Case Study

Process Analytics in Polyethylene (PE) Plants

Chemical Industry

For the production of polyethylene a variety of processes is Polyolefins are made by joining together small molecules
in use depending on what final products are intended to be (monomers) to form long-chain molecules (polymers) with
produced. However, regardless of the process type, all thousands of individual links using a variety of catalysts.
plants require process analytical equipment to collect
reliable and accurate information for process control, The base monomer for PE is ethylene, which is a gas at
product quality, plant safety and environmental compliance. room temperature, but when linked together as polymers,
it forms tough, flexible plastic materials with a large variety
Siemens, a leader in process analytical instrumentation, has of applications. The linking of molecules is referred to as
proven over decades its capability to plan, engineer, polymerization. There are various commercial technologies
manufacture, implement and service analyzer systems for used to manufacture polyethylene. Each technology
polyethylene plants worldwide. produces unique combinations of polymer characteristics.

This Case Study provides an overview of the processes Polyolefins (Polyethylene and Polypropylene) are the world‘s
typically used and describes how Siemens with its analyzer mostly produced and fastest growing polymer family
and application know-how meets best the process because
requirements. • Modern polyolefins cost less to produce and process than
other plastics or conventional materials
Polyethylene • Polyolefins are available in many varieties. They range
from rigid materials, which are used for car parts, to soft
Polyethylene (PE) is a generic name for a family of materials such as flexible fibres. Some are as clear as glass;
semicrystalline polymers. PE, as well as polypropylene others are completely opaque. Some, such as microwave
(PP), belong to the group of polyolefins, that are derived food containers, have high heat resistance while others
from a group of base chemicals known as olefins. melt easily.

usa.siemens.com/analyticalproducts
Polyethylene production processes
Polyethylene high-pressure poymerization processes. • Monomers and diluents are recovered
LDPE is a translucent solid. and fed again to the process.
Polyethylene is made in a polymerization • LLDPE
reaction by building long molecular chains Linear Low-Density PolyEthylene is a Gas-Phase Polymerization
comprised of ethylene monomers, mostly substantially linear polymer, with
by using catalysts. The type and nature significant numbers of short branches, In gas-phase polymerization (Fig. 2,
of the catalysts are of great influence on produced mainly by copolymerization left) the ethylene is contacted with solid
the polymerization. As catalysts became of ethylene with longer-chain olefins. catalyst material intimately dispersed in
more efficient, the polyethylene products LLDPE is a translucent solid. an agitated bed of dry polymer powder.
became purer and more versatile and the Two different methods are used to carry
production process became simplier and Production Processes out this reaction
more efficient.
A large number of production processes • In the fluidized-bed process the
Polyethylene (PE) is a family of resins exist for PE with some general similarities. monomer flows through a perforated
made from the polymerization of ethylene But the processes are evolving continuously. distribution plate at the reactor bottom
gas. It is produced either in radical So the specifics can be significantly different and rapid gas circulation ensures
polymerization reactions or in catalytic and the following descriptions and graphic fluidization and heat removal. Unreacted
polymerization reactions. Most PE displays should be, therefore, considered polymer is separated from the polymer
molecules contain "branches" in their exemplarily only with no direct relation to particles at the top of the reactor and
chains which are formed spontaneously existing plant or process designs. recycled. Fluidized-bed plants are able to
in case of radical polymerization or produce either LLDPE or HDPE and are
deliberately by copolymerization of Generic polymerization process free of constraints from viscosity
ethylene with α−olefins in case of Similarities between the processes (solution process) or solubility (slurry
catalytic polymerization. follow a generic olefin polymerization process). A modification uses a second
process scheme as shown in Fig. 1 reactor connected in series to perform
PE resins are classified according to their (from left): copolymerization.
density which partly depends on the type of • Feedstock materials and additives must • The stirred-bed process uses a horizontal
branching. be purified and catalyst material must be or vertical reactor with compartments,
• HDPE prepared. And - in case of a high pressure in which the bed of polymer particles is
High Density PolyEthylene has almost process - the gas must be compressed in agitated by mixing blades.
no branching and thus has stronger several stages.
intermolecular forces. It is produced • Polymerization takes place either in the The gas-phase polymerization technology
mainly in slurry and gas-phase gas phase (fluidized bed or stirred is economical and flexible and can
polymerization processes. HDPE is a reactor), the liquid phase (slurry or accomodate a large variety of catalysts.
white opaque solid. solution), or in a high pressure It is by far the most common process in
• MDPE environment. Polymerization is the heart modern ethylene production plants.
Medium Density PolyEthylene has a of the processes. On any one unit, only Some processes are listed in Table 1.
high degree of resistance to chemicals one of the three processes is used. More
and is very easy to keep clean. details will be explained on the next
• LDPE pages.
Low-Density PolyEthylene has random • Polymer particles are then separated
long branching, with branches on from still existing monomers and
branches. It is produced mainly in diluents, pelletized, dried and dispatched.

Feedstock Gas-phase
(Options) Process
Feed Purification
Ethylene Separation Drying
Propylene Liquid-phase
Gas Compression
Comonomer Process Recovery Pelletizing
Solvent
Nitrogen Catalyst Preparation High pressure
Oxygen Process

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

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 Primary gas-phase reactor Copolymer gas-phase reactor Recycle Recycle Gas phase reactor

Loop reactor

Catalyst Flash
Ethylene LP Catalyst dryer
HP
Separator Separator
Primary
Dispatch Compressor
Secondary Product
Compressor Extruder Diluent
Initiator

Ethylene
Vinyl Acetate Tubular Reactor Hydrogen
Monomer Hydrogen Comonomer Hydrogen Comonomer

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

Liquid-Phase Polymerization High Pressure Processes A tubular reactor typically consists of

several hundred meters of jacketed high-
In liquid-phase processes (slurry or In high pressure processes (Fig. 2, center) pressure tubing arranged as a series of
suspension, Fig. 2, right) catalyst and autoclave or tubular reactors (pressure in straight sections connected by 180°
polymer particles are suspended in an inert excess of 3,000 bar) are used, but the bends.
solvent, typically a light or heavy processes are similar, comprising
hydrocarbon. Super-critical slurry compression, polymerization, pelletizing, High pressure processes can produce
polymeriza-tion processes use supercritical and dispatch as major steps. Fresh LLDPE homopolymers and vinyl acetate
propane as diluent. ethylene enters the reactor and is mixed copoymers in addition to the normal
with the low pressure recycle. After range of LDPEs.
Slurry processes run in loop reactors with further compression the mixture enters
the solvent circulating, stirred tank the reactor for polymerization. Oxygen or Some processes are listed in Table 1.
reactors with a high boiling solvent or a peroxide may be used as initiators.
“liquid pool“ in which polymerization takes
place in a boiling light solvent. A variety of
catalysts can be used in these processes. Gas-phase processes
Processes in solution require, as their last Lupotech G® A fluidized-bed process for manufacturing of HDPE, MDPE, and LLDPE
step, the stripping of the solvent. Unipol® PE A fluidized-bed process for manufacturing of HDPE and LLDPE

Supercritical polymerization in the slurry

loop provides advantages (e.g. higher Liquid-phase processes
productivity, improved product properties) Hostalen® A low-pressure slurry process for manufacturing of bimodal HDPE
over subcritical polymerization. Borstar® PE A supercritical slurry process, which combines a loop reactor and a gas-phase reactor

Phillips A slurry process for manufacturing of HDPE

Advanced processes combine a loop
reactor with one or two gase-phase
reactors, placed in series, where the High pressure processes (selected)
second stage of the reaction takes place in
Lupotech T® High-pressure process for manufacturing of broad range LDPE
the gas-phase reactors. For bimodal
polymers, lower molecular weights are ExxonMobil High-pressure tubular process for LDPE
formed in the loop reactor, while high Equistar High-pressure tubular and autoclave processes for LDPE
molecular weights are formed in the gas-
phase reactor. Some processes are listed in Table 1: Common PE production processes

Table 1.

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Use of process analyzers

Analyzer Tasks Analyzers and sampling points are interfaced to a plant wide data
communication system for direct data
Process analytical equipment is an Different analyzers are used in ethylene transfer from and to the analyzers.
indispensable part of any ethylene plant plants ranging from simple sensor type The total number of analyzers installed
because it provides the control system monitors to high technology process in a plant varies from plant to plant
and the operator with key data from the gas chromatographs. depending on the type of process,
process and its environment. individual plant conditions and user
The list typically includes requirements.
Four major applications
• Process gas chromatographs An example of typical sampling locations,
Analyzer applications can be divided in • Continuous gas analyzers analyzers, and measuring components
four groups depending on how the (paramagnetic oxygen analyzers, and ranges is given in Fig. 3 for a
analyzer data are used: NDIR analyzers, total hydrocarbon HDPE plant using a gas-phase fluidized
content analyzers) bed reactor:
• Closed-loop control for process and • Analyzers for moisture and O2 traces
product optimization • Low Explosion Level (LEL) analyzers • Feed of monomer, comonomers,
This application helps to increase yield, catalyst, and additives to the reactor
reduce energy consumption, achieve Analyzer installation (1-4)
smooth operation, and keep product • Cycle gas line (5)
quality accoding to the specification Analyzers are installed partially in the • Product line or feed to a second reactor
field close to the sampling location (6)
• Quality control and documentation and/or in an analyzer house (shelter). • Safety measurements at different
for ISO compliance In modern plants most of the analyzers locations of the plant (7)

• Plant monitoring and alarms

Sampling point Meas. Range Suitable
This application protects personnel Sampling stream Component [ppm] Analyzer
and plant from possible hazard from
1 Ethylene CO 0 ... 2 MAXUM
toxic or explosive substances purification CO2 0 ... 2 MAXUM
Methanol 0 ... 10 MAXUM
• Emission control Acetylene 0 ... 5 MAXUM
Total S 0 ... 2 MAXUM
This application helps to keep emission Ethane 0 ... 400 MAXUM
levels in compliance with local Moisture 0 ... 5 TPA
regulations. O2 0 ... 2 OXYMAT 6
2 Comonomer Moisture 0 ... 100 TPA
purification
3 Nitrogen Moisture 0 ... 10 TPA
purification O2 0 ... 10 OXYMAT 6
Gas-phase
4 Catalyst feed O2 0 ... 10 % OXYMAT 6
fluidized bed reactor
5 Cycle gas Nitrogen 0 ... 100% MAXUM or MicroSAM
Hydrogen 0 ... 50% CALOMAT 6
CO 0 ... 10 ppm ULTRAMAT 6
Catalyst hopper
Plant area 7 Methane 0 ... 10% ULTRAMAT 6
5 Ethane 0 ... 20% MAXUM or MicroSAM
4
Ethylene 0 ... 100% MAXUM or MicroSAM
N-Butane 0 ... 5% MAXUM or MicroSAM
ISO-Butan 0 ... 5% MAXUM or MicroSAM
Product 1-Butene 0 ... 25% MAXUM or MicroSAM
Nitrogen granules
6
Trans-2-Butene 0 ... 1% MAXUM or MicroSAM
3 purification ISO-Butene 0 ... 5% MAXUM or MicroSAM
CIS-2-Butene 0 ... 2% MAXUM or MicroSAM
Hexane 0 ... 10% MAXUM or MicroSAM
1-Hexene 0 ... 20% MAXUM or MicroSAM
Ethylene C6 inerts 0 ... 10% MAXUM or MicroSAM
1 purification
6 Product Moisture 0 ... 5 TPA
Comonomer 7 Plant area Various
2 purification
TPA: Third party analyzer

Fig. 3: Typical sampling points of a fluidized-bed HDPE plant Table 2: Typical measuring components and ranges acc. to Fig. 3

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Siemens Process Analytics at a Glance
Product overview

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
Fig. 8 Series 6 gas analyzer (rack design)
analysers into automations systems in
the process industry.

From demanding analysis tasks in the

chemical, oil and gas and petrochemical Fig. 12 MAXUM edition II Process GC
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
Fig. 9 Series 6 gas analyzer (field design) Fig. 13 MicroSAM Process GC

The product line of Siemens Process

Analytics comprises

• extractive and in-situ continuous gas

analyzers (fig. 8-11)
• process gas chromatographs
(fig. 12-13)
• sampling systems
• auxiliary equipment

Analyzers and chromatographs are

available in different versions for rack or
field mounting, explosion protection, Fig. 10 LDS 6 in-situ laser gas analyzer Fig. 14 SITRANS CV Natural Gas Analyzer
corrosion resistant etc.

A flexible networking concept allows

interfacing to DCS and maintenance
stations via 4-20 mA, PROFIBUS, OPC,
Modbus or industrial ethernet.

Fig. 11 SITRANS SL In-situ laser gas analyser

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Product Scope
Siemens Continuous Gas Analyzers and Process Gas Chromatographs

Extractive Continuous Gas Analyzers FIDAMAT 6 Process Gas Chromatographs

(CGA) The FIDAMAT 6 measures the total (Process GC)
hydrocarbon content in air or even in high
ULTRAMAT 23 boiling gas mixtures. It covers nearly all MAXUM edition II
The ULTRAMAT 23 is a cost-effective requirements, from trace hydrocarbon MAXUM edition II is very well suited
multicomponent analyzer for the detection in pure gases to measurement to be used in rough industrial environments
measurement of up to 3 infrared of high hydrocarbon concentrations, and performs a wide range of duties in the
sensitive gases (NDIR principle) plus even in the presence of corrosive gases. chemical and petrochemical industries and
oxygen (electrochemical cell). The refineries. MAXUM II features e. g. a
ULTRAMAT 23 is suitable for a wide ULTRAMAT 6 flexible, energy saving single or dual oven
range of standard applications. The ULTRAMAT 6 uses the NDIR measuring concept, valveless sampling and column
Calibration using ambient air eliminates principle and can be used in all applications switching, and parallel chromatography
the need of expensive calibration gases. from emission monitoring to process using multiple single trains as well as a
control even in the presence of highly wide range of detectors such as TCD, FID,
CALOMAT 6/62 corrosive gases. ULTRAMAT 6 is able to FPD, PDHID, PDECD and PDPID.
The CALOMAT 6 uses the thermal measure up to 4 infrared sensitive
conductivity detection (TCD) method to components in a single unit. MicroSAM
measure the concentration of certain MicroSAM is a very compact explosion
process gases, preferably hydrogen.The ULTRAMAT 6 / OXYMAT 6 proof micro process chromatograph.
CALOMAT 62 applies the TCD method as Both analyzer benches can be combined Using silicon-based micromechanical
well and is specially designed for use in in one housing to form a multi-component components it combines miniaturization
application with corrosive gases such as device for measuring up to two IR with increased performance at the same
chlorine. components and oxygen. time. MicroSAM is easy to use and its
rugged and small design allows mounting
OXYMAT 6/61/64 right at the sampling point. MicroSAM
The OXYMAT 6 uses the paramagnetic In-situ Continuous Gas Analyzers features drastically reduced cycle times,
measuring method and can be used (CGA) provides valveless sample injection and
in applications for process control, column switching and saves installation,
emission monitoring and quality LDS 6 maintenance, and service costs.
assurance. Due to its ultrafast response, LDS 6 is a high-performance in-situ
the OXYMAT 6 is perfect for monitoring process gas analyzer. The measurement SITRANS CV
safety-relevant plants. The corrosionproof (through the sensor) occurs directly in SITRANS CV is a micro process gas
design allows analysis in the presence of the process stream, no extractive sample chromatograph especially designed for
highly corrosive gases. The OXYMAT 61 is line is required. The central unit is reliable, exact and fast analysis of natural
a low-cost oxygen analyser for standard separated from the sensor by using fiber gas. The rugged and compact design
applications. The OXYMAT 64 is a gas optics. Measurements are carried out in makes SITRANS CV suitable for extreme
analyzer based on ZrO2 technology to realtime. This enables a pro-active control areas of use, e.g. off-shore exploration
measure smallest oxygen concentrations of dynamic processes and allows or direct mounting on a pipeline. The
in pure gas applications. fast, cost-saving corrections. special software "CV Control" meets the
requirements of the natural gas market,
e.g. custody transfer.

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Siemens Process Analytics – Solutions

Analyzer System
Manager (ASM)

Industrial Ethernet

Gas Chromatographs

Fig. 15 Analyzer house (shelter)

Continuous
Gas Analyzers
Serial Link
DCS: Distributed Control System
ASM: Analyzer System Manager Process Control Maintenance
CEMS: Continuous Emission
Monitoring System
DCS Integration: ASM
Modbus
4-20 mA
PROFIBUS Central 3rd Party
Industrial Ethernet Analyzer
Maintenance Access
OPC via Ethernet

Fig. 17 Communication technologies

Single Device System Analyzer networking for

data communication

Decentralized Centralized Engineering and manufacturing of

process analytical solutions increasingly
comprises "networking". It is getting
Continuous
Process GC
Third Party Field Shelter, a standard requirement in the process
Gas analyzer Analyzer Installation CEMS industry to connect analyzers and
analyzer systems to a communication
network to provide for continuous and
direct data transfer from and to the
Fig. 16 Networking for DCS integration and maintenance support
analysers. The two objectives are (fig. 16).
• To integrate the analyzer and analyzer
Analytical solutions are always driven by We rely on many years of world-wide systems seamless into the PCS / DCS
the customer’s requirements. We offer experience in process automation and system of the plant
an integrated design covering all steps engineering and a collection of specialized and
from sampling point and sample knowledge in key industries and • To allow direct access to the analyzers
preparation up to complete analyzer industrial sectors. We provide Siemens or systems from a maintenance
cabinets or for installation in analyzer quality from a single source with a station to ensure correct and reliable
shelters (fig. 15). This includes also signal function warranty for the entire system. operation including preventive or
processing and communications to the predictive maintenance (fig. 17).
control room and process control system. Read more in chapter "Our services".
Siemens Process Analytics provides
networking solutions to meet the demands
of both objectives.

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Siemens Process Analytics –
Our Services
Siemens Process Analytics is your
competent and reliable partner
worldwide for Service, Support and Plant life cycle
Consulting.
Planning & Engineering & Installation & Operation &
Our rescources for that are Design Development Commissioning Maintenance
Modernization

• Expertise Online Support

As a manufacturer of a broad variety FEED for Process Analytics
of analyzers, we are very much
Engineering
experienced in engineering and
manufacturing of analytical systems and Installation and commissioning
analyzer houses. We are familiar with Repairs and spare parts
communication networks, well trained
Field service
in service and maintenance and familiar
with many industrial processes and Service contracts
industries. Thus, Siemens Process Optimization and modernization
Analytics owns a unique blend of overall
Technical Support
analytical expertise and experience.
• Global presence Training
With our strategically located centers
of competence in Germany, USA,
Singapore, Dubai and Shanghai, we are Fig. 18 Portfolio of services provided by Siemens Process Analytics
globally present and acquainted with
all respective local and regional FEED for Process Analytics Whether you are plant operators
requirements, codes and standards. or belong to an EPC Contractor you
All centers are networked together. Front End Engineering and Design will benefit in various ways from
(FEED for PA) is part of the planning and FEED for Process Analytics by Siemens:
Service portfolio engineering phase of a plant construction
or modification project and is done after • Analytics and industry know how
Our wide portfolio of services is conceptual business planning and prior to available, right from the beginning
segmented into Consulting, Support and detail design. During the FEED phase, best of the project
Service. It comprises really all measures, opportunities exist for costs and time • Superior analyzer system performance
actions and advises that may be required savings for the project, as during this with high availability
by our clients throughout the phase most of the entire costs are defined • Established studies, that lead to
entire lifecycle of their plant: and changes have least impact to the realistic investment decisions
• Site survey project. Siemens Process Analytics holds a • Fast and clear design of the analyzer
• Installation check unique blend of expertise in analytical system specifications, drawings and
• Functionality tests technologies, applications and in providing documentation
• Site acceptance test complete analytical solutions to many • Little project management and
• Instruction of plant personnel on site industries. coordination effort, due to one
• Preventive maintenance responsible contact person and
• On site repair Based on its expertise in analytical less time involvement
• Remote fault clearance technology,application and engineering, • Additional expertise on demand,
• Spare part stock evaluation Siemens Process Analytics offer a wide without having the costs, the
• Spare part management scope of FEED services focused on effort and the risks of building
• Professional training center analyzing principles, sampling up the capacities
• Process optimisation technologies, application solutions as well • Lowest possible Total Costs of
• Internet-based hotline as communication system and given Ownership (TCO) along the
• FEED for Process Analytics standards (all related to analytics) to lifecycle regarding investment
• Technical consullting support our clients in maximizing costs, consumptions, utilities
performance and efficiency of their supply and maintenance
projects.

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Notes:

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Notes:

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For more information, please contact:

Siemens Industry, Inc.

5980 West Sam Houston Parkway North
Suite 500
Houston, TX 77041
Phone: 713-939-7400
Email: [email protected]

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