Siemens AG 2007

Process Analytics
in Polypropylene (PP) Plants
Polypropylene
Polypropylene (PP) is a generic
name for a family of semicrystalline
polymers. PP, as well as polyethyl-
ene (PE), belongs to the group of

December 2007
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 thou-
sands of individual links using a
variety of catalysts.
The base monomer for PP is propy-
lene, which is a gas at room temper-
ature, but when linked together as

Case Study
polymers, it forms tough, flexible
plastic materials with a large variety
of applications. The linking of mole-
cules is referred to as polymeriza-
tion. There are various commercial
technologies used to manufacture
polypropylene. 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 micro-
wave food containers, have high
heat resistance while others melt
easily.

For the production of polypropylene Siemens, a leader in process analytical

a variety of processes is in use instrumentation, has proven over
depending on what final products are decades its capability to plan, engi-
intended to be produced. However, neer, manufacture, implement and
regardless of the process type, all service analyzer systems for polypro-
plants require process analytical pylene plants worldwide.
equipment to collect reliable and This Case Study provides an over-
accurate information for process con- view of the processes typically used
trol, product quality, plant safety and and describes how Siemens with its
environmental compliance. analyzer and application know-how
meets best the process requirements.
 Siemens AG 2007

Polypropylene production processes

Polypropylene Production Processes Gas-Phase Polymerization

is made in a polymerization reaction by Various production processes exist for In gas-phase polymerization (Fig. 2a)
building long molecular chains com- PP with some general similarities. But the propylene is contacted with solid
prised of propylene monomers, mostly the processes are evolving continu- catalyst material intimately dispersed in
by using catalysts. The type and nature ously. So the specifics can be signifi- an agitated bed of dry polymer powder.
of the catalysts are of great influence on cantly different and the following Two different methods are used to carry
the polymerization. As catalysts became descriptions and graphic displays out this reaction
more efficient, the polypropylene prod- should be, therefore, considered In the fluidized-bed process the
ucts became purer and more versatile exemplarily only with no direct relation monomer flows through a perforated
and the production process became to existing plant or process designs. distribution plate at the reactor bot-
simplier and more efficient. tom and rapid gas circulation ensures
Generic polymerization process
fluidization and heat removal. Unre-
Similarities between the processes
Polypropylene (PP) is a family of resins acted polymer is separated from the
follow a generic olefin polymerization
made from the polymerization of propy- polymer particles at the top of the
process scheme as shown in Fig. 1
lene gas. It is produced either in radical reactor and recycled. Fluidized-bed
(from left):
polymerization reactions or in catalytic plants are able to produce a wide
polymerization reactions.
Feedstock materials and additives range of polypropylene. A modifica-
must be purified and catalyst material tion uses a second reactor connected
must be prepared. And - in case of a in series to perform copolymeriza-
Polypropylene is a tough, rigid plastic high pressure process (not used for tion.
and produced in a variety of molecular PP) - the gas must be compressed in
several stages.
The stirred-bed process uses a
weights and crystallinities. Three main horizontal or vertical reactor with
types of PP exist: Polymerization of propylene takes compartments, in which the bed
Homopolymers, which have high place either in the gas phase of polymer particles is agitated by
heat resistance and good rigidity, (fluidized bed or stirred reactor) or mixing blades.
making them suitable for a wide a liquid phase (slurry or solution).
The gas-phase polymerization technol-
range of applications Polymer particles are then separated ogy is economical and flexible and can
Copolymers, which are made by from still existing monomers and accomodate a large variety of catalysts.
incorporating different monomers, diluents, pelletized, dried and It is by far the most common process in
are extremely resilient materials and dispatched. modern polypropylene production
are widely used in automotive and Monomers and diluents are recovered plants.
industrial applications and fed again to the process. Some gas-phase processes are listed
Random copolymers, which are in Table 1.
made by introducing ethylene links
into the PP-chain, have improved
optical properties such as transpar-
ency.

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

2
 Siemens AG 2007

Liquid-Phase Primary gas-phase reactor Copolymer gas-phase reactor

Polymerization
In liquid-phase processes (slurry or sus-
pension, Fig. 2b) catalyst and polymer Catalyst
particles are suspended in an inert sol-
vent, typically a light or heavy hydrocar-
bon. Super-critical slurry polymerization
processes use supercritical propane as Dispatch
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 Monomer Hydrogen Comonomer Hydrogen
takes place in a boiling light solvent. A
variety of catalysts can be used in these Fig. 2a: PP gas-phase production example
processes. Processes in solution require,
as their last step, the stripping of the
solvent.
Supercritical polymerization in the Recycle Gas phase reactor
slurry loop provides advantages (e.g.
higher productivity, improved product Loop reactor
properties) over subcritical polymeriza-
tion. Catalyst
Flash
dryer
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 Product
Diluent
in the gas-phase reactors. For bimodal
polymers, lower molecular weights are
formed in the loop reactor, while high
Ethylene
molecular weights are formed in the
Hydrogen
gas-phase reactor. Comonomer
Some liquid-phase processes are listed
in Table 1. Fig. 2b: PP liquid-phase production example

Gas-phase processes
Unipol PP A fluidized-bed process with one or two reactors for the production of PP
homopolymers, random polymers and impact polymers.
Novolen A gas-phase stirred-bed process with two reactors in series for the produc-
tion of PP

Liquid-phase processes
Borstar PP A supercritical slurry process, which combines a loop reactor with two gas-
phase reactors
Spheripol A slurry process for the production of PP homopolymer plus random copol-
ymers

Table 1: Common PP production processes

3
 Siemens AG 2007

Use of process analyzers

Analyzer Tasks Analyzers and sampling points An example of typical sampling loca-
Different analyzers are used in PP plants tions, analyzers, and measuring compo-
Process analytical equipment is an indis- nents and ranges is given in Fig. 3 for a
pensable part of any polypropylene ranging from simple sensor type moni-
tors to high technology process gas PP plant using two gas-phase reactors in
plant because it provides the control series:
system and the operator with key data chromatographs.
from the process and its environment. The list typically includes Feed of monomer, comonomers,
catalyst, and additives to the
Process gas chromatographs reactor (1-5)
Four major applications Continuous gas analyzers Cycle gas lines (6-7)
(paramagnetic oxygen analyzers,
Analyzer applications can be structured Product line (8)
NDIR analyzers, thermal conductivity
in four groups depending on how the
and total hydrocarbon analyzers) Safety measurements at various
analyzer data are used:
Analyzers for moisture and O2 traces locations of the plant (9)
Closed-loop control for process
and product optimization Low Explosion Level (LEL) analyzers
This application helps to increase
yield, reduce energy consumption,
achieve smooth operation, and keep Analyzer installation
product quality accoding to the speci- Analyzers are installed partially in the
fication field close to the sampling location
Quality control and documentation and/or in an analyzer house (shelter).
for ISO compliance In modern plants most of the analyzers
are interfaced to a plant wide data com-
Plant monitoring and alarms munication system for direct data trans-
This application protects personnel fer from and to the analyzers.
and plant from possible hazard from
toxic or explosive substances
The total number of analyzers installed
Emission control in a plant varies from plant to plant
This application helps to keep emis- depending on the type of process,
sion levels in compliance with local individual plant conditions and
regulations. user requirements.

Sampling point Component Meas. Range Suitable Analyzer

Sampling stream [ppm]
1 Nitrogen feed Moisture 0 ... 1 TPA
O2 0 ... 5 TPA
2 Hydrogen feed Moisture 0 ... 1 TPA
O2 0 ... 5 TPA
3 Propylene feed Moisture 0 ... 5 TPA
Primary
reactor Plant area 9 O2 0 ... 5 TPA
CO2 0 ... 5 MAXUM
6 Ethylene 0 ... 20 MAXUM
Copolymer H2S 0 ... 2 MAXUM
reactor
COS 0 ... 1 MAXUM
Catalyst Total S 0 ... 5 MAXUM
7 4 Catalyst feed O2 0 ... 40 % OXYMAT 6
4 5 Comonomer Moisture 0 ... 100 TPA
feed
Product 8 6 Cycle gas Nitrogen 0 ... 100 % MAXUM or MicroSAM
Purification 1
Nitrogen
7 Cycle gas Hydrogen 0 ... 15 % CALOMAT 6
CO 0 ... 100 ULTRAMAT 6
Purification 2 Methane 0 ... 2 % ULTRAMAT 6
Hydrogen Ethane 0 ... 5 % MAXUM or MicroSAM
Ethylene 0 ... 10 % MAXUM or MicroSAM
Purification 3 5 Propane 0 ... 50 % MAXUM or MicroSAM
Propylene Propylene 0 ... 100 % MAXUM or MicroSAM
Purification
8 Product Moisture 0 ... 5 TPA
Comonomer 9 Plant area Various
Fig. 3: Typical sampling points of a PP production plant with 2 reac- Table 2: Typical measuring components and ranges acc. to Fig. 4
tors in series

4
 Siemens AG 2007

Siemens Process Analytics at a glance

Products

Siemens Process Analytics Extractive Continuous Gas Analyzers (CGA)

Siemens Process Analytics is a leading ULTRAMAT 23 The ULTRAMAT 23 is a cost-effective multicomponent analyser for the
measurement of up to 3 infrared sensitive gases (NDIR principle) plus
provider of process analyzers and pro- oxygen (electrochemical cell). The ULTRAMAT 23 is suitable for a wide
cess analysis systems. We offer our glo- range of standard applications. Calibration using ambient air eliminates
bal customers the best solutions for the need of expensive calibration gases.
their applications based on innovative CALOMAT 6/62 The CALOMAT 6 uses the thermal conductivity detection (TCD) method
analysis technologies, customized sys- to measure the concentration of certain process gases, preferably hydro-
tem engineering, sound knowledge of gen.The CALOMAT 62 applies the TCD method as well and is specially
customer applications and professional designed for use in application with corrosive gases such as chlorine.
support. And with Totally Integrated OXYMAT 6/61/64 The OXYMAT 6 uses the paramagnetic measuring method and can be
Automation (TIA). Siemens Process used in applications for process control, emission monitoring and quality
assurance. Due to its ultrafast response, the OXYMAT 6 is perfect for
Analytics is your qualified partner for monitoring safety-relevant plants. The corrosion-proof design allows
efficient solutions that integrate pro- analysis in the presence of highly corrosive gases.
cess analysers into automations sys- The OXYMAT 61 is a low-cost oxygen analyser for standard applications.
tems in the process industry. The OXYMAT 64 is a gas analyzer based on ZrO2 technology to measure
smallest oxygen concentrations in pure gas applications.
From demanding analysis tasks in the
ULTRAMAT 6 The ULTRAMAT 6 uses the NDIR measuring principle and can be used in
chemical, oil & gas and petrochemical all applications from emission monitoring to process control even in the
industry to combustion control in presence of highly corrosive gases.
power plants to emission monitoring at ULTRAMAT 6 is able to measure up to 4 infrared sensitive components in
waste incineration plants, the highly a single unit.
accurate and reliable Siemens gas chro- ULTRAMAT 6 / Both analyzer benches can be combined in one housing to form a multi-
matographs and continuous analysers OXYMAT 6 component device for measuring up to two IR components and oxygen.
will always do the job.
FIDAMAT 6 The FIDAMAT 6 measures the total hydrocarbon content in air or even in
Siemens process Analytics offers a wide high-boiling gas mixtures. It covers nearly all requirements, from trace
and innovative portfolio designed to hydrocarbon detection in pure gases to measurement of high hydrocar-
meet all user requirements for compre- bon concentrations, even in the presence of corrosive gases.
hensive products and solutions. In-situ Continuous Gas Analyzer (CGA)
LDS 6 LDS 6 is a high-performance in-situ process gas analyser. The measure-
Our Products ment (through the sensor) occurs directly in the process stream,
no extractive sample line is required. The central unit is separated from
The product line of Siemens Process the sensor by using fiber optics. Measurements are carried out in real-
Analytics comprises extractive and in- time. This enables a pro-active control of dynamic processes and allows
situ continuous gas analyzers (fig. 4 to fast, cost-saving corrections.
7), process gas chromatographs (fig.8 Fig. 5: Product scope Siemens Continuous Gas Analyzers
to 11), sampling systems and auxiliary
equipment. Analyzers and chromato-
graphs are available in different ver-
sions for rack or field mounting, explo-
sion 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.

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

5
 Siemens AG 2007

Siemens Process Analytics at a glance

Products (continued) and Solutions

Process Gas Chromatographs (Process GC)

MAXUM edition II MAXUM edition II is very well suited to be used in rough industrial envi-
ronments and performs a wide range of duties in the chemical and pet-
rochemical industries and refineries.
MAXUM II features e. g. a flexible, energy saving single or dual oven con-
cept, valveless sampling and column switching, and parallel chromatog-
raphy 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 chromato-
graph. 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 mount-
ing 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 com-
Fig. 8: MAXUM edition II Process GC
pact design makes SITRANS CV suitable for extreme areas of use, e.g. off-
shore 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
Analytical solutions are always driven We rely on many years of world-wide
by the customers requirements. We experience in process automation and
offer an integrated design covering all engineering and a collection of special-
Fig. 9: MicroSAM Process GC
steps from sampling point and sample ized knowledge in key industries and
preparation up to complete analyser industrial sectors. We provide Siemens
cabinets or for installation in analyser quality from a single source with a func-
shelters (fig. 12). This includes also sig- tion warranty for the entire system.
nal processing and communications to Read more in "Our Services.
the control room and process control
system.

Fig. 10: SITRANS CV Natural Gas Analyzer

Fig. 12: Analyzer house (shelter)

6
 Siemens AG 2007

Siemens Process Analytics at a glance

Solutions (continued) and Services

Our solutions ...

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Siemens Process Analytics provides net- Global presence

working solutions to meet the demands With our strategically located centers
of both objectives. of competence in Germany, USA,
Singapore, Dubai and Shanghai, we
Our Services are globally present and acquainted
with all respective local and regional
*DV&KURPDWRJUDSKV Siemens Process Analytics is your com-
requirements, codes and standards.
petent and reliable partner world wide
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for Service, Support and Consulting.
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Expertise
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Thus, Siemens Process Analytics owns
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expertise and experience.
Fig. 15: Portfolio of services

7
 Siemens AG 2007

Siemens Process Analytics at a glance

Services, continued

Our Services ...

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Site acceptance test
Based on its expertise in analytical tech- Additional expertise on demand,
Instruction of plant personnel on site nology, application and engineering , without having the costs, the effort
Preventive maintenance Siemens Process Analytics offer a wide and the risks of building up the capac-
On site repair scope of FEED services focused on anal- ities
ysing principles, sampling technologies, Lowest possible Total Costs of Owner-
Remote fault clearance application solutions as well as commu- ship (TCO) along the lifecycle regard-
Spare part stock evaluation nication system and given standards (all ing investment costs, consumptions,
Spare part management related to analytics) to support our cli- utilities supply and maintenance.
Professional training center ents in maximizing performance and
efficiency of their projects.
Process optimisation
Whether you are plant operators or
Internet-based hotline belong to an EPC Contractor you will
FEED for Process Analytics benefit in various ways from FEED for
Technical consullting Process Analytics by Siemens:
Analytics and industry know how
FEED for Process Analytics available, right from the beginning
Front End Engineering and Design of the project
(FEED) is part of the planning and engi-
neering phase of a plant construction or
Superior analyzer system perfor-
mance with high availability
modification project and is done after
conceptual business planning and prior Established studies, that lead to
to detail design. During the FEED phase, realistic investment decisions
best opportunities exist for costs and Fast and clear design of the analyzer
time savings for the project, as during system specifications, drawings and
this phase most of the entire costs are documentation
defined and changes have least impact Little project management and
to the project. Siemens Process Analyt- coordination effort, due to one
ics holds a unique blend of expertise in responsible contact person and
analytical technologies, applications less time involvement
and in providing complete analytical
solutions to many industries.

8
 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 Siemens Energy & Automation Inc. Siemens Pte. Limited
A&D SC PA, Process Analytics 7101 Hollister Road A&D SC PS/PA CoC
stliche Rheinbrckenstr. 50 Houston, TX 77040 60 MacPherson Road
76187 Karlsruhe USA Singapore 348615
Germany

Phone: +49 721 595 3829 Phone: +1 713 939 7400 Phone: +65 6490 8728
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processanalytics.automation@siemens.com
www.siemens.com/prozessanalytics www.siemens.com/processanalytics www.siemens.com/processanalytics

Siemens Ltd., China Siemens LLC

A&D SC, Process Analytics A&D 2B.
7F, China Marine Tower PO Box 2154,
No.1 Pu Dong Avenue Dubai, U.A.E.
Shanghai, 200120
P.R.China

Phone: +86 21 3889 3602 Phone: +971 4 366 0159

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www.ad.siemens.com.cn www.siemens.com/processanalytics

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