Siemens AG 2007

Process Analytics
in Polyethylene (PE) Plants

For the production of polyethylene

a variety of processes is in use
depending on what final products are
intended to be produced. However,
regardless of the process type, all
plants require process analytical
equipment to collect reliable and
accurate information for process control, product quality, plant safety and
environmental compliance.

Siemens, a leader in process analytical

instrumentation, has proven over
decades its capability to plan, engineer, manufacture, implement and
service analyzer systems for polyethylene plants worldwide.
This Case Study provides an over-view
of the processes typically used and
describes how Siemens with its analyzer and application know-how
meets best the process requirements.

Case Study

Polyethylene (PE) is a generic name

for a family of semicrystalline polymers. PE, as well as polypropylene
(PP), belong to the group of polyolefins, that are derived from a group
of base chemicals known as olefins.
Polyolefins are made by joining
together small molecules (monomers) to form long-chain molecules
(polymers) with thousands of individual links using a variety of catalysts.
The base monomer for PE is ethylene, which is a gas at room temperature, but when linked together as
polymers, it forms tough, flexible
plastic materials with a large variety
of applications. The linking of molecules is referred to as polymerization. There are various commercial
technologies used to manufacture
polyethylene. Each technology produces unique combinations of polymer characteristics.
Polyolefins (Polyethylene and
Polypropylene) are the worlds
mostly produced and fastest growing polymer family because
modern polyolefins cost less to
produce and process than other
plastics or conventional materials
polyolefins are available in many
varieties. They range from rigid
materials, which are used for car
parts, to soft materials such as
flexible fibres. Some are as clear
as glass; others are completely
opaque. Some, such as microwave food containers, have high
heat resistance while others melt
easily.

December 2007

Polyethylene

 Siemens AG 2007

Polyethylene production processes

Polyethylene

LLDPE

is made in a polymerization reaction by

building long molecular chains comprised of ethylene monomers, mostly
by using catalysts. The type and nature
of the catalysts are of great influence on
the polymerization. As catalysts became
more efficient, the polyethylene products became purer and more versatile
and the production process became
simplier and more efficient.
Polyethylene (PE) is a family of resins
made from the polymerization of ethylene gas. It is produced either in radical
polymerization reactions or in catalytic
polymerization reactions. Most PE
molecules contain branches in their
chains which are formed spontaneously
in case of radical polymerization or
deliberately by copolymerization of
ethylene with olefins in case of
catalytic polymerization.
PE resins are classified according to
their density which partly depends on
the type of branching.
HDPE
High Density PolyEthylene has almost
no branching and thus has stronger
intermolecular forces. It is produced
mainly in slurry and gas-phase polymerization processes. HDPE is a white
opaque solid.
MDPE
Medium Density PolyEthylene has a
high degree of resistance to chemicals and is very easy to keep clean.
LDPE
Low-Density PolyEthylene has random long branching, with branches
on branches. It is produced mainly in
high-pressure poymerization processes. LDPE is a translucent solid.

Feedstock
(Options)
Ethylene
Propylene
Comonomer
Solvent
Nitrogen
Oxygen

Feed Purification
Gas Compression

Catalyst Preparation

Linear Low-Density PolyEthylene is a

substantially linear polymer, with significant numbers of short branches,
produced mainly by copolymerization
of ethylene with longer-chain olefins.
LLDPE is a translucent solid.

Production Processes
A large number of production processes
exist for PE with some general similarities. But the processes are evolving continuously. So the specifics can be significantly different and the following
descriptions and graphic displays
should be, therefore, considered exemplarily only with no direct relation to
existing plant or process designs.
Generic polymerization process
Similarities between the processes
follow a generic olefin polymerization
process scheme as shown in Fig. 1
(from left):
Feedstock materials and additives
must be purified and catalyst material
must be prepared. And - in case of a
high pressure process - the gas must
be compressed in several stages.
Polymerization takes place either in
the gas phase (fluidized bed or
stirred reactor), the liquid phase
(slurry or solution), or in a high pressure environment. Polymerization is
the heart of the processes. On any
one unit, only one of the three processes is used. More details will be
explained on the next pages.
Polymer particles are then separated
from still existing monomers and diluents, pelletized, dried and dispatched.
Monomers and diluents are recovered
and fed again to the process.

In gas-phase polymerization (Fig. 2,

left) the ethylene is contacted with solid
catalyst material intimately dispersed in
an agitated bed of dry polymer powder.
Two different methods are used to carry
out this reaction
In the fluidized-bed process the
monomer flows through a perforated
distribution plate at the reactor bottom and rapid gas circulation ensures
fluidization and heat removal. Unreacted polymer is separated from the
polymer particles at the top of the
reactor and recycled. Fluidized-bed
plants are able to produce either
LLDPE or HDPE and are free of constraints from viscosity (solution process) or solubility (slurry process).
A modification uses a second reactor
connected in series to perform copolymerization.
The stirred-bed process uses a horizontal or vertical reactor with compartments, in which the bed of
polymer particles is agitated by mixing blades.
The gas-phase polymerization technology is economical and flexible and can
accomodate a large variety of catalysts.
It is by far the most common process in
modern ethylene production plants.
Some processes are listed in Table 1.

Gas-phase
Process
Liquid-phase
Process
High pressure
Process

Fig. 1: Generic Polyethylene (olefin) polymerization process, simplified

Gas-Phase Polymerization

Separation

Drying

Recovery

Pelletizing

 Siemens AG 2007

Primary gas-phase reactor Copolymer gas-phase reactor

Recycle

Recycle

Gas phase reactor

Loop reactor

Catalyst

Ethylene

Dispatch

HP
separator

Primary
compressor

Initiator

Monomer Hydrogen

Comonomer Hydrogen

Secondary
compressor

Vinyl acetate

Catalyst

LP
separator

Extruder

Tubular reactor

Flash
dryer

Product

Diluent

Ethylene
Hydrogen
Comonomer

Fig. 2: PE production principles: gas-phase, high-pressure, liquid-phase (from left)

Liquid-Phase
Polymerization
In liquid-phase processes (slurry or suspension, Fig. 2, right) catalyst and polymer particles are suspended in an inert
solvent, typically a light or heavy hydrocarbon. Super-critical slurry polymerization processes use supercritical propane
as diluent.
Slurry processes run in loop reactors
with the solvent circulating, stirred tank
reactors with a high boiling solvent or a
liquid pool in which polymerization
takes place in a boiling light solvent.
A variety of catalysts can be used in
these processes. Processes in solution
require, as their last step, the stripping
of the solvent.
Supercritical polymerization in the
slurry loop provides advantages (e.g.
higher productivity, improved product
properties) over subcritical polymerization.
Advanced processes combine a loop
reactor with one or two gase-phase
reactors, placed in series, where the
second stage of the reaction takes place
in the gas-phase reactors. For bimodal
polymers, lower molecular weights are
formed in the loop reactor, while high
molecular weights are formed in the
gas-phase reactor.
Some processes are listed in Table 1.

High Pressure Processes

In high pressure processes (Fig. 2, center) autoclave or tubular reactors (pressure in excess of 3,000 bar) are used,
but the processes are similar, comprising compression, polymerization, pelletizing, and dispatch as major steps.
Fresh ethylene enters the reactor and is
mixed with the low pressure recycle.
After further compression the mixture
enters the reactor for polymerization.
Oxygen or peroxide may be used as initiators.
A tubular reactor typically consists of
several hundred meters of jacketed
high-pressure tubing arranged as a
series of straight sections connected
by 180 bends.

High pressure processes can produce

LLDPE homopolymers and vinylacetate
copoymers in addition to the normal
range of LDPEs.
Some processes are listed in Table 1.

Gas-phase processes
Lupotech G

A fluidized-bed process for manufacturing of HDPE, MDPE, and LLDPE

Unipol PE

A fluidized-bed process for manufacturing of HDPE and LLDPE

Liquid-phase processes
Hostalen

A low-pressure slurry process for manufacturing of bimodal HDPE

Borstar PE

A supercritical slurry process, which combines a loop reactor and a gasphase reactor

Phillips

A slurry process for manufacturing of HDPE

High pressure processes (selected)

Lupotech T

High-pressure process for manufacturing of broad range LDPE

ExxonMobil

High-pressure tubular process for LDPE

Equistar

High-pressure tubular and autoclave processes for LDPE

Table 1: Common PE production processes

 Siemens AG 2007

Use of process analyzers

Analyzer Tasks

Analyzers and sampling points

Different analyzers are used in ethylene
plants ranging from simple sensor type
monitors to high technology process
gas chromatographs.
The list typically includes
Process gas chromatographs
Continuous gas analyzers
(paramagnetic oxygen analyzers,
NDIR analyzers, total hydrocarbon
content analyzers)
Analyzers for moisture and O2 traces
Low Explosion Level (LEL) analyzers

Process analytical equipment is an indispensable part of any ethylene plant

because it provides the control system
and the operator with key data from the
process and its environment.
Four major applications
Analyzer applications can be divided in
four groups depending on how the analyzer data are used:
Closed-loop control for process
and product optimization
This application helps to increase
yield, reduce energy consumption,
achieve smooth operation, and keep
product quality accoding to the specification
Quality control and documentation
for ISO compliance
Plant monitoring and alarms
This application protects personnel
and plant from possible hazard from
toxic or explosive substances
Emission control
This application helps to keep emission levels in compliance with local
regulations.

Analyzer installation
Analyzers are installed partially in the
field close to the sampling location
and/or in an analyzer house (shelter).
In modern plants most of the analyzers
are interfaced to a plant wide data communication system for direct data transfer from and to the analyzers.

Sampling point
Sampling stream
1 Ethylene
purification

2
Gas-phase
fluidized bed reactor

Catalyst hopper
7

Plant area

Nitrogen
purification

Ethylene
purification

Comonomer
purification

Product
granules

Fig. 3: Typical sampling points of a fluidized-bed HDPE plant

Comonomer
purification
Nitrogen
purification
Catalyst feed
Cycle gas

The total number of analyzers installed

in a plant varies from plant to plant
depending on the type of process, individual plant conditions and user
requirements.
An example of typical sampling locations, analyzers, and measuring components and ranges is given in Fig. 3 for a
HDPE plant using a gas-phase fluidized
bed reactor:
Feed of monomer, comonomers,
catalyst, and additives to the reactor
(1-4)
Cycle gas line (5)
Product line or feed to a second reactor (6)
Safety measurements at different
locations of the plant (7)

Component
CO
CO2
Methanol
Acetylene
Total S
Ethane
Moisture
O2
Moisture

Moisture
O2
4
O2
5
Nitrogen
Hydrogen
CO
Methane
Ethane
Ethylene
N-Butane
ISO-Butan
1-Butene
Trans-2-Butene
ISO-Butene
CIS-2-Butene
Hexane
1-Hexene
C6 inerts
6 Product
Moisture
7 Plant area
Various
TPA: Third party analyzer

Meas. Range
[ppm]
0 ... 2
0 ... 2
0 ... 10
0 ... 5
0 ... 2
0 ... 400
0 ... 5
0 ... 2
0 ... 100

Suitable Analyzer

0 ... 10
0 ... 10
0 ... 10 %
0 ... 100%
0 ... 50%
0 ... 10 ppm
0 ... 10%
0 ... 20%
0 ... 100%
0 ... 5%
0 ... 5%
0 ... 25%
0 ... 1%
0 ... 5%
0 ... 2%
0 ... 10%
0 ... 20%
0 ... 10%
0 ... 5

TPA
OXYMAT 6
OXYMAT 6
MAXUM or MicroSAM
CALOMAT 6
ULTRAMAT 6
ULTRAMAT 6
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
MAXUM or MicroSAM
TPA

MAXUM
MAXUM
MAXUM
MAXUM
MAXUM
MAXUM
TPA
OXYMAT 6
TPA

Table 2: Typical measuring components and ranges acc. to Fig. 3

 Siemens AG 2007

Siemens Process Analytics at a glance

Products

Siemens Process Analytics

Siemens Process Analytics is a leading
provider of process analyzers and process analysis systems. We offer our global customers the best solutions for
their applications based on innovative
analysis technologies, customized system engineering, sound knowledge of
customer applications and professional
support. And with Totally Integrated
Automation (TIA). Siemens Process
Analytics is your qualified partner for
efficient solutions that integrate process analysers into automations systems in the process industry.
From demanding analysis tasks in the
chemical, oil & gas and petrochemical
industry to combustion control in
power plants to emission monitoring at
waste incineration plants, the highly
accurate and reliable Siemens gas chromatographs and continuous analysers
will always do the job.
Siemens process Analytics offers a wide
and innovative portfolio designed to
meet all user requirements for comprehensive products and solutions.

Our Products
The product line of Siemens Process
Analytics comprises extractive and insitu continuous gas analyzers (fig. 4 to
7), process gas chromatographs (fig.8
to 11), sampling systems and auxiliary
equipment. Analyzers and chromatographs are available in different versions for rack or field mounting, explosion protection, corrosion resistant etc.
A flexible networking concept allows
interfacing to DCS and maintenance
stations via 4 to 20 mA, PROFIBUS,
Modbus, OPC or industrial ethernet.

Extractive Continuous Gas Analyzers (CGA)

ULTRAMAT 23
The ULTRAMAT 23 is a cost-effective multicomponent analyser for the
measurement of up to 3 infrared sensitive gases (NDIR principle) plus
oxygen (electrochemical cell). The ULTRAMAT 23 is suitable for a wide
range of standard applications. Calibration using ambient air eliminates
the need of expensive calibration gases.
CALOMAT 6/62
The CALOMAT 6 uses the thermal conductivity detection (TCD) method
to measure the concentration of certain process gases, preferably hydrogen.The CALOMAT 62 applies the TCD method as well and is specially
designed for use in application with corrosive gases such as chlorine.
OXYMAT 6/61/64 The OXYMAT 6 uses the paramagnetic measuring method and can be
used in applications for process control, emission monitoring and quality
assurance. Due to its ultrafast response, the OXYMAT 6 is perfect for
monitoring safety-relevant plants. The corrosion-proof design allows
analysis in the presence of highly corrosive gases.
The OXYMAT 61 is a low-cost oxygen analyser for standard applications.
The OXYMAT 64 is a gas analyzer based on ZrO2 technology to measure
smallest oxygen concentrations in pure gas applications.
ULTRAMAT 6
The ULTRAMAT 6 uses the NDIR measuring principle and can be used in
all applications from emission monitoring to process control even in the
presence of highly corrosive gases.
ULTRAMAT 6 is able to measure up to 4 infrared sensitive components in
a single unit.
ULTRAMAT 6 /
Both analyzer benches can be combined in one housing to form a multiOXYMAT 6
component device for measuring up to two IR components and oxygen.
FIDAMAT 6

The FIDAMAT 6 measures the total hydrocarbon content in air or even in

high-boiling gas mixtures. It covers nearly all requirements, from trace
hydrocarbon detection in pure gases to measurement of high hydrocarbon concentrations, even in the presence of corrosive gases.
In-situ Continuous Gas Analyzer (CGA)
LDS 6
LDS 6 is a high-performance in-situ process gas analyser. The measurement (through the sensor) occurs directly in the process stream,
no extractive sample line is required. The central unit is separated from
the sensor by using fiber optics. Measurements are carried out in realtime. This enables a pro-active control of dynamic processes and allows
fast, cost-saving corrections.
Fig. 5: Product scope Siemens Continuous Gas Analyzers

Fig. 4: Series 6 gas analyzer (rack design)

Fig. 6: Series 6 gas analyzer (field design)

Fig. 7: LDS 6 in-situ laser gas analyzer

 Siemens AG 2007

Siemens Process Analytics at a glance

Products (continued) and Solutions

Fig. 8: MAXUM edition II Process GC

Process Gas Chromatographs (Process GC)

MAXUM edition II MAXUM edition II is very well suited to be used in rough industrial environments and performs a wide range of duties in the chemical and petrochemical industries and refineries.
MAXUM II features e. g. a flexible, energy saving single or dual oven concept, valveless sampling and column switching, and parallel chromatography using multiple single trains as well as a wide range of detectors
such as TCD, FID, FPD, PDHID, PDECD and PDPID.
MicroSAM
MicroSAM is a very compact explosion-proof micro process chromatograph. Using silicon-based micromechanical components it combines
miniaturization with increased performance at the same time.
MicroSAM is easy to use and its rugged and small design allows mounting right at the sampling point. MicroSAM features drastically reduced
cycle times, provides valveless sample injection and column switching
and saves installation, maintenance, and service costs.
SITRANS CV
SITRANS CV is a micro process gas chromatograph especially designed
for reliable, exact and fast analysis of natural gas. The rugged and compact design makes SITRANS CV suitable for extreme areas of use, e.g. offshore exploration or direct mounting on a pipeline.
The special software "CV Control" meets the requirements of the natural
gas market, e.g. custody transfer.
Fig. 11: Product scope Siemens Process Gas Chromatographs

Our solutions
Fig. 9: MicroSAM Process GC

Analytical solutions are always driven

by the customers requirements. We
offer an integrated design covering all
steps from sampling point and sample
preparation up to complete analyser
cabinets or for installation in analyser
shelters (fig. 12). This includes also signal processing and communications to
the control room and process control
system.

Fig. 10: SITRANS CV Natural Gas Analyzer

Fig. 12: Analyzer house (shelter)

We rely on many years of world-wide

experience in process automation and
engineering and a collection of specialized knowledge in key industries and
industrial sectors. We provide Siemens
quality from a single source with a function warranty for the entire system.
Read more in "Our Services.

 Siemens AG 2007

Siemens Process Analytics at a glance

Solutions (continued) and Services

Our solutions ...

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Analyzer networking for

data communication
Engineering and manufacturing of process analytical solutions increasingly
comprises "networking". It is getting a
standard requirement in the process
industry to connect analyzers and
analyzer systems to a communication
network to provide for continuous and
direct data transfer from and to the
analysers.
The two objectives are (fig. 14):
To integrate the analyzer and
analyzer systems seamless into the
PCS / DCS system of the plant
and
To allow direct access to the analyzers
or systems from a maintenance
station to ensure correct and reliable
operation including preventive or
predictive maintenance (fig.13).
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Siemens Process Analytics provides networking solutions to meet the demands

of both objectives.

Our Services
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Fig. 13: Communication technologies

Siemens Process Analytics is your competent and reliable partner world wide
for Service, Support and Consulting.
Our rescources for that are
Expertise
As a manufacturer of a broad variety
of analyzers, we are very much experienced in engineering and manufacturing of analytical systems and
analyzer houses.
We are familiar with communication
networks, well trained in service and
maintenance and familiar with many
industrial pro cesses and industries.
Thus, Siemens Process Analytics owns
a unique blend of overall analytical
expertise and experience.

Global presence

With our strategically located centers

of competence in Germany, USA,
Singapore, Dubai and Shanghai, we
are globally present and acquainted
with all respective local and regional
requirements, codes and standards.
All centers are networked together.

Fig. 15: Portfolio of services

 Siemens AG 2007

Siemens Process Analytics at a glance

Services, continued

Our Services ...

Service portfolio
Our wide portfolio of services is segmented into Consulting, Support and
Service (fig. 15 to 16). It comprises
really all measures, actions and advises
that may be required by our clients
throughout the entire lifecycle of their
plant. It ranges from site survey to
installation check, from instruction of
plant personnel to spare part stock management and from FEED for Process
Analytics (see below) to internet-based
service Hotline.
Our service and support portfolio
(including third-party equipment) comprises for example:
Installation check
Functionality tests
Site acceptance test
Instruction of plant personnel on site
Preventive maintenance
On site repair
Remote fault clearance
Spare part stock evaluation
Spare part management
Professional training center
Process optimisation
Internet-based hotline
FEED for Process Analytics
Technical consullting
FEED for Process Analytics
Front End Engineering and Design
(FEED) is part of the planning and engineering phase of a plant construction or
modification project and is done after
conceptual business planning and prior
to detail design. During the FEED phase,
best opportunities exist for costs and
time savings for the project, as during
this phase most of the entire costs are
defined and changes have least impact
to the project. Siemens Process Analytics holds a unique blend of expertise in
analytical technologies, applications
and in providing complete analytical
solutions to many industries.

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Fig. 16: Portfolio of services provided by Siemens Process Analytics

Based on its expertise in analytical technology, application and engineering ,

Siemens Process Analytics offer a wide
scope of FEED services focused on analysing principles, sampling technologies,
application solutions as well as communication system and given standards (all
related to analytics) to support our clients in maximizing performance and
efficiency of their projects.
Whether you are plant operators or
belong to an EPC Contractor you will
benefit in various ways from FEED for
Process Analytics by Siemens:
Analytics and industry know how
available, right from the beginning
of the project
Superior analyzer system performance with high availability
Established studies, that lead to
realistic investment decisions
Fast and clear design of the analyzer
system specifications, drawings and
documentation
Little project management and
coordination effort, due to one
responsible contact person and
less time involvement

Additional expertise on demand,

without having the costs, the effort

and the risks of building up the capacities
Lowest possible Total Costs of Ownership (TCO) along the lifecycle regarding investment costs, consumptions,
utilities supply and maintenance.

 Siemens AG 2007

Case Study
Siemens Process Analytics - Answers for industry

If you have any questions, please contact your local sales representative or any of the contact addresses below:
Siemens AG
A&D SC PA, Process Analytics
stliche Rheinbrckenstr. 50
76187 Karlsruhe
Germany

Siemens Energy & Automation Inc.

7101 Hollister Road
Houston, TX 77040
USA

Siemens Pte. Limited

A&D SC PS/PA CoC
60 MacPherson Road
Singapore 348615

Phone: +49 721 595 3829

Fax: +49 721 595 6375
E-mail:

Phone: +1 713 939 7400

Fax: +1 713 939 9050
E-mail: [email protected]

Phone: +65 6490 8728

Fax: +65 6490 8729
E-mail: [email protected]

www.siemens.com/prozessanalytics

www.siemens.com/processanalytics

www.siemens.com/processanalytics

Siemens Ltd., China

A&D SC, Process Analytics
7F, China Marine Tower
No.1 Pu Dong Avenue
Shanghai, 200120
P.R.China

Siemens LLC
A&D 2B.
PO Box 2154,
Dubai, U.A.E.

Phone: +86 21 3889 3602

Fax: +86 21 3889 3264
E-mail: [email protected]
www.ad.siemens.com.cn

Phone: +971 4 366 0159

Fax: +971 4 3660019
E-mail: [email protected]
www.siemens.com/processanalytics

Siemens AG

www.siemens.com/processanalytics

[email protected]

Automation and Drives

Sensors and Communication
Process Analytics
76181 KARLSRUHE
GERMANY

Siemens AG 2007
Subject to change