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OPTICAL CHEMICAL SENSORS FOROPTICAL CHEMICAL SENSORS FOROPTICAL CHEMICAL SENSORS FOROPTICAL CHEMICAL SENSORS FORPROCESS CHEMICAL ANALYSISPROCESS CHEMICAL ANALYSISPROCESS CHEMICAL ANALYSISPROCESS CHEMICAL ANALYSIS
Prof. Dr. Guillermo OrellanaProf. Dr. Guillermo Orellana
Optical Chemosensors & Applied Photochemistry GroupUNIVERSIDAD COMPLUTENSE de MADRIDUCM
12)Concept of “process analysis”Concept of “process analysis”
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p p yp p y
Real time measurements of reactants intermediatesReal time measurements of reactants intermediates
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A, UReal-time measurements of reactants, intermediates
and/or products that provide direct information about the process or reaction its efficiency and yield for
Real-time measurements of reactants, intermediates and/or products that provide direct information about the process or reaction its efficiency and yield for
rmo
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control, optimization and other decision-making steps.the process or reaction, its efficiency and yield for control, optimization and other decision-making steps.
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Includes ©Includes... sampling pretreatment pretreatment measurement interpretation application of data
12)Industrial incentives for process analyzer Industrial incentives for process analyzer
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technologytechnology
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Automated process control
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Automated process control Optimal operating efficiency
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Total product quality control Comply with governmental regulations ©p y g g
• industrial safety• hygieneyg• air/water/land quality
K.J. Clevett, Process Control Qual. 1994, 6, 81
12)Development of process analyzers is also Development of process analyzers is also
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driven by analytical technologydriven by analytical technology
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Origins: IR absorption recorders and l (l ‘30 )
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Differential thermal conductimeters & di till ti t l (‘40s)
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rdistillation-type analyzers (‘40s) UV/vis spectrometers (‘50s) Gas chromatographs (‘60s) © Gas chromatographs ( 60s) Process mass spectrometers (‘70s)
NIR analyzers (‘80s) NIR analyzers (‘80s) FT-IR, NIR, Raman/fiber optics/chemometrics
R.E. Sherman, “Analytical Instrumentation: Practical Guides for Measurement and Control”, Instrum. Soc. of America, NC, 1996
12)Main categories of process measurementsMain categories of process measurements
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PROCESS STREAM
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PPSample
loop
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S
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OFF-LINE ANALYSIS Discontinuous ©
Discontinuous Manual sampling & transport Sophisticated lab instruments Detailed quality control (long-term)
ON-LINE PROBES A t ti li & t t Detailed quality control (long-term)
AT-LINE ANALYSIS Manual sampling
Automatic sampling & transport Autonomous analysis Intermittent measurementsIN LINE PROBES
F. McLennan & B.R.Kowalski (eds.), “Process p g
Trained personnel Reduced time delays
IN-LINE PROBES Eliminates sampling Continuous measurements
Kowalski (eds.), ProcessAnalytical Chemistry”,Blackie, London, 1995
12)Requirements of process analyzersRequirements of process analyzers
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Highly automated (unattended operation)
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Rugged, operable in hazardous areas Simple serviceable by untrained personnel
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Simple, serviceable by untrained personnel Adequate vendor technical support Calibrated for long time/automatic recalibration
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r Calibrated for long time/automatic recalibration Fast enough measurement rate
R ©
R
R
k
1
i: process time constantk: chemical reaction rate constantR: reactor volume/volumetric flow rate
R.A. Potyrailo, in “Elsevier Enciclopedia of Materials”, 2001
12)Sampling strategiesSampling strategies
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A sampling system is “an assembly of components and equipment with the function of taking a representative sample from the process conditionA sampling system is “an assembly of components and equipment with the function of taking a representative sample from the process condition
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A, Uthe function of taking a representative sample from the process, condition
it, transporting and presenting it to the analyzer, and disposing of it”.the function of taking a representative sample from the process, conditionit, transporting and presenting it to the analyzer, and disposing of it”.
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the type of line analysis
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the process analytes the information required the type of analyzer ©yp y
Analyzer interfacing is one of the most important issues!
( li h dli i 85% f th bl ith / i l li ht(e.g. sampling handling issues are 85% of the problems with uv/vis process analyzers, light source failures contribute 5%, opto-electronic problems and others make the rest) (Sherman, 1996)
Pay attention to spatial heterogeneity of the sampled materialE.A. Houser, “Principles of Sample Handling and Sampling Systems Design for Process Analysis”, ISA, Pittsburgh, PA, 1972
Pay attention to spatial heterogeneity of the sampled material
12)Process optical spectroscopic techniquesProcess optical spectroscopic techniques
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Electronic spectroscopies UV + optical fiber (+sensor)
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Fluorescence
Vibrational spectroscopies
p ( )
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Raman Refraction index Image analysis
12)Process UV/Vis spectroscopyProcess UV/Vis spectroscopy
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S i l
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Photodiode array analyzers
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AGILENT
12)Process analysis by UV-VIS sensorsProcess analysis by UV-VIS sensors
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Ind st ial cleaning alidation
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12)Process analysis by UV-VIS sensorsProcess analysis by UV-VIS sensors
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On line anal sis of pol me s
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and additives
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12)Process analysis by UV-VIS sensorsProcess analysis by UV-VIS sensors
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Monolithic spect omete s
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Automated measurements of permanganate time
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r Automated measurements of permanganate time Analysis of aromatic hydrocarbons (BTX) in process water Optical dissolution analysis and control I li l i f fl d ©
In-line analysis of flavored waters Agricultural harvest machines Color measurements
12)Process analysis by fluorescent sensorsProcess analysis by fluorescent sensors
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Monito i ation of e t act content
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and cell count in beer brewing
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T S h t l U i HT. Scheper et al. Uni. HanoverGilde Brauerei AG, HanoverDelta Light & Optics, Denmark
12)Process analysis by fluorescent sensorsProcess analysis by fluorescent sensors
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Monitorization of alcohols in
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unleaded petrol blending linesN
N
N
S NH2
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N
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G. Orellana et al., Anal. Chem. 1995, 34, 2231G. Orellana et al., Span. Pat. 2065268
12)Process analysis by luminescent sensorsProcess analysis by luminescent sensors
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Sma t food packaging
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O2 [Ru(dip)3]2+
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CO2 [Ru(dip)3]2+/BTB
(Ireland)
12)Process analysis by NIR sensorsProcess analysis by NIR sensors
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Dete mination of octane n mbe
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Chemometrics!!!Patented wavelengths:Maggard, US Pat. 5,349,189 (1994)(1994)
12)Process analysis by NIR sensorsProcess analysis by NIR sensors
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Determination of octane number
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12)Process analysis by FT-IR fiberoptic sensorsProcess analysis by FT-IR fiberoptic sensors
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Phosgenation of diamines
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H2N-R-NH2 + 2 COCl2 OCN-R-NCO + 4 HCl1810 cm-1 2260 cm-1
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1810 cm 1 2260 cm 1
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22601810
ReacTIR®
12)Process analysis by Raman sensorsProcess analysis by Raman sensors
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Monitorization of emulsion polymerization reactions
Important process for:• paints
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• adhesive products• sinthetic rubbers• solid supports
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pp(free radical)
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785 LD
KAISER OPTICAL SYSTEMS, Inc.785 nm LD exc.
50 m opt. fiber (excit.)100 m opt. fiber (return)
12)Process analysis by Raman sensorsProcess analysis by Raman sensors
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Monitorization of emulsion polymerization reactions
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KAISER OPTICAL SYSTEMS, Inc.(ratiometric)