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    For the production of polyethylenea variety of processes is in usedepending on what final products areintended to be produced. However,regardless of the process type, allplants require process analyticalequipment to collect reliable andaccurate information for process con-trol, product quality, plant safety andenvironmental compliance.

    Siemens, a leader in process analyticalinstrumentation, has proven overdecades its capability to plan, engi-neer, manufacture, implement andservice analyzer systems for polyethyl-ene plants worldwide.

    This Case Studyprovides an over-viewof the processes typically used anddescribes how Siemens with its ana-

    lyzer and application know-howmeets best the process requirements.

    PolyethylenePolyethylene (PE) is a generic namefor a family of semicrystalline poly-mers. PE, as well as polypropylene(PP), belong to the group of polyole-fins, that are derived from a groupof base chemicals known as olefins.Polyolefins are made by joiningtogether small molecules (mono-mers) to form long-chain molecules(polymers) with thousands of indi-vidual links using a variety of cata-lysts.

    The base monomer for PE is ethyl-ene, which is a gas at room temper-ature, but when linked together aspolymers, it forms tough, flexibleplastic materials with a large varietyof applications. The linking of mole-cules is referred to as polymeriza-tion. There are various commercialtechnologies used to manufacturepolyethylene. Each technology pro-duces unique combinations of poly-mer characteristics.

    Polyolefins (Polyethylene andPolypropylene) are the worldsmostly produced and fastest grow-

    ing polymer family because modern polyolefins cost less to

    produce and process than otherplastics or conventional materials

    polyolefins are available in manyvarieties. They range from rigidmaterials, which are used for carparts, to soft materials such asflexible fibres. Some are as clearas glass; others are completelyopaque. Some, such as micro-wave food containers, have highheat resistance while others melteasily.

    Process Analyticsin Polyethylene (PE) Plants

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    2

    Polyethylene production processes

    Polyethyleneis made in a polymerization reaction bybuilding long molecular chains com-prised of ethylene monomers, mostlyby using catalysts. The type and natureof the catalysts are of great influence onthe polymerization. As catalysts becamemore efficient, the polyethylene prod-ucts became purer and more versatileand the production process becamesimplier and more efficient.

    Polyethylene (PE) is a family of resinsmade from the polymerization of ethyl-

    ene gas. It is produced either in radicalpolymerization reactions or in catalyticpolymerization reactions. Most PEmolecules contain branches in theirchains which are formed spontaneouslyin case of radical polymerization ordeliberately by copolymerization ofethylene with olefins in case ofcatalytic polymerization.

    PE resins are classified according totheir density which partly depends onthe type of branching.

    HDPEHigh Density PolyEthylene has almost

    no branching and thus has strongerintermolecular forces. It is producedmainly in slurry and gas-phase poly-merization processes. HDPE is a whiteopaque solid.

    MDPEMedium Density PolyEthylene has ahigh degree of resistance to chemi-cals and is very easy to keep clean.

    LDPELow-Density PolyEthylene has ran-dom long branching, with brancheson branches. It is produced mainly inhigh-pressure poymerization pro-

    cesses. LDPE is a translucent solid.

    LLDPELinear Low-Density PolyEthylene is asubstantially linear polymer, with sig-nificant numbers of short branches,produced mainly by copolymerizationof ethylene with longer-chain olefins.LLDPE is a translucent solid.

    Production ProcessesA large number of production processesexist for PE with some general similari-ties. But the processes are evolving con-tinuously. So the specifics can be signif-icantly different and the followingdescriptions and graphic displaysshould be, therefore, considered exem-plarily only with no direct relation toexisting plant or process designs.

    Generic polymerization process

    Similarities between the processesfollow a generic olefin polymerizationprocess scheme as shown in Fig. 1(from left):

    Feedstock materials and additivesmust be purified and catalyst materialmust be prepared. And - in case of ahigh pressure process - the gas mustbe compressed in several stages.

    Polymerization takes place either inthe gas phase (fluidized bed orstirred reactor), the liquid phase(slurry or solution), or in a high pres-sure environment. Polymerization isthe heart of the processes. On anyone unit, only one of the three pro-cesses is used. More details will beexplained on the next pages.

    Polymer particles are then separatedfrom still existing monomers and dilu-ents, pelletized, dried and dis-patched.

    Monomers and diluents are recoveredand fed again to the process.

    Gas-Phase PolymerizationIn gas-phase polymerization (Fig. 2,left) the ethylene is contacted with solidcatalyst material intimately dispersed inan agitated bed of dry polymer powder.Two different methods are used to carryout this reaction

    In the fluidized-bed process themonomer flows through a perforateddistribution plate at the reactor bot-tom and rapid gas circulation ensuresfluidization and heat removal. Unre-acted polymer is separated from the

    polymer particles at the top of thereactor and recycled. Fluidized-bedplants are able to produce eitherLLDPE or HDPE and are free of con-straints from viscosity (solution pro-cess) or solubility (slurry process).A modification uses a second reactorconnected in series to perform copo-lymerization.

    The stirred-bed process uses a hori-zontal or vertical reactor with com-partments, in which the bed ofpolymer particles is agitated by mix-ing blades.

    The gas-phase polymerization technol-ogy is economical and flexible and canaccomodate a large variety of catalysts.It is by far the most common process inmodern ethylene production plants.

    Some processes are listed in Table 1.

    Feedstock(Options)

    EthylenePropyleneComonomer

    SolventNitrogenOxygen

    Feed Purification

    Gas Compression

    Catalyst Preparation High pressureProcess

    Separation

    Recovery

    Drying

    Pelletizing

    Gas-phaseProcess

    Liquid-phaseProcess

    Feedstock(Options)

    EthylenePropyleneComonomer

    SolventNitrogenOxygen

    Feed Purification

    Gas Compression

    Catalyst Preparation High pressureProcessHigh pressureProcess

    Separation

    Recovery

    Drying

    Pelletizing

    Gas-phaseProcessGas-phaseProcess

    Liquid-phaseProcessLiquid-phaseProcess

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

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    Liquid-PhasePolymerizationIn liquid-phase processes (slurry or sus-pension, Fig. 2, right) catalyst and poly-mer particles are suspended in an inertsolvent, typically a light or heavy hydro-carbon. Super-critical slurry polymeriza-tion processes use supercritical propaneas diluent.Slurry processes run in loop reactorswith the solvent circulating, stirred tankreactors with a high boiling solvent or aliquid pool in which polymerization

    takes place in a boiling light solvent.A variety of catalysts can be used inthese processes. Processes in solutionrequire, as their last step, the strippingof the solvent.

    Supercritical polymerization in theslurry loop provides advantages (e.g.higher productivity, improved productproperties) over subcritical polymeriza-tion.

    Advanced processes combine a loopreactor with one or two gase-phasereactors, placed in series, where thesecond stage of the reaction takes placein the gas-phase reactors. For bimodalpolymers, lower molecular weights areformed in the loop reactor, while highmolecular weights are formed in thegas-phase reactor.

    Some processes are listed in Table 1.

    High Pressure ProcessesIn high pressure processes (Fig. 2, cen-ter) autoclave or tubular reactors (pres-sure in excess of 3,000 bar) are used,but the processes are similar, compris-ing compression, polymerization, pel-letizing, and dispatch as major steps.Fresh ethylene enters the reactor and ismixed with the low pressure recycle.After further compression the mixtureenters the reactor for polymerization.Oxygen or peroxide may be used as ini-tiators.

    A tubular reactor typically consists ofseveral hundred meters of jacketedhigh-pressure tubing arranged as aseries of straight sections connectedby 180 bends.

    High pressure processes can produceLLDPE homopolymers and vinylacetatecopoymers in addition to the normalrange of LDPEs.

    Some processes are listed in Table 1.

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

    Table 1: Common PE production processes

    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 HDPEBorstar PE A supercritical slurry process, which combines a loop reactor and a gas-

    phase 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

    Primary gas-phase reactor

    Catalyst

    Monomer Hydrogen Comonomer Hydrogen

    Copolymer gas-phase reactor

    Dispatch

    Primary gas-phase reactor

    Catalyst

    Monomer Hydrogen Comonomer Hydrogen

    Copolymer gas-phase reactor

    Dispatch

    Ethylene

    Extruder

    LPseparator

    HPseparator

    Tubular reactor

    Initiator

    Primarycompressor

    Secondarycompressor

    Recycle

    Vinyl acetate

    Ethylene

    Extruder

    LPseparator

    HPseparator

    Tubular reactor

    Initiator

    Primarycompressor

    Secondarycompressor

    Recycle

    Vinyl acetate

    Ethylene

    HydrogenComonomer

    Loop reactor

    Catalyst

    Gas phase reactor

    Product

    Flash

    dryer

    Recycle

    Diluent

    Ethylene

    HydrogenComonomer

    Loop reactor

    Catalyst

    Gas phase reactor

    Product

    Flash

    dryer

    Recycle

    Diluent

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    4

    Use of process analyzers

    Analyzer TasksProcess analytical equipment is an indis-pensable part of any ethylene plantbecause it provides the control systemand the operator with key data from theprocess and its environment.

    Four major applications

    Analyzer applications can be divided infour groups depending on how the ana-lyzer data are used:

    Closed-loop control for processand product optimization

    This application helps to increaseyield, reduce energy consumption,achieve smooth operation, and keepproduct quality accoding to the speci-fication

    Quality control and documentationfor ISO compliance

    Plant monitoring and alarmsThis application protects personneland plant from possible hazard fromtoxic or explosive substances

    Emission controlThis application helps to keep emis-sion levels in compliance with local

    regulations.

    Analyzers and sampling pointsDifferent analyzers are used in ethyleneplants ranging from simple sensor typemonitors to high technology processgas chromatographs.

    The list typically includes

    Process gas chromatographs Continuous gas analyzers

    (paramagnetic oxygen analyzers,NDIR analyzers, total hydrocarboncontent analyzers)

    Analyzers for moisture and O2 traces

    Low Explosion Level (LEL) analyzers

    Analyzer installation

    Analyzers are installed partially in thefield close to the sampling locationand/or in an analyzer house (shelter).In modern plants most of the analyzersare interfaced to a plant wide data com-munication system for direct data trans-fer from and to the analyzers.

    The total number of analyzers installedin a plant varies from plant to plantdepending on the type of process, indi-vidual plant conditions and userrequirements.

    An example of typical sampling loca-tions, analyzers, and measuring compo-nents and ranges is given in Fig. 3 for aHDPE plant using a gas-phase fluidizedbed reactor:

    Feed of monomer, comonomers,catalyst, and additives to the reactor(1-4)

    Cycle gas line (5) Product line or feed to a second reac-

    tor (6)

    Safety measurements at differentlocations of the plant (7)

    Gas-phase

    fluidized bed reactor

    Catalyst hopper

    Nitrogenpurification

    Comonomer

    purification

    Ethylene

    purification

    Productgranules

    1

    6

    54

    3

    2

    Plant area 7

    Gas-phase

    fluidized bed reactor

    Catalyst hopper

    Nitrogenpurification

    Nitrogenpurification

    Comonomer

    purification

    Comonomer

    purification

    Ethylene

    purification

    Ethylene

    purification

    ProductgranulesProductgranules

    11

    66

    5544

    33

    22

    Plant area 77

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

    Sampling pointSampling stream

    Component Meas. Range[ppm]

    Suitable Analyzer

    1 Ethylenepurification

    COCO2MethanolAcetyleneTotal SEthaneMoistureO2

    0 ... 20 ... 20 ... 100 ... 50 ... 20 ... 4000 ... 50 ... 2

    MAXUMMAXUMMAXUMMAXUMMAXUMMAXUMTPAOXYMAT 6

    2 Comonomerpurification

    Moisture 0 ... 100 TPA

    3 Nitrogenpurification

    MoistureO2

    0 ... 100 ... 10

    TPAOXYMAT 6

    4 Catalyst feed O2 0 ... 10 % OXYMAT 6

    5 Cycle gas NitrogenHydrogen

    COMethaneEthaneEthyleneN-ButaneISO-Butan1-ButeneTrans-2-ButeneISO-ButeneCIS-2-ButeneHexane1-HexeneC6 inerts

    0 ... 100%0 ... 50%

    0 ... 10 ppm0 ... 10%0 ... 20%0 ... 100%0 ... 5%0 ... 5%0 ... 25%0 ... 1%0 ... 5%0 ... 2%0 ... 10%0 ... 20%0 ... 10%

    MAXUM or MicroSAMCALOMAT 6

    ULTRAMAT 6ULTRAMAT 6MAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAMMAXUM or MicroSAM

    6 Product Moisture 0 ... 5 TPA

    7 Plant area Various

    TPA: Third party analyzer

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

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    Siemens Process Analytics at a glanceProducts

    Siemens Process AnalyticsSiemens Process Analytics is a leadingprovider of process analyzers and pro-cess analysis systems. We offer our glo-bal customers the best solutions fortheir applications based on innovativeanalysis technologies, customized sys-tem engineering, sound knowledge ofcustomer applications and professionalsupport. And with Totally IntegratedAutomation (TIA). Siemens ProcessAnalytics is your qualified partner forefficient solutions that integrate pro-

    cess analysers into automations sys-tems in the process industry.

    From demanding analysis tasks in thechemical, oil & gas and petrochemicalindustry to combustion control inpower plants to emission monitoring atwaste incineration plants, the highlyaccurate and reliable Siemens gas chro-matographs and continuous analyserswill always do the job.

    Siemens process Analytics offers a wideand innovative portfolio designed tomeet all user requirements for compre-hensive products and solutions.

    Our ProductsThe product line of Siemens ProcessAnalytics comprises extractive and in-situ continuous gas analyzers (fig. 4 to7), process gas chromatographs (fig.8to 11), sampling systems and auxiliaryequipment. 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 allowsinterfacing to DCS and maintenancestations via 4 to 20 mA, PROFIBUS,

    Modbus, OPC or industrial ethernet.

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

    Fig. 5: Product scope Siemens Continuous Gas Analyzers

    Extractive Continuous Gas Analyzers (CGA)

    ULTRAMAT 23 The ULTRAMAT 23 is a cost-effective multicomponent analyser for themeasurement of up to 3 infrared sensitive gases (NDIR principle) plusoxygen (electrochemical cell). The ULTRAMAT 23 is suitable for a widerange of standard applications. Calibration using ambient air eliminatesthe need of expensive calibration gases.

    CALOMAT 6/62 The CALOMAT 6 uses the thermal conductivity detection (TCD) methodto measure the concentration of certain process gases, preferably hydro-gen.The CALOMAT 62 applies the TCD method as well and is speciallydesigned for use in application with corrosive gases such as chlorine.

    OXYMAT 6/61/64 The OXYMAT 6 uses the paramagnetic measuring method and can beused in applications for process control, emission monitoring and qualityassurance. Due to its ultrafast response, the OXYMAT 6 is perfect formonitoring safety-relevant plants. The corrosion-proof design allowsanalysis 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 measuresmallest oxygen concentrations in pure gas applications.

    ULTRAMAT 6 The ULTRAMAT 6 uses the NDIR measuring principle and can be used inall applications from emission monitoring to process control even in thepresence of highly corrosive gases.ULTRAMAT 6 is able to measure up to 4 infrared sensitive components ina single unit.

    ULTRAMAT 6 /OXYMAT 6

    Both analyzer benches can be combined in one housing to form a multi-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 inhigh-boiling gas mixtures. It covers nearly all requirements, from tracehydrocarbon detection in pure gases to measurement of high hydrocar-bon 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 measure-ment (through the sensor) occurs directly in the process stream,no extractive sample line is required. The central unit is separated fromthe sensor by using fiber optics. Measurements are carried out in real-time. This enables a pro-active control of dynamic processes and allowsfast, cost-saving corrections.

    Fig. 6: Series 6 gas analyzer (field design) Fig. 7: LDS 6 in-situ laser gas analyzer

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    Siemens Process Analytics at a glanceProducts (continued) and Solutions

    Fig. 8: MAXUM edition II Process GC

    Fig. 9: MicroSAM Process GC

    Fig. 10: SITRANS CV Natural Gas Analyzer

    Our solutionsAnalytical solutions are always drivenby the customers requirements. Weoffer an integrated design covering all

    steps from sampling point and samplepreparation up to complete analysercabinets or for installation in analysershelters (fig. 12). This includes also sig-nal processing and communications tothe control room and process controlsystem.

    We rely on many years of world-wideexperience in process automation andengineering and a collection of special-

    ized knowledge in key industries andindustrial sectors. We provide Siemensquality from a single source with a func-tion warranty for the entire system.

    Read more in "Our Services.

    Fig. 12: Analyzer house (shelter)

    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 detectorssuch 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 combinesminiaturization 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 reducedcycle times, provides valveless sample injection and column switchingand saves installation, maintenance, and service costs.

    SITRANS CV SITRANS CV is a micro process gas chromatograph especially designedfor reliable, exact and fast analysis of natural gas. The rugged and com-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 naturalgas market, e.g. custody transfer.

    Fig. 11: Product scope Siemens Process Gas Chromatographs

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    Siemens Process Analytics at a glanceSolutions (continued) and Services

    Our solutions ...

    Analyzer networking fordata communication

    Engineering and manufacturing of pro-cess analytical solutions increasinglycomprises "networking". It is getting astandard requirement in the processindustry to connect analyzers andanalyzer systems to a communicationnetwork to provide for continuous anddirect data transfer from and to theanalysers.The two objectives are (fig. 14):

    To integrate the analyzer andanalyzer systems seamless into thePCS / DCS system of the plantand

    To allow direct access to the analyzersor systems from a maintenancestation to ensure correct and reliableoperation including preventive orpredictive maintenance (fig.13).

    Siemens Process Analytics provides net-working solutions to meet the demandsof both objectives.

    Our ServicesSiemens Process Analytics is your com-petent and reliable partner world widefor Service, Support and Consulting.

    Our rescources for that are

    ExpertiseAs a manufacturer of a broad variety

    of analyzers, we are very much expe-rienced in engineering and manufac-turing of analytical systems andanalyzer houses.We are familiar with communicationnetworks, well trained in service andmaintenance and familiar with manyindustrial pro cesses and industries.Thus, Siemens Process Analytics ownsa unique blend of overall analyticalexpertise and experience.

    Global presenceWith our strategically located centersof competence in Germany, USA,Singapore, Dubai and Shanghai, weare globally present and acquaintedwith all respective local and regionalrequirements, codes and standards.All centers are networked together.

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    Fig. 14: Networking for DCS integration and maintenance support

    Fig. 15: Portfolio of services

    Fig. 13: Communication technologies

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    8

    Siemens Process Analytics at a glanceServices, continued

    Our Services ...

    Service portfolio

    Our wide portfolio of services is seg-mented into Consulting, Support andService (fig. 15 to 16). It comprisesreally all measures, actions and advisesthat may be required by our clientsthroughout the entire lifecycle of theirplant. It ranges from site survey toinstallation check, from instruction ofplant personnel to spare part stock man-agement and from FEED for ProcessAnalytics (see below) to internet-basedservice Hotline.

    Our service and support portfolio(including third-party equipment) com-prises 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 engi-neering phase of a plant construction ormodification project and is done afterconceptual business planning and prior

    to detail design. During the FEED phase,best opportunities exist for costs andtime savings for the project, as duringthis phase most of the entire costs aredefined and changes have least impactto the project. Siemens Process Analyt-ics holds a unique blend of expertise inanalytical technologies, applicationsand in providing complete analyticalsolutions to many industries.

    Based on its expertise in analytical tech-nology, application and engineering ,Siemens Process Analytics offer a widescope of FEED services focused on anal-ysing principles, sampling technologies,application solutions as well as commu-nication system and given standards (allrelated to analytics) to support our cli-ents in maximizing performance andefficiency of their projects.

    Whether you are plant operators orbelong to an EPC Contractor you willbenefit in various ways from FEED forProcess Analytics by Siemens:

    Analytics and industry know howavailable, right from the beginningof the project

    Superior analyzer system perfor-mance with high availability

    Established studies, that lead to

    realistic investment decisions Fast and clear design of the analyzer

    system specifications, drawings anddocumentation

    Little project management andcoordination effort, due to oneresponsible contact person andless time involvement

    Additional expertise on demand,without having the costs, the effortand the risks of building up the capac-ities

    Lowest possible Total Costs of Owner-ship (TCO) along the lifecycle regard-

    ing investment costs, consumptions,utilities supply and maintenance.

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

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    www.siemens.com/processanalytics Siemens AG 2007Subject to change

    Case Study

    Siemens AG

    Automation and DrivesSensors and CommunicationProcess Analytics76181 KARLSRUHE

    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 AGA&D SC PA, Process Analyticsstliche Rheinbrckenstr. 5076187 KarlsruheGermany

    Phone:+49 721 595 3829Fax: +49 721 595 6375E-mail:[email protected]/prozessanalytics

    Siemens Ltd., ChinaA&D SC, Process Analytics7F, China Marine TowerNo.1 Pu Dong AvenueShanghai, 200120P.R.China

    Phone:+86 21 3889 3602Fax: +86 21 3889 3264E-mail: [email protected]

    Siemens Energy & Automation Inc.7101 Hollister RoadHouston, TX 77040USA

    Phone:+1 713 939 7400Fax: +1 713 939 9050E-mail: [email protected]

    www.siemens.com/processanalytics

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

    Phone:+971 4 366 0159Fax: +971 4 3660019E-mail: [email protected]/processanalytics

    Siemens Pte. LimitedA&D SC PS/PA CoC60 MacPherson RoadSingapore 348615

    Phone:+65 6490 8728Fax: +65 6490 8729E-mail: [email protected]

    www.siemens.com/processanalytics