LINEAR LOW-DENSITY POLYETHYLENE (LLDPE) (100 kt/yr)

1. Introduction on LLDPE Background:

Linear low-density polyethylene (LLDPE) is a substantially linear polyethylene, with

significant numbers of short branches, commonly made by copolymerization of ethylene with
longer-chain olefins. Linear low-density polyethylene differs structurally from conventional
low-density polyethylene because of the absence of long chain branching. The linearity of
LLDPE results from the different manufacturing processes of LLDPE and LDPE. In general,
LLDPE is produced at lower temperatures and pressures by copolymerization of ethylene and
such higher alpha olefins as butene, hexene, or octene. The copolymerization process produces
an LLDPE polymer that has a narrower molecular weight distribution than conventional LDPE
and in combination with the linear structure, significantly different rheological properties.

The production of LLDPE is initiated by transition metal catalysts, particularly Ziegler

or Philips type of catalyst. The actual polymerization process can be done in either solution
phase or gas phase reactors. Usually, octene is the copolymer in solution phase while butene
and hexene are copolymerized with ethylene in a gas phase reactor. The LLDPE resin produced
in a gas phase reactor is in granular form and may be sold as granules or processed into pellets.
LLDPE has higher tensile strength and higher impact and puncture resistance than LDPE. It is
very flexible and elongates under stress. It can be used to make thinner films, with better
environmental stress cracking resistance. It has good resistance to chemicals and to ultraviolet
radiation. It has good electrical properties. However it is not as easy to process as LDPE, has
lower gloss, and narrower range for heat sealing.

LDPE and LLDPE have unique theoretical or melt flow properties. LLDPE is less shear
sensitive because of its narrower molecular weight distribution and shorter chain branching.
During a shearing process, such as extrusion, LLDPE remains more viscous and, therefore,
harder to process than an LDPE of equivalent melt index. The lower shear sensitivity of LLDPE
allows for a faster stress relaxation of the polymer chains during extrusion, and, therefore, the
physical properties are susceptible to changes in blow-up ratios. In melt extension, LLDPE has
lower viscosity at all strain rates. This means it will not strain harden the way LDPE does when
elongated. As the deformation rate of the polyethylene increases, LDPE demonstrates a
dramatic rise in viscosity because of chain entanglement. This phenomena is not observed with
LLDPE because of the lack of long-chain branching in LLDPE allows the chains to slide by
one another upon elongation without becoming entangled. This characteristic is important for
film applications because LLDPE films can be down gauged easily while maintaining high
strength and toughness. The rheological properties of LLDPE are summarized as "stiff in shear"
and "soft in extension". It is not taken in most curbside pickups in communities. LLDPE can
be recycled though into other things like trash can liners, lumber, landscaping ties, floor tiles,
compost bins, and shipping envelopes.

Process types:

a) Slurry process: - it is also called basells hastalen slurry process. It consists of two
continuous stirred tank reactors operated in parallel or in series according to the grade
of polymer required. The process is designed to produce uni or bimodal polymer using
Ziegler Natta catalyst. The polymer is produced at relatively low temperature (70 - 110
C) and low pressure (1 - 5 MPa) in a saturated hydrocarbon medium. The polymer
form suspension or mobile slurry. The reaction medium is removed and polymer is
separated from the hydrocarbon inert diluents. The obtained powder is mixed with
stabilizers and generally extruded into pellets.
b) Gas phase process: - In this process the catalyst and the co-monomer are fed to a slurry
stirred reactor in which pre polymerization occur. Pre polymerization under mild
conditions help to prevent hot spots or it will hinder the process. The polymer is
transferred to a dryer where hot nitrogen evaporates the solvent. Then the polymer
powder acts as a catalyst for the main polymerization reactor and is fed continuously to
the fluidized bed reactor.

The fluidization reactor comprises of two main parts which are cylindrical part and
disengagement part. The cylindrical part is equipped with gas distribution in order to fluidize
the content of the bed. The disengagement reduces the velocity of flowing gas and constantly
disengages the polymer particle from output gas. Finally, the gases are compressed and
returned to bottom of the reactor ethylene, butene, or hexane, H2 as a chain terminator and N2
as an inert gas is introduced at different points to assure perfect mixing and prevent
condensation which could damage the blades of the compressor. The circulating gas fluidizes
the bed and removes the heat of the reaction.
Comparison of Gas phase process and slurry process:

In slurry process due to use of solvent, same additional equipment is required like
solvent stores , purifiers etc. therefore gas phase processes are more compact, simpler,
have lower cost and environmental impact is less.
In gas process, it creates no wall sheeting or fouling due to the ployethenes solubilities
in solvent medium which is the main problem in slurry process.
In slurry process there are some useful points like mild operating conditions, ease of
heat removal, ease of processing and high monomer conversions.
In gas phase process, production of more off spec polymer during grade change
especially changing from 1 catalyst to another catalyst type.
In gas phase process, agglomeration and lump due to poor heat removal from growing
polymer practices leading to the formation of hot spots followed by sintering of the
polymer.
In gas phase process, disintegration of growing polymer particle due to undesirable
stress leading to the formation of fines. Increasing the fines content in the gas phase
reactor is catastrophic for all gas phase plants, leading a loss of homogeneity of
fluidization and eventually leading to the blockage of subsequent process unit.
In gas phase process, electrostatic charge leading to agglomerate formation are wall
sheeting especially near the inclined part of the disengagement zone of gas phase
reactor.
Slurry reactors have a very efficient heat removal and wide co monomer range but the
product range is limited due to solubility of the produced polymer.

LLDPE has penetrated almost all traditional markets for polyethylene, it is used for plastic bags
and sheets (where it allows using lower thickness than comparable LDPE), plastic wrap, stretch
wrap, pouches, toys, covers, lids, pipes, buckets and containers, covering of cables, geo-
membranes, and mainly flexible tubing.
 2. Licensor Selection:

Licensor : LyondellBasell

Technology : Spherilene: Flexible gas-phase process technology for the production of the
entire range of polyethylene products.

The Spherilene technology from LyondellBasell is a fluidized-bed, gas-phase process for the
production of the entire density range of polyethylene (PE) products, from linear low density
(LLDPE) to medium density (MDPE) and high density (HDPE). The flexibility of this
technology, which is demonstrated by an extensive portfolio of grades, enables licensees to
effectively manage the continuously dynamic polyethylene markets well into the future.

The combination of extended process flexibility, very competitive capital costs and very low
operating costs, especially due to efficient monomer recovery, underscores the attractiveness
of this technology for world scale plants. The proven plant reliability enables the scale-up of
the design, based on simple principles, to capacities of up to 600 kt/a. The extensive Spherilene
PE portfolio includes HDPE grades (0.940 0.965 g/cm3), MDPE grades (0.930 0.940
g/cm3) and LLDPE grades (0.918 0.930 g/cm3), which have been developed by
LyondellBasell and are marketed by the company and a growing number of licensees in all
major markets. Products also cover the full range of melt index (190 C, 2.16 kg) values, from
0.01 g/10min to 100 g/10 min and beyond, as well as monomodal, broad and bimodal molecular
weight distributions that ensure good process ability in all applications.

3. Process Description:

Catalyst components are mixed and fed directly to a pre contact vessel where the
catalyst is activated under controlled conditions. The activated catalyst system flows
continuously into the first gas-phase reactor (GPR). A cooler on the circulation gas loop
removes the reaction heat. Product containing still active catalyst is continuously discharged
from the first GPR via a proprietary device to a second GPR with similar configuration.
Resultant discharged gas is recovered and no gas from the first GPR enters the second GPR
due to a proprietary lock-hopper system. The second GPR is independently supplied with
necessary monomer, comonomer and hydrogen to maintain reaction conditions truly
independent from the first GPR. This gives Spherilene process the ability to produce truly
bimodal HDPE grades and the added freedom to obtain inverse comonomer distribution in the
final product by selectively feeding comonomer only where necessary. Pressure and
Temperature in the GPRs are also independently controlled while no additional feed to catalytic
components to the second GPR is required. The polymer in spherical form with particle size
ranging from approximately 0.5mm to 3mm, is then discharged in a receiver recovering the
resultant gas and to a proprietary unit for monomer stripping and neutralization of any
remaining catalyst activity. Residual hydrocarbons in the polymer are stripped out and recycled
back to reaction. The polymer is dried by a closed loop nitrogen system and with no volatile
substances is sent to liquid and/or solid additives incorporation step before extrusion.

4. Process Flow Diagram: