The Catalyst Review June 2020 - 8

SPECIAL FEATURE
*	

Brand owners and consumers are more concerned with the aesthetics, the goods durability, health and sustainability/safety
issues and the environmental impact.

Catalysts can be assembled to address the commodity markets and/or differentiated spaces. Among the catalysts system
components, the internal donor captures much of the attention of research groups in academia and industry. It is certainly a key
element of the ZN technology, but other elements (activators, external donors and supports) are also critical to providing the desired
performance (Rego 2017).
The author has recently written some articles titled "Polymerization Catalysts: Technology Advances and Market" (Ali, 2019) and
"Polyolefin Catalyst Technology Overview" (Ali, 2015). These articles analyzed the polymerization catalyst technology and market. In
this article the author, focuses his analysis particularly on the catalyst system components (activators, stereoregulators and supports)
and their influence on on product/process performances. Find in section 2 the main features, role and contribution of activators,
stereo-regulators and supports to the recent technology advances of most used coordination catalyst technologies as ZN, chromium
oxide, and SSC (metallocene and post-metallocene catalysts). Find in section 3 a review of the catalyst components market dynamics
and major suppliers.
Catalyst System Components Technology Advances/Cycles
The catalysts currently used for polyolefin production can be classified according to the type of polymer they produce (PP, HDPE,
LLDPE), the basis catalyst family (ZN, chromium oxide or SSC/metallocene), the polymerization process/reactor type where they are
used (slurry, bulk, solution or gas phase, fluidized bed/loop/agitated vessel reactor). The precise compositions and characteristics
of the hundreds of catalyst grades currently in commercial use to produce the above resins are not available in the public domain;
in the following, some exemplary supported catalyst compositions related to certain widely used process technology are reviewed
on the basis of public technical literature/patent. See in Table 1 a summary of such technologies and typical catalyst productivity
related to polyolefins. See also in Table 2 the major licensed PE/PP process technology, their main features (type and number of
polymerization reactors) and licensors.
Table 1: Exemplary polyolefins using supported catalyst technologies.
ZN PP catalysts supported mainly
on magnesium chloride (MgCl2)
are used for the production of PP
homopolymers, random and impact
copolymers using the commercial bulk
and gas phase process technologies.
Really, these technologies produce PP
homopolymers and random copolymers
in a first stage that could use both bulk
loop (BL) or gas phase fluidized bed
Source: Ali 2015
reactors (GP) and impact copolymers
in a second stage for the
Table 2: Major PE/PP licensed process technology.
copolymerization of ethylene
that is always GP. In particular,
Novolen and Innovene PP
process technologies utilize
respectively gas phase vertical
or horizontal stirred reactors.
While there are many routes
to the production of these
supported catalysts, most
Source: Author
of these catalysts are based
upon the preparation of a
magnesium chloride ethanolate (MgCl2:EtOH) support and the deposition of titanium tetrachloride (TiCl4) on the high surface area of
the MgCl2 support. A carefully selected Lewis bases as di-iso butyl-phthalate (DIBP) internal donor, is added to the catalyst system to
improve conveniently the catalyst stereo-specificity. During the polymerization an aluminum alkyl activator, usually triethyl aluminum
(TEAL), and an external donor (e.g. silanes) are added.
Ziegler PE silica supported catalysts are used for the production of about 40% of global capacity of linear PE (HD/MDPE, LLDPE, and
other PE-based copolymers) with a reduced hexane extractable content in GP process (e.g., Unipol PE single GP reactor licensed
by Univation). According to a patent assigned to Union Carbide (Jorgensen Patent, 1994), the basic catalyst used in this process is
8

The Catalyst Review											

June 2020



The Catalyst Review June 2020

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The Catalyst Review June 2020 - cover
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