Chemical and Petroleum Engineering, Vol. 44, Nos.

7–8, 2008

COMPARATIVE ANALYSIS OF VARIOUS

POLYETHYLENE PRODUCTION
TECHNOLOGIES

A. N. Bulkatov

Four methods of low-pressure polyethylene production, namely, suspension, solution, gas phase, and combined
(suspension + gas phase), with a single- or two-reactor technological scheme are examined. A molecular-mass
distribution curve is shown for various types of polyethylene. Catalysts and comonomers used are indicated,
and merits and demerits of the examined polyethylene production technologies are discussed.

Currently, four methods of low-pressure single- or two-reactor polyethylene production technologies are used in the
world. These methods are suspension, solution, gas phase, and combined (suspension + gas phase).
The properties of polyethylene of a particular type depend on the composition (assembly) of the high-molecular
macromolecules, each of which differs from the other in chain length and degree of short-chain branching.
The branching pattern depends only on the type of comonomer (propylene, butene-1, hexene-1, 4-methylpentene-1,
octene-1, etc.), and the mean statistical degree of branching depends essentially on the amount of comonomer fed into the
reactor and the selectivity of the catalyst used. The composition (assembly) of the macromolecules across the length (molec-
ular-mass distribution – MMD), on the other hand, is quite difficult to control and has serious limitations if a single-reactor
production scheme is used.
Synthesis of polymers in a single reactor, regardless of the catalyst type for all catalytic systems used in practice, is
characterized by Gaussian distribution curve, on which the acutely pointed high “hump” (peak) with short side branches cor-
responds to narrow MMD and the more oval hump with long side branches, to wide MMD (Fig. 1.).
Polyethylene with a narrow MMD is essentially molding types of polyethylene with a high level of technological,
physical, and mechanical properties. In general, it is produced on highly active Ziegler–Natta catalysts (titanium-magnesium).
For more demanding areas of application (pressure gas and water pipelines, large blown-out containers, fuel tanks, cable insu-
lation, and high-strength films), polyethylene with a wide MMD is required. In this regard, the single-reactor process has def-
inite limitations expressed in reduced degree of branching of higher-molecular fractions as compared to lower-molecular ones.
Two-reactor technology, on the other hand, makes it possible to increase the degree of branching of higher-molecular fractions
of polyethylene, which favorably influences the strength characteristics of the polymer, especially in operations under static
loads (pressure pipes, containers for storing corrosive and surface-active media, cable insulation, etc.).
The two-reactor (bimodal) suspension process CX of the Japanese firm Mitsui Chemicals is implemented in a
heavy solvent, namely, hexane. The type of the reactor is a vessel having a stirrer with a vapor-phase seal, where one type of
Ziegler–Natta catalyst based on titanium compounds and one type of comonomer, namely, butene-1, are used. For producing
several types of polyethylene, it is also possible to use propylene as the comonomer. The density range of the polymers pro-
duced is 0.935–0.970 g/cm3.
An advantage of the CX technology is much milder process conditions: temperature 75–85°C, pressure 0.3–0.9 MPa,
and time of contact with the catalyst 1.5–2 h.

Management Company − Strategic Assets (Upravlyayushchaya Kompaniya – Strategicheskie Aktivy), Moscow, Russia.
Translated from Khimicheskoe i Neftegazovoe Mashinostroenie, No. 8, pp. 10–12, August, 2008.

0009-2355/08/0708-0429 ©2008 Springer Science+Business Media, Inc. 429

 Fractional composition

Low molecular High molecular

mass mass

Molecular mass

Fig. 1. Typical MMD curves for polyethylene produced in a single reactor:

1) narrow MMD, low molecular mass (molding-type polyethylene); 2) wide
MMD, medium and high molecular mass (extrusion, including tube, extru-
sion-blowout, and cable types of polyethylene); and 3) very wide MMD,
large proportion of macromolecules with very high molecular mass.

Brief contact with the catalyst, good conditions for reaction mass homogenization in the reactor, and presence of one
type of catalyst and one type of comonomer ensure optimum conditions (time) for passage of one polyethylene type to another
(up to 4 h) with yield of minimum amount of nonstandard product.
Thanks to the advantages of the two-reactor scheme, the range of high-density polyethylene (HDPE) and medium-den-
sity polyethylene (MDPE) types can be considered as one of the best. This is confirmed by the presence in the type range of
high-density (0.962 g/cm3) blowout type of polyethylene with the highest resistance to cracking (more than 600 h).
A disadvantage of the CX process is use of heavy solvent, namely hexane, which necessitates installation of addi-
tional equipment: sedimentor-type centrifuge, drier, and solvent regeneration unit.
The two-reactor (bimodal) suspension process Hostalen of the German firm Basel is also implemented by using
the heavy solvent hexane.
The type of the reactor is an autoclave having a stirrer (like the one in the Mitsui Chemicals process) with a gas-phase
seal. Use is made of one type of catalyst (Ziegler–Natta) when it is introduced only into the first reactor and of one type of
comonomer (butene-1). In some cases (for molding-type polyethylene), propylene is used.
The process parameters are: temperature 78–85°C, pressure less than 1 MPa, catalyst contact time 1–3 h, and degree
of conversion in one cycle 99.5%, which makes recycle of the ethylene unnecessary.
Brief contact with the catalyst, good mass exchange conditions in the reactor, and presence of one type of catalyst
and one type of comonomer provide the optimum conditions for passage from one type to another (1–3 h). According to the
data of the firm, the density of the obtained product is 0.938–0.970 g/cm3.
The recommended HDPE and MDPE type range meets the highest demands of the current market.
Polyethylene pipes using Hostalen technology are made with a wide range of additives that corresponds to market
requirements. The recent development of the Hostalen process allows the polymer yield to be raised from 50 to 150 kg/g
of catalyst.
The major flaws of the Hostalen process, from the point of current market requirements, are the same as those of
the CX process. The limited polymer density range (0.938–0.970 g/cm3) precludes the possibility of linear low-density
polyethylene (LLDPE) production.
Use of heavy solvent (hexane) necessitates installation of additional equipment for its extraction.
Single-reactor suspension process of the US firm Chevron Phillips in a light solvent (isobutane). The loop-type
reactor operates in the circulation regime. Polymerization temperature 75–109°C, pressure 4.2 MPa, and comonomer used
hexene-1.

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 The density of the polymer obtained is 0.915–0.970 g/cm3. To produce various types of polyethylene, four types of
catalyst are used:
• chromium oxide – for pipe, blowout, and film types of high- and medium-density (0.935–0.964 g/cm3) polyethylene;
• titanium and chromium-titanium – for molding types of polyethylene, types for rotary molding, and film filaments
and monofilaments; and
• metallocene – for linear low-density polyethylene (LLDPE) and medium-density polyethylene (MDPE).
The geometric shape of the loop-type reactor of Chevron Phillips in the form of curved pipe of a considerable length
(with a cooling jacket), fitted with a pump placed in a liquid phase, provides favorable conditions for removal of reaction heat
and for mass exchange.
Brief contact of the catalyst (1 h) ensures quick passage from one polyethylene type to another for the suspension
processes within the range of one catalytic system (in 2 h). If the catalyst is replaced, the passage may take as much as 10 h.
The necessity for using several catalysts to ensure production of the whole range of polyethylene types is one of the
flaws of this process.
The two-reactor (bimodal) combined (suspension plus gas phase) process Borstar of the Belgian firm Borealis.
In the proposed technology, use has been made of the best engineering solutions of suspension and gas phase technologies.
In this process, Chevron Phillips reactor is used as the first reactor and gas phase reactor of a conventional design
as the second. The reactors operate in sequence.
The main merit of the original Borstar process is optimum synthesis conditions in each reactor in conjunction with
the use of a super-light solvent (propane).
The reactors operate in sequence: the first one under super-forced operation conditions at 6.5 MPa pressure and
65°C, and the second (gas phase) one, under normal conditions at 2.0 MPa pressure and 80–100°C. The catalyst is injected
into the first reactor in the form a prepolymer.
Operation of the first reactor under conditions not normal for the suspension process in this case makes it possible
to accelerate reaction and increase conversion in the first stage and, thanks to pressure drop upon feeding of the reaction mass
into the separator and further into the second (gas phase) reactor from 6.5 down to 2.0 MPa, to practically dispense with the
super-light solvent (propane) without additional equipment.
The Borstar process, unlike the CX and Holstalen technologies, eliminates three technological operations: cen-
trifuging (squeezing out from the solvent), drying of the polymer from the residual solvent, and regeneration of the solvent.
A demerit of the Borstar process is longer time of transition from one type to another (3–7 h) compared to dissolu-
tion (solvent) processes of DSM (Netherlands) and Chevron Phillips as well as of CX and Hostalen processes, but shorter
time relative to purely gas phase process (as much as 20 h).
The gas phase single reactor process of the British firm BP Amoco is one of the most advanced single-reactor
technologies implemented in the gas phase.
The demerits typical of single-reactor technology and, in particular, of the gas phase technology are maximally leveled
out because of the following features of the proposed process:
• use of two catalysts: highly active Ziegler catalyst for getting polymers with a narrow MMD and chromium catalyst
for getting polyethylene with a wide MMD;
• use of two comonomers (butene-1 and hexane-1);
• thorough cleaning of the gaseous products exiting the reactor from fine polymer particles and returning them to the
reactor, which prevents contamination of the product by polymer particles formed in the loop that may be the cause
of gel formation, which is particularly impermissible for the film types; and
• use of heat exchanger for cooling the gas mixture with condensation of the high-boiling products, followed by sep-
aration of the liquid in a gas-liquid separator.
The technology allows conversion of one polymer type into another with less loss in contrast to the gas phase pro-
cess used in Russia because this process can be implemented where the reactor operates at 40–50% of its capacity without
change in polymer properties. Under the most unfavorable transition conditions upon substitution of catalyst the amount of
the transition product may be about 100 tons.

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 The advances made by BP Amoco in the domain of modification of catalytic systems made it possible to offer the
widest type range of HDPE, MDPE, and LLDPE with a density range of 0.918–0.965 g/cm3.
The total number of types developed is about 150.
The single-reactor gas phase process Unipol developed by the US firm Univation is the simplest in apparatus
assembly and technology. It is implemented without solvents, residual catalyst washing-out systems, drying, and regenera-
tion. Thanks to its simplicity, ecological cleanness, and low cost, the process is in high demand in the global market.
In principle, this technology does not differ from the BP Amoco process because the latter is a modified version of
the previously developed Unipol technology. In number and properties the obtained polyethylene types fall somewhat short
of the product obtained by this technology, though the general level of physicomechanical and technological properties of
Unicol polyethylene is fairly high.
The type range includes PE (polyethylene)-80 class of pipe type, the type for high-strength films 10–15 µm in thick-
ness, cable, and molding types.
The single-reactor dissolution process of the Dutch firm DSM is implemented in the heavy solvent hexane.
The reactor type is a vessel having a stirrer, the catalyst is of the Ziegler type, and the monomers used are butene-1 and octene-1.
The process parameters are: 170–200°C, 9 MPa pressure, and catalyst contact time 10–12 min. The chief advantages
of the DSM process over those referred above are the shortest catalyst contact time, best conditions for reaction mass homog-
enization, the minimum time of transition from one type to another (0.5–1 h), and minimum reactor volume.
This process, thanks to the physical state of the polymerized mass (in the form of solution), has two basic differ-
ences from the other processes. On the one hand, the best conditions for functioning of the catalytic system, which allows
production of the highest quality of commercial film-type polyethylene with the minimum density of as low as 0.911 g/cm3,
on the other, it is impossible to produce high-molecular types of polymers because with increase of molecular mass the vis-
cosity of the solution rises steeply and the positive qualities of the technology are lost completely.
In this process, for getting the highest-quality polyethylene types, it is proposed to use a high-molecular comonomer
(octene-1), which has a high price in the global market.
The most significant demerit of this process is that it is impossible to produce high-quality pipe types of polyethylene
and cheap and strong film types with a high density of the polymer (0.946–0.952 g/cm3).
The Hostalen and CX two-reactor suspension processes in a heavy solvent provide the market with the following
types of polyethylene of the highest quality:
• pipe types for manufacture of high-pressure gas and water pipes, including PE-100;
• high-molecular film types based on HDPE for strong thin films 7–20 µm in thickness;
• types for extrusion-blowout molding, gasoline tanks, and high-strength large and small containers;
• extrusion types for pipeline insulation and cable types; and
• main types for rotary molding.
The Borstar two-reactor combined (suspension and gas phase) process provides the market with high-quality
polyethylene, whose range almost fully covers all pipe, film, blowout, and cable types as well as types for rotary molding and
gas pipeline insulation.
In spite of relatively recent use of the Borstar process, the product obtained by this process has a higher rating than
similar polymers produced by the other gas-phase method.
The Chevron Phillips single-reactor suspension process in a light solvent allows production of PE-80 and PE-100
pipe-type polyethylene. However, PE-100 polyethylene is produced only in two stages, followed by mixing of the two poly-
mers at the granulation stage, which is a technological flaw of this process. The main range of blowout, film, and molding
types of polyethylene as well as of polyethylene types for cable industry and rotary molding is a high-quality product.
The DSM single-reactor process virtually rules out production of HDPE of high-molecular pipe and film types.
Note that LLDPE of film types, including polyethylene with a super-low density (0.911 g/cm3) polyethylene, types
for rotary molding, molding types, including high-elasticity polyethylene, and types for pressure-free flexible pipes and hoses
manufactured by Basel are of high quality.

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