KarlHeinz Koch Process AnalyticalChemistry Springer-Verlag Berlin Heidelberg GmbH Karl Heinz Koch Process Analytical Chemistry Control,Optimization,Quality, Economy With97figures Springer ProfessorDr.KarlHeinz Koch AufdemMiihlenhofe41 D-44267Dortmund TitleoftheGermanedition:IndustrielleProzeBanalytik,Springer-Verlag Berlin Heidelberg1997 LibraryofCongressCataloging-in-PublicationData Koch,KarlHeinz: ProcessAnalyticalChemistry:Control,Optimization,Quality,Economy/KarlHeinzKoch.-Berlin; Heidelberg;NewYork;Barcelona;HongKong;London;Milan;Paris;Singapore;Tokyo: Springer,1999 Dt.Ausg.u.d.T.:IndustrielleProzeBanalytik,1997 ISBN 978-3-642-08468-3 ISBN 978-3-662-03772-0 (eBook) DOI 10.1007/978-3-662-03772-0 Thisworkissubject tocopyright.Allrightsarereserved,whether thewholepartofthematerialisconcer ned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation,broadcasting,reproduc tiononmicroftlmorinanyotherway,andstorageindatabanks.Duplication ofthispublicationorpartsthe reofispermittedonlyundertheprovisionsoftheGermanCopyrightLawofSeptember9,1965,initscurrent version,andpermissionforusemustalwaysbeobtainedfromSpringer-Verlag.Violationsareliableforpros ecutionundertheGermanCopyrightLaw. ©Springer-VerlagBerlinHeidelberg1999 OriginallypublishedbySpringer-VerlagBerlinHeidelbergNew York in1999. Softcoverreprintofthehardcover Istedition 1999 Theuseofgeneraldescriptivenames,registerednames,trademarks,etc.inthispublicationdoesnotimply, evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevantprotectivelawsand regulationsandthereforefreeforgeneraluse. Cover-Design:Design&Production,Heidelberg Typesetting: MEDIOGmbH,Berlin SPIN:10687202 52/3020-543210- Printedonacid-freepaper Preface Industrial process analytics is,like the whole field of analytical chemistry, an integraland essential partofeveryindustrialcompanybasedon chemical reac tions. It provides decision aids in the series ofprocess steps,so its results have decisivetechnical, economic and ecological effects.Therefore, this partof ana lytics must hence be included in the teaching of modern "applied" analytical chemistry.Onlyinthiswaycanthestudent,particularlytheadvanced one,recog nisethe realrelevanceofthis scientificmatter,and learnthewaythe methodsof analyticsare applied forsolutionsto problemsin actual practice: adiscrepancy between universitytrainingand workingliferealities isavoided and the variety in"instrumental"(physical) analytics becomesmore comprehensible. This bookistherefore aimed, on the one hand, at advanced students ofana lyticalchemistry,chemical engineering(chemical process technology),material sciencesand,ontheotherhand,attheanalyticalpractitioner,thechemicalengi neer and the process engineerwho requires informationaboutthe possibilities and methodsofprocess analytics and knowledge abouttheirefficiency,e.g.with regard to industrial process optimization.In this case,the chemical engineers and chemicalengineeringtechniciansworkinginsmalland medium-sizedcom panies arealsoincluded,thesehaving tosolveprocess analyticalproblemswith out an experienced analyst by their sides. For this purpose, lists of suppliers added to particularchapters,which naturallycannot make any claims to com pleteness, are intended to be helpful, and can make practical problem solving easier.Forthe advancedstudentsinterestedinanalytics thisvolume isintended to impartinsightsinto the necessity forthe developmentand the applicationof analytical methods in industrialpractice, and itcan possibly serve the purpose oforientationforadvancedstudies. This presentation ofindustrial process analytics issupposedto be asupple ment toproven textbooksand manualsand ismade intheknowledge that more recent booksinthe fieldofindustrialanalyticsarescarce. Forthe descriptionofthe contentsofthe first chapters,dividedaccordingto the aggregate states,the scientific basis ofthe methods isbriefly presentedand after that the state-of-the-artisdescribedbyexamples.The references annexed toeachchapterareintendedtoprovidemore profoundaccesstothematter.The publicationscited can provide furtherhelp. In some chapters examples for the interaction and the mutual dependence and reciprocal influencing ofvarious disciplines are described. In this way,for VI Preface example,the future analystor chemicalengineerisdirectlyacquaintedwith the necessityofan interdisciplinarydialogue. Inaconcludingchaptertheintegrationofqualityassurance- aconceptwhich in connection with the European Market has become of considerable impor tance forthewholeindustryand fortheanalytics- into process engineeringand process analyticsisdealtwith. Finallyitshouldbe mentioned that, when dealing with particularsub-areas, the scientificbasis ofthe analyticalmethodsisgenerallypresupposed. For stimulating discussions and helpful indications the undersigned would liketo thankmost sincerelyProf.Dr.ManfredGrasserbauer.Furthermore,spe cial thanks to Dr.J. Flock,Dortmund,for preparing numerous figures. Finally, manythanks to the Springer-Verlagfor the unbroken realizationofthis project withoutanyproblem. Dortmund/Vienna,1999 K.H.Koch Table of Contents 1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 FieldsofApplicationofIndustrialAnalytics . . . . . . 1.2 On the HistoryofProcess AnalyticalChemistry . . . . 7 1.3 EconomicImportanceofProcess AnalyticalChemistry 10 1.4 PresentationandOrganizationalFormsof Process AnalyticalChemistry 11 1.5 ImportanceofSampling 12 References . 15 2 ProcessAnalyticsofGases 17 2.1 Importancefor IndustryandSociety 17 2.2 SamplingofGases . 19 2.3 Analysis of Gases . . . . . . . . 21 z.j.i MeasurementofPhysicalEffects 21 2.3.1.1 Paramagnetism . . 21 2.3.1.2 Heat Conductivity . 22 2.3.1.3 Heat Change . . . . . . . 23 2.3.1.4 Reactionson SemiconductorSurfaces 25 2.3.2 SpectroscopicMethods . . . 26 2.3.2.1 UV,VISandIRSpectroscopy 26 2.3.2.2 MassSpectrometry . . 31 2.3.2.3 Chemiluminescence 32 2.3.3 ElectrometricMethods 33 2.3.4 GasChromatography . 36 2.4 Suppliersfor GasAnalyzers andGasSensors 37 2.4.1 ParamagneticGasAnalyzers . . . . . . . 37 2.4.2 Heat ConductivityMeasuringEquipment 38 2.4.3 GasSensorsBasedon Heat ofReaction 38 2-4-4 SemiconductorSensors . . . . . . . 38 2.4.5 UV-IVIS-/NIR-Process Photometers 38 2-4.6 IRProcess Photometers . . . .. 39 2-4-7 MassSpectrometricGasAnalyzers 39 2.4.8 ChemiluminescenceSensors . . . 39 VIII Tableof Contents 2-4.9 ElectrometricMeasuringSystems 39 2.4.10 Process Chromatographs 40 2.4.11 Remarks 40 References . 40 3 ProcessAnalyticsofLiquidPhases 42 J.1 SamplingofLiquid Phases .. 42 3·1.1 AqueousandOrganicMaterials 42 3·1.2 MeltsofMetallicMaterials ... 44 3·2 Analysis ofLiquid Phases . . . . 44 3·2.1 AqueousandOrganicMaterials 44 3·2.1.1 On-LineConcepts . 44 3·2.1.2 In-Line AnalyticsandSensorTechnology 55 3·2·1.3 Off-LineConcepts . 57 3·2.2 Melts . 62 3·3 Suppliersfor Process AnalyzersandOff-LineAnalytical Equipmentfor Process Control 3·3·1 ProcessTitrators ... . . 3·3·2 ElectrochemicalAnalyzers . . 3·3·3 ProcessPhotometers . . . .. 3-3-4 X-RayFluorescenceSpectrometer/X-Ray DiffractionSpectrometer . . 3.3.5 FT-IR/RamanSpectrometer 3.3.6 LaboratoryRobots .. . . . 3.3.7 Fluorescence/StrayLightSensors 3.3.8 Remarks References . 4 ProcessAnalyticsofSolidMaterials 4·1 SamplingofProductFlows . . 67 4·2 AnalyticalMethodsforSolids 70 4·2.1 X-RayFluorescenceAnalysis 70 4·2.2 X-RayDiffraction . 72 4·2·3 NeutronScattering . 72 4·2·4 MicrowaveTransmission . . 74 4·3 Examples for IndustrialApplications 74 4·3·1 Process ControlofCementProduction 74 4.3.2 On-LineAnalysis ofFlotationProcesses 77 4·3·3 ProcessAnalyticsofCopperMetallurgy 80 4·3·4 ContinuousControlofIronOreSinter Production 81 4·3·5 On-Line Analysis ofLump Materials . 84 4·4 Suppliersfor SamplingandSample Preparation Devices andforAnalyticalandAutomationSystems 86 4·4·1 SamplingandSample Preparation . . . . . . . . . 86 Tableof Contents IX 442 Wavelength-DispersiveX-RayFluorescenceSpectrometers 86 443 Energy-DispersiveX-RayFluorescenceSpectrometers 86 4.4.4 X-RayDiffractometers ..... 87 4.4.5 RadiometricAnalyticalSystems 87 446 Remarks 87 References . 87 5 ProcessAnalyticsintheChemicalIndustry 5.1 The RoleofAnalyticsin the ChemicalIndustry 5.2 Process Analyticsfor Dye-Stuff Production (Batch Process Control) . 90 5.3 On-LineAnalyticsandBiosensoricsin Biotechnology 92 5.3.1 Biotechnologyand Bioprocesses . . . . 92 5.3-2 TotalChemical Analysis Systems (TAS) . 93 5.3.3 FlowInjectionAnalysis (FIA) . 95 5.3.4 High PerformanceLiquid Chromatography(HPLC) 98 5.3.5 CapillaryElectrophoresis (CE) ... 98 5.4 Suppliersfor Sensorsand Appliances 99 5.4.1 Remarks 99 References . 99 6 MetallurgicalProcessTechnologyandChemicalProcessAnalytics 101 6.1 Introduction................ .... ... 101 6.1.1 EconomicImportanceofIron (Steel)anditsMetallurgy 101 6.1.2 PresenceofIron inNature 103 6.1.3 History 104 6.1.4 The MetallurgicalProductsPigIron andSteel 105 6.2 Process Analyticsofthe BlastFurnaceProcess 108 6.2.1 MetallurgyanditsAnalyticalRequisites . 108 6.2.2 Process TechnologyandProcess Analytics . . 112 6.3 Process AnalyticsofSteelProduction 118 6.3-1 MetallurgyanditsAnalyticalPresuppositions 118 6.3.2 MethodsofProcess Analytics 126 6.3.2.1 SamplingandSample Preparation . 126 6.3.2.2 AnalyticalMethods . . . . . . . . . 128 6.3.2.3 AutomatizationofProcess Analytics Methodsin CentralLaboratories 131 6.3.2.4 On-SiteAnalytics . . . . . . . . . . 134 6.3.2.5 In-LineAnalytics . . . . . . . . . . 137 6.4 Process Analyticsin Non-FerrousMetallurgy 138 6.5 AnalyticalInvestigationsofMetalFormingandAnnealing ProcessesforSheet Production . . . 139 6.6 ControlofSurface CoatingProcesses 146 6.7 AnalyticsofMetallic Materials . . . 148 X Tableof Contents 6.7.1 MaterialPropertiesandTraceAnalysis ofSteelMaterials 148 6.7.2 Phase andMicroanalytics 150 6.7.3 Surface TechnologyandSurfaceAnalytics . . . . . . . 152 6.7.3-1 ImportanceofSurface AnalyticalMethods . . . . . . . 152 6.7.3.2 Applicationof GlowDischargeEmissionSpectrometry 155 6.7.3.3 InvestigationsofCoatedMaterialswithSecondaryNeutral ParticleMassSpectrometry 159 6.8 SuppliersofSampling,Sample Preparation,Analysis and AutomationSystems 163 6.8.1 SamplingProbes 163 6.8.2 PneumaticTubeSystems forSample Transport 163 6.8.3 AutomatedSample PreparationbyCutting,Grindingor CrushingandPressingRespectively . . 164 6.8.4 LaboratoryAutomation 164 6.8.5 CalibrationSamples/ReferenceMaterials 164 6.8.6 OpticalEmission Spectrometer 164 6.8.7 X-RayFluorescenceSpectrometer . . . 165 6.8.8 Analysersfor the DeterminationofCarbon,Sulphur, Nitrogen,Oxygenand Hydrogenin Metals 165 6.8.9 Container/CabinLaboratories 165 6.8.10 MobileSpectrometer 165 6.8.11 Remarks 165 References 166 7 ProcessAnalyticsintheSemiconductorIndustry 7.1 Introduction . . . . . . . . 169 7.1.1 MicroelectronicTechnology 169 7.1.2 SemiconductorTechnology . 170 7.1.3 Solar Technology . . . . . . 171 7.2 InvestigationofSiliconSubstrates 172 7.3 Surface andThinLayerAnalytics 174 7.4 AnalyticalControlofUltra-PureChemicalsand ChemicalProcesses . . . . . . . . . . . . . . . 177 7.5 ContaminationControlofProcessesandProductionInstallations 177 References 180 8 ProcessTechnologyandEnvironment . . . . . 8.1 Protectionofthe EnvironmentandSociety . 183 8.2 Analysis ofAirandits Pollutants . . . . . . . . . . . . . 186 8.3 Analysis ofthe ConstituentsofDrinkingWater,Water Fit for IndustrialUseandWasteWater . . . . . 188 8·3·1 Process TechnologyandLegislation . ... 188 8·3.2 Water TreatmentandWasteWaterAnalytics 190 8·3·3 WasteWater LawandWasteWaterAnalytics 194