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”

UCM

(20

1

p p yp p y

Real time measurements of reactants intermediatesReal time measurements of reactants intermediates

LLAN

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

OREthe process or reaction, its efficiency and yield for

control, optimization and other decision-making steps.the process or reaction, its efficiency and yield for control, optimization and other decision-making steps.

© G

uille

r

Includes ©Includes... sampling pretreatment pretreatment measurement interpretation application of data

12)Industrial incentives for process analyzer Industrial incentives for process analyzer

UCM

(20

1

technologytechnology

LLAN

A, U

Automated process control

rmo

ORE

Automated process control Optimal operating efficiency

© G

uille

r

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

UCM

(20

1

driven by analytical technologydriven by analytical technology

LLAN

A, U

Origins: IR absorption recorders and l (l ‘30 )

rmo

OREparamagnetic oxygen analyzers (late ‘30s)

Differential thermal conductimeters & di till ti t l (‘40s)

© G

uille

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

UCM

(20

1

PROCESS STREAM

LLAN

A, U

PPSample

loop

rmo

ORE

S

© G

uille

rSS

S

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

UCM

(20

1

Highly automated (unattended operation)

LLAN

A, U Highly automated (unattended operation)

Rugged, operable in hazardous areas Simple serviceable by untrained personnel

rmo

ORE

Simple, serviceable by untrained personnel Adequate vendor technical support Calibrated for long time/automatic recalibration

© G

uille

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

UCM

(20

1

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

LLAN

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”.

rmo

OREDepends on the nature of...

the type of line analysis

© G

uille

r

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

UCM

(20

1LL

ANA,

U

Electronic spectroscopies UV + optical fiber (+sensor)

rmo

ORE VIS

Fluorescence

Vibrational spectroscopies

p ( )

© G

uille

r Vibrational spectroscopies NIR IR ©

Raman Refraction index Image analysis

12)Process UV/Vis spectroscopyProcess UV/Vis spectroscopy

UCM

(20

1

S i l

LLAN

A, U Scanning analyzers

Photodiode array analyzers

rmo

ORE

© G

uille

r©

AGILENT

12)Process analysis by UV-VIS sensorsProcess analysis by UV-VIS sensors

UCM

(20

1

Ind st ial cleaning alidation

LLAN

A, UIndustrial cleaning validation

rmo

ORE

© G

uille

r©

12)Process analysis by UV-VIS sensorsProcess analysis by UV-VIS sensors

UCM

(20

1

On line anal sis of pol me s

LLAN

A, UOn-line analysis of polymers

and additives

rmo

ORE

© G

uille

r©

12)Process analysis by UV-VIS sensorsProcess analysis by UV-VIS sensors

UCM

(20

1

Monolithic spect omete s

LLAN

A, UMonolithic spectrometers

rmo

ORE

Automated measurements of permanganate time

© G

uille

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

UCM

(20

1

Monito i ation of e t act content

LLAN

A, UMonitorization of extract content

and cell count in beer brewing

rmo

ORE

© G

uille

r©

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

UCM

(20

1

Monitorization of alcohols in

LLAN

A, U

unleaded petrol blending linesN

N

N

S NH2

rmo

ORE

N

© G

uille

r©

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

UCM

(20

1

Sma t food packaging

LLAN

A, USmart food packaging

rmo

ORE

© G

uille

r

O2 [Ru(dip)3]2+

©

CO2 [Ru(dip)3]2+/BTB

(Ireland)

12)Process analysis by NIR sensorsProcess analysis by NIR sensors

UCM

(20

1

Dete mination of octane n mbe

LLAN

A, UDetermination of octane number

rmo

ORE

© G

uille

r©

Chemometrics!!!Patented wavelengths:Maggard, US Pat. 5,349,189 (1994)(1994)

12)Process analysis by NIR sensorsProcess analysis by NIR sensors

UCM

(20

1

Determination of octane number

LLAN

A, U

rmo

ORE

© G

uille

r©

12)Process analysis by FT-IR fiberoptic sensorsProcess analysis by FT-IR fiberoptic sensors

UCM

(20

1

Phosgenation of diamines

LLAN

A, UPhosgenation of diamines

H2N-R-NH2 + 2 COCl2 OCN-R-NCO + 4 HCl1810 cm-1 2260 cm-1

rmo

ORE

1810 cm 1 2260 cm 1

© G

uille

r©

22601810

ReacTIR®

12)Process analysis by Raman sensorsProcess analysis by Raman sensors

UCM

(20

1

Monitorization of emulsion polymerization reactions

Important process for:• paints

LLAN

A, Upolymerization reactions • paints

• adhesive products• sinthetic rubbers• solid supports

rmo

ORE

pp(free radical)

© G

uille

r©

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

UCM

(20

1

Monitorization of emulsion polymerization reactions

LLAN

A, Upolymerization reactions

rmo

ORE

© G

uille

r©

KAISER OPTICAL SYSTEMS, Inc.(ratiometric)