MPa correspond to pressure processes compared to which it has
the needs of the chromium-based Phillips cata- lower capital and operating costs, particularly if
lyst and the required productivity. The diluent it can be assumed that customers are able to use
used is isobutane which facilitates the subse- ex-reactor granules directly (not assumed in Ta-
quent flash separation and, being a poor solvent ble 10). Many fluidized-bed units have been built
for polyethylene, permits higher operating tem- as dual-purpose plants (‘‘swing plants’’) with the
peratures than the higher alkanes. The catalyst is ability to produce either LLDPE or HDPE ac-
flushed into the reactor with diluent from the cording to demand. The fluidized-bed process
metering device at the base of the catalyst slurry can produce a very wide range of MFIs and
tank. The polymer is taken off from a sedimen- densities since it is free of the viscosity con-
tation leg which enables the slurry to be passed straints of the solution process and the solubility
to the flash tank at a concentration of 55 – 65 % constraints of the slurry process. Ranges of
instead of the 30 – 35 % circulating in the loop < 0.01 to > 100 in MFI and densities from
reactor [111]. The isobutane diluent evaporates 890 to 970 kg/m3 have been claimed [117,
in the flash tank and is then condensed and 118]. Originally the process used butene as the
recycled. Residual isobutane is removed in a comonomer for LLDPEs, but later hexene was
nitrogen-flushed conveyor. Pelletization is car- introduced for high-performance copolymers.
ried out in a powder-fed extruder in a similar BP uses 4-methylpentene for its high-perfor-
way to the Hoechst process. mance LLDPEs.