Optimized Ziegler-Natta Catalysts for

Bulk PP Processes

lyondellbasell.com
 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

I. Introduction
As the worlds largest producer of polypropylene (PP) and associated catalysts, LyondellBasell has
experience that dates back to the original discovery of the Ziegler-Natta polymerization of olefins.
Developed originally for the benchmark Spheripol process, and more recently extended to the
state-of-the-art Spherizone process, the companys Avant catalyst range is used to make all the
major product applications.
Polypropylene process technologies Changing the catalysts used in a PP
can be divided into three major plant requires careful consideration.
categories: bulk, gas-phase and This type of major change typically
slurry processes. The majority of the can only be justified if substantial
worlds PP production capacity utilizes benefits in product characteristics,
bulk processes, followed by gas- plant throughput and/or costs can
phase processes and slurry processes beachieved.
respectively, with the latter in the
This brochure provides information
process of becoming obsolete.
about the variety of catalysts that
Within the category of bulk processes, are tailored for use in bulk processes
an additional distinction can be made other than Spheripol, highlighting
between the type of polymerization aspects relevant to the operation of
reactor in use loop reactor(s) or PP plants and focusing on products
stirred tank reactor(s) (CSTRs). manufactured using different
catalysttypes.
In addition to world-class Spheripol
plants LyondellBasell has operated
through its predecessor companies
and joint ventures, a variety of other
bulk plants for several decades. All
of these plants use the companys
Avantcatalysts.

Topics
I. Introduction 2
II. LyondellBasell technology business 3
III. LyondellBasells bulk process experience 4
IV. LyondellBasells bulk process catalyst range 6
V. Case studies 13
VI. Summary 15

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

II. LyondellBasell Technology Business

Polyolefin technology licensing and catalyst manufacturing
are key elements of the LyondellBasell Technology business.

Licensed Polypropylene technologies

Spheripol Spherizone Metocene

Leading polypropylene Latest-generation polypropylene Innovative add-on technology
technology for the production technology, based on a for the production of specialty
of homopolymer, random and multizone reactor for the polypropylene products using
heterophasic copolymers production of polypropylene single-site catalyst systems
and novel polyolefins

Polypropylene catalyst portfolio

Avant ZN Avant M
Multi-purpose catalysts for Single-site catalysts for the
abroad range of demanding production of specialty
value applications polypropylene products

Licensed Polyethylene technologies

Lupotech Hostalen Spherilene

Leading high-pressure tubular Leading low-pressure slurry Advanced swing-gas-phase
and autoclave processes for the process for the production of process for the production of
production of LDPE and EVA high-end multimodal HDPE LLDPE, MDPE, monomodal
copolymers andbimodal HDPE

Polyethylene catalyst portfolio

Avant Z Avant C
Catalysts for leading multimodal Chromium catalysts for a broad
HDPE grades in slurry technologies. range of HDPE applications
Controlled morphology catalysts
for full range of LLD+MD+HD
products in gas-phase technology

The powerful combination of leading process technologies and cutting edge

catalysts, provides important synergies. LyondellBasell as a leading process
licensor and catalyst producer has an extensive understanding of the interaction
between catalysts and process technologies.

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

III.LyondellBasells PP
Bulk Technology Experience*
For decades, LyondellBasell has operated plants that
utilizea variety of PP bulk processes.

LyondellBasell operates three PP In addition, LyondellBasell has been

plants that utilize the LIPP process, supplying Avant ZN catalysts to third
which uses a CST reactor to produce -party bulk plants for decades.
homopolymer and random copolymer * Exclusive of Spheripol process capacity
grades. Through its joint ventures,
LyondellBasell also operates several
Hypol lines which use a combination
of CSTRs and gas-phase reactors, and
a Showa Denka loop plant with two
loop reactors. With a total capacity of
720 kt/a, the plants use LyondellBasells
Avant ZN catalysts.

LyondellBasells Experience in Bulk PP Processes

LIPP HYPOL**

** Operated under license agreement

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

In 2008, global PP production Of the bulk capacity, approximately two-thirds is produced using the Spheripol
process and about one-third using other bulk processes.
exceeded 52million tonnes.
Of this quantity, approximately General characteristics of bulk PP processes:
55% is produced using the
Bulk processes use very even polymerization conditions (temperature
Spheripol process and other within0.5 C) which translates into high product consistency.
bulk processes. Gas-phase
High catalyst yields are achieved due to very high monomer concentration.
processes account for 38%
of the total volume, while the Hydrogen concentration is limited by either design pressure (CSTR)
orsolubility(Loops).
remaining 7% is produced
using slurry processes. Maximum temperature in the reactor is limited by the design pressure.

Market breakdown by process technology 2008

2008 PP Market 2008 Bulk Market

Total 52.1 million tonnes Total 28.5 million tonnes

Bulk 55% Slurry 7% Gas Phase 38% Spheripol 66% Other Bulk 34%

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

IV.LyondellBasells Bulk Catalyst Range

Modern PP catalysts for bulk processes and the kinetic profile which is very to their operational and product
consist of a magnesium dichloride important for the operability of the property advantages.
(MgCl2) support, which is treated plant. The external donor influences
A large number of external donors
with a mixture of TiCl4 (Titanium these characteristics to a lesser extent
are used in combination with these
tetrachloride) and an internal donor and is primarily used to control the
catalysts. Whereas EB catalysts would
to yield the final catalyst. The physical xylene solubles (XS) of the products as
typically use PEEB (para-ethoxy
form of the catalyst can range well as to fine-tune product properties. ethylbenzoate) as a selectivity control
from amorphous flakes to highly There are four catalyst families for bulk agent, the other families typically use
spherical. Through the phenomenon processes in LyondellBasells portfolio, dialkyldimethoxysilanes as an external
of replication, the polymer product based on different internal donors: donor. A large variety of donors
formed in the reactor takes on the can be used; C, P and D donors are
basic form of the catalyst. Typically Third-generation ethylbenzoate (EB) included in the formulas shown below.
the catalyst is combined with an catalysts that were commercialized In addition, catalyst systems that use
aluminium alkyl for the activation in the early 1980s. mixtures of internal or external donors
of the active center and an external A catalyst family using phthalates as are used, which render the overall
donor for selectivity control, also the internal donor; these catalysts picture very complex.
known as the selectivity control represent the workhorse of the It is important to recognize that patent
agent(SCA). PPindustry. protection is in force for many of the
The internal donor is the single most More recently LyondellBasell has newer internal and external donors.
important factor that determines a commercialized fifth-generation
number of main characteristics such as diether and succinate catalysts that
activity, hydrogen response, selectivity are increasingly being used due

Basic Catalyst Components

Internal Donors Catalyst Types

o o o o o
R R
R R R
o R o o
R
R R
o R o o R
R
R
o
Benzoate Phthalate Diether Succinate

External Donors
COOC2H5

Si Si
Si
OC2H5 o o o o o o
PEEB CHMMS (C) DPDMS (P) DCPDMS (D)

Many internal/external donor combinations exist which affect reactor performance and product properties

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

Catalyst Kinetics Understandably, this has consequences up to 80 C. The relevance of this

for the relationship between characteristic is related to the extent to
The behavior of a catalyst in a bulk which a polymer particle is deactivated
reactor-residence time and effective
reactor is mainly determined by during processing steps downstream
catalystyield.
the internal donor that is used to of the reactor(s). High residual
make the catalyst. Both the relative Another very important aspect of the activity in these circumstances can
level of activity and the decrease of kinetics is the behavior at different lead to blockages in the downstream
the activity with time (the catalyst temperatures. As illustrated in the equipment, which makes catalyst
decay) are mainly determined by the graph on the right, the catalyst families types with lower activity at higher
internal donor. EB catalysts show differ considerably in this respect. In temperatures easier to run in aplant.
rapid decay after a high initial activity, the commercially relevant temperature
whereas phthalate, diether and range between 70 and 80 C, the
succinate catalysts exhibit a relatively activity of EB and diether catalysts
low rate of decay. This is shown in begins to diminish, dropping from
the graph on the left, representing 70 to 80 C, whereas the succinate
batch experiments with the different catalyst activity remains constant and
catalystfamilies. the phthalate catalyst activity increases

How does the catalyst behave in a reactor?

Benzoate Phthalate Diether Succinate

250 160

200
140
Relative Activity %

Relative Activity %

150
120
100

100
50

80
0 10 20 30 40 50 60 70 72 74 76 78 80
Time (minutes) Temperature (C)

A complete understanding of catalyst kinetic behaviour is key to ensuring good plant performance

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

How does LyondellBasell implement its catalysts in various technologies?

The answer lies in the companys Also kinetic investigations are done on The final step in the process is to
ability to rapidly scale up its catalyst bench-scale reactors. These determine conduct trials on a full commercial
developments. the catalyst decay and the behavior at scale to confirm the pilot results and
different temperatures. produce commercial quantities for
LyondellBasells fundamental catalyst
customer trials.
research, which includes new donors The next scale-up step typically is to
and supports, is conducted in its R&D run the catalyst in continuous bulk Only after this rigorous testing has
labs in Ferrara (Italy) and Frankfurt pilot plants, capable of producing taken place can new catalysts be
(Germany). several hundred kg/day. Here, industrialized in LyondellBasells
operational aspects such as reactor commercial lines.
The first stage of the companys
control can be tested; it also provides
catalyst testing investigates the
enough product to examine properties
basic properties of the catalysts
for thevariousapplications.
such as hydrogen response and
selectivity response. This is done
inbulkautoclaves.

Catalyst Scale-up

Autoclaves: Bulk pilot plant: Industrial plants:

Basic properties Product studies World scale production

LyondellBasell has been successful in scaling-up from lab to plant due to its in-house facilities.

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

LyondellBasell offers PP catalysts with four different internal Selectivity range

donors the well known benzoate and phthalate catalysts Selectivity refers to the external donors
as well asthe more advanced diether and succinate ability to influence the product, which
(fifthgeneration)catalysts. is normally controlled in the range
of 15% wt. The catalyst must be
highly selective with low external
Catalyst Yield Powder Bulk Density
donor concentration to exhibit a good
Operating conditions such as reactor The bulk density of the polymer balance between product versatility
temperature, hydrogen concentration produced is very important in and economics.
and residence time influence the bulk processes, because it has
catalyst yield. Poisons including a long consequences for the maximum Oligomer content
list of polar contaminants, notably throughput of the plant as well as for
The low molecular weight fraction of
oxygen and sulphur containing the economics of its operation. It is
the polymer is important, as these light
compounds, can negatively influence a complex function of internal donor
hydrocarbons are relatively volatile and
catalyst yield. characteristics, catalyst support design
can be emitted during final product
and operatingconditions.
processing in the form of die drool
Kinetic Behavior
andfuming.
Hydrogen Response
Both the decay characteristics of the
catalyst as well as its temperature Hydrogen is used to control the
dependence determine the behavior average molecular weight (expressed
in the reactor and in the downstream as MFR) of the polymer. The catalyst
section of theplant. must have a good hydrogen response
so that the full range of products can
be produced within the constraints of
the hardware.

LyondellBasells Bulk Catalyst Range

The internal donor in the catalyst influences:

Catalyst yield MW distribution Hydrogen response Microtacticity

Decay characteristics Selectivity range Oligomers content

o o o o R
o
R R
o R o R R
R o
R
o R o
R
o
R R
R
o
Benzoate Phthalate Diether Succinate

The Avant ZN catalyst range includes all these internal donors and uses highly spherical supports

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

Molecular weight distribution To operate an existing PP line reliably catalysts. If a higher final product MFR
and economically, the operator is required this is normally achieved
The width of the molecular weight
must work within the constraints by peroxide cracking during extrusion.
distribution (MWD) is normally
of the process to extend product Changes in the external donor can
expressed by the polydispersity index,
properties using different catalyst give a moderate increase in the MFR.
or PI. Different product applications
anddonorchoices. Diether catalysts can by virtue of their
require a different PI. Whereas fiber
high hydrogen response make at
applications in general require a Let us consider how product properties
least 100MFR products directly in the
narrow distribution with a PI less than can be influenced by these variables.
reactor without the use of peroxides,
3.5, a broader distribution is generally
With regard to MWD, the leading to a higher product quality.
favored for BOPP film with a PI of at
polydispersity index can only be
least 4.5. Finally the usefulness of the various
varied by approximately +/-0.1 in one
catalysts to produce random
reactor operation by changing the
Microtacticity copolymers can be mentioned.
reactor temperature or the external
Although in principle all of the catalyst
The microtacticity is a measure of the donor. However, to make significant
systems can be used to make random
stereo-regularity of the polymer chain. changes in the PI that the customer
copolymers, diether catalysts are
can detect, a change in catalyst is
It is measured by NMR and expressed preferred because of their superior
required. For instance, changing from
as the percentage of n-pentads. Note balance between the amount of
diether to succinate will increase the
that this is not equivalent to the XS. ethylene incorporated and the final
PI at least two points, which will result
XSof the product.
in a corresponding large increase
instiffness. In summary, major changes in product
properties can only be achieved by
Constraints in design pressure
changing catalysts, and fine-tuning can
frequently limit the maximum MFR that
be achieved by external donors and
can be obtained from a bulk reactor
plant conditions.
when using benzoate or phthalate

Degrees of freedom in an existing PP line

To extend product properties, the operator must work within the constraints of the process, external donor and catalyst.

Property Process External Donor Catalyst

Modify MWD (PI) 0.1* 0.2 1.5 Diether Succinate

Increase reactor MFR 1.2x 1.5x > 10x Diether

Major changes in product properties can only be achieved by selecting the correct catalyst
* Mono-modal reactor operation

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

As stated previously, there are many Phthalate catalysts produce broader At the broad end of the MWD
internal-external donor combination MWD than diether catalysts, and are scale are benzoate catalysts which
possibilities and thus the overall capable of making a wide range of are suitable for BOPP and general
catalyst picture is quite complex. In standard polypropylene grades. injection molding grades. Their
order to put this into perspective, the inability to produce high crystallinity
LyondellBasells new succinate catalysts
relationship between LyondellBasells homopolymers limits the product
produce even broader MWD. This
catalysts (used in one reactor window of this catalyst.
catalyst is capable of producing high
setup) and the major homopolymer
crystallinity, high stiffness odourless LyondellBasells catalyst range
applications is shown inthe
products. Until now, equivalent covers the complete spectrum of
graphbelow.
products were only possible with polypropyleneapplications.
Starting from the left hand side, cascaded reactortechnology.
LyondellBasells diether catalysts
produce very narrow MWD products.
These resins are ideal for such
applications as high speed, low denier
fibres or high clarity, thin wall injection
molding grades.

Avant ZN Catalyst Clustering Homopolymer

6.0 5th generation diether & succinate

catalysts extend the product
envelope achievable with older
Pipe BOPP Injection catalyst systems
Sheet Molding
Avant ZN catalysts cover a wide
5.0 range of PP applications

Minor product property changes

Polydispersity Index

are possible by fine-tuning the

BCF process & external donor
Raffia

4.0 Cast
Film

TWIM

3.0

Spun Bond Melt

Benzoate Diether Blown
Phthalate Succinate
2.0
0.1 1 10 100 1000

MFR

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

The graph below compares combined with the ability to make a in the reactor, efficient pneumatic
LyondellBasells catalyst families from wide product portfolio. transport and good degassing
aprocess operation point of view. behavior. For this reason the particle
The fifth-generation succinate catalysts
size must match the characteristics of
The third-generation benzoate catalyst, are easier to operate compared to the process.
although very easy to use due to its phthalate catalysts, and their broad
rapid decay and high temperature MWD combined with low xylene To preserve the morphological
deactivation, is rather limited in terms solubles is favored for high-stiffness integrity of the polymer particles,
applications. pre-polymerization (start of the
of selectivity and hydrogen response.
polymerization reaction under mild
The fourth-generation phthalate Apart form the internal donor conditions) can be applied. Some
catalysts are definitely more of a chemistry, another very important bulk processes are equipped with in-
challenge to operate in a bulk process, aspect that determines operability in line pre-polymerization facilities. For
bulk processes is the morphology of processes that are not equipped with
but the advantage is a wider product
the polymer particles, including particle such facilities, LyondellBasell offers a
portfolio.
shape, average particle size, particle range of pre-polymerized catalysts.
Fifth-generation diether catalysts offer size distribution and fines content. The
ease of operation and a high yield, particle size has to enable good mixing

How to choose the right Avant Catalyst?

Catalyst Yield

Raco C2 Incorporation Ease of Operation

Ethylbenzoate
Phthalate
Diether H2 Response
Succinate

The catalyst choice is a balance between PP market strategy and process capability

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

V. Case studies
The following information The first case study is an example The second case study deals with a
of an improvement in operational product upgrade in a line comprised
contains descriptions
aspects, with a loop reactor plant that of a bulk CSTR followed by a stirred
of two case studies used phthalate catalysts to produce gas phase reactor to produce a full
where bulk processes homopolymer and high ethylene range of products. The line used a
have been converted to content random copolymer. The phthalate catalyst; increasing demand
operation was hampered by reactor for high-performance products was
LyondellBasellcatalysts.
fouling issues which limited capacity the motivation for change. The
and occasionally caused the line to solution was an upgrade to fifth-
stop for cleaning. generation succinate catalysts in
combination with a patented external
Following an upgrade to a
donor. The result was a significant
LyondellBasell diether/external donor,
improvement in homopolymer and
plant operations were smooth and
impact copolymer properties at a
fouling was eliminated. Plant capacity
higher catalyst yield coupled with
increased significantly because of
excellent plant operability. Ultimately,
a better heat transfer coefficient.
better operability along with improved
Notwithstanding the lower residence
product properties at reduced costs
time, the catalyst yield increased
were achieved.
by 20%, resulting in a lower
productioncost.

Case Studies

Case study 1 Case study 2

Description Description
Bulk loop process using phthalate for CSTR with gas-phase reactor using
homopolymer and high ethylene raco. phthalates to produce the full
productrange
Motivation for change Motivation for change
Reactor fouling issues hampered Increasingly demanding market
operation
Value proposition Value proposition
Upgrade to LyondellBasell diether Upgrade to LyondellBasell succinate
catalyst/external donor combination catalyst/external donor combination
Result Result
Smooth operation without fouling Significant improvement in product
Significant capacity increase properties (impact/stiffness)
Catalyst yield increase Catalyst yield increase
Improved operability

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

Obviously, the benefits of changing to The deactivation of the catalysts that Other factors that may increase the
LyondellBasell bulk process catalysts takes place at higher temperatures is a maximum hourly throughput of the
depend on a number of factors positive aspect of the diether catalyst plant (notably the bulk density of the
including current product mix, plant compared to phthalate catalysts. This polymer) can be of great value because
configuration and the catalyst system characteristic will lead to significantly normally the extra throughput can be
currently in use. The table below gives less problems in downstream achieved without changing hardware.
an indication of the benefits that can equipment, avoiding downtime and
Finally the improved product quality
be expected in the conversion of a cleaning costs. The maintenance
can offer additional value. Although it
200kt bulk plant from phthalate to costs associated with downstream
could be difficult to extract this value
diether catalysts. equipment blockages can be estimated
from the market, an upgrade may be
at 200.000/yr. The gain in occupancy
The high yield of diether catalysts required just to stay in business in a
that is achieved by avoiding downtime
means that less catalyst and donor will competitive environment.
of the plant can be easily be valued at
be consumed, which reduces catalyst
approximately 900.000/yr
system costs. Typically this could be
a savings in the order of 500.000/ As stated previously, the incentive for a
yr. Higher hydrogen response leads catalyst change is highly dependent on
to hydrogen savings and peroxide the specific plant characteristics under
savings used for chemical cracking, consideration, such as bottlenecks and
since the higher melt index out of the business strategy.
reactor is attainable. This savings can
However, this typical example indicates
be estimated at between 200.000
that savings of around 1 million /yr
300.000.
are feasible in a plant of this size.

Indicative Benefit Breakdown

Scenario, conversion of a 200 kt/y bulk PP line from phthalate catalyst million /yr
to LyondellBasell fifthgeneration diether catalyst
Savings
Catalyst + donor 0.5(1)
H2 + peroxide 0.3
Maintenance/cleaning 0.2
Total 1.0
Further potential benefits
Increased production 0.9(2)
Product quality improvement premium?
(1)
Actual savings dependent on product mix, plant configuration and catalyst currently used.
(2)
Assuming no propylene constraint.

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 Optimized Ziegler-Natta Catalysts for Bulk PP Processes

VI. Summary
LyondellBasell has a long history of LyondellBasells commercially available
developing and implementing Ziegler- catalysts for bulk processes are drop-in,
Natta catalysts for PP processes. The and have been in use for many years
companys catalyst range is extensive in different commercial bulk plants
and addresses a variety of different around the world.
product applications.
Conversion to LyondellBasell
Our experience in a wide range of catalysts has demonstrated that
processes ensures that we can adapt process operability improvements,
catalyst characteristics to optimally fit product property enhancements
the requirements of each process. and conversion cost reductions can
beachieved.

15
About LyondellBasell

LyondellBasell Industries is one of the worlds largest

polymers, petrochemicals and fuels companies. We are
the global leader in polyolefins technology, production
and marketing; a pioneer in propylene oxide and
derivatives; and a significant producer of fuels and
refined products, including biofuels. Through research
and development, LyondellBasell develops innovative
materials and technologies that deliver exceptional
customer value and products that improve quality of
life for people around the world.

LyondellBasell Industries

Technology Business
Industriepark Hoechst
Building B852, 5th floor
65926 Frankfurt am Main
Germany

You can find out more about us by visiting

our website at: lyondellbasell.com/technology

Before using a LyondellBasell product, customers and other users

should make their own independent determination that the product
is suitable for the intended use. They should also ensure that they
can use the LyondellBasell product safely and legally. This document
does not constitute a warranty, express or implied, including a
warranty of merchantability or fitness for a particular purpose.
In addition, no immunity under LyondellBasells or third parties
intellectual property rights shall be implied from this document. No
one is authorized to make any warranties, issue any immunities or
assume any liabilities on behalf of LyondellBasell except in a writing
signed by an authorized LyondellBasell employee. Unless otherwise
agreed in writing, the exclusive remedy for all claims is replacement
of the product or refund of the purchase price at LyondellBasells
option, and in no event shall LyondellBasell be liable for special,
consequential, incidental, punitive or exemplary damages.

Avant, Spherizone, Spheripol, Hostalen, Spherilene, Lupotech,

Metocene, Glacido, Superflex, Prodflex,Isomplus and Vacido are
trademarks owned or used by LyondellBasell group companies.

Avant, Spherizone, Spheripol, Hostalen and Isomplus are registered

in the U.S. Patent and Trademark Office.

LB 09 124 e 1109