Liquid Injection valve testing for Micro-GC adaptation - University … · 2012-11-27 · •...

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Liquid Injection valve testing for Micro-GC adaptation IFPAC – 2012 Ramy Abou Naccoul, Ph.D. Claude Bernard University Lyon *Claude Bernard University, LSA team – **SRA instruments, + IFPEN, France LSA/TAP - IFPAC 2012 - Baltimore MD V. Malicet*, I. Mokbel*, R. Cozic**, J. Jose*, F. Baco-Antoniali +

Transcript of Liquid Injection valve testing for Micro-GC adaptation - University … · 2012-11-27 · •...

Page 1: Liquid Injection valve testing for Micro-GC adaptation - University … · 2012-11-27 · • Injection of alkane mixture in Fast GC configuration HPLIS • Direct connection of the

Liquid Injection valve testing for Micro-GC adaptation

IFPAC – 2012

Ramy Abou Naccoul, Ph.D. Claude Bernard University Lyon

*Claude Bernard University, LSA team – **SRA instruments, + IFPEN, France

LSA/TAP - IFPAC 2012 - Baltimore MD

V. Malicet*, I. Mokbel*, R. Cozic**, J. Jose*, F. Baco-Antoniali+

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LSA/TAP - IFPAC 2012 - Baltimore MD

Context: needs of micro-analyzers and micro-sensors

Difficulties to implement on industrial sites and R&D laboratories, because of:

- Unsatisfactory accordance between analyzers and industrials needs

- Some laboratories techniques not adapted for in situ application

Problematic of the existing micro-analyzers and micro-sensors:

To analyze at the closest of the process, needs are:

- micro analyzers, micro sensors

- coupled with sampling microsystems

directly integrated into the process

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Instrumentalists

Laboratories

Industries

LSA/TAP - IFPAC 2012 - Baltimore MD

How to answer to the needs for micro analysis?

Project “INnovAL”

INDUSTRIES (Arkema, Rhodia, Bluestar, Perstrop, IFPEN) Request – Validation - Optimization

LABORATORIES (University Lyon) Ecole des Mines (St Etienne)

Research

INSTRUMENTALISTS (SRA, EIF) Development & Industrialization

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LSA/TAP - IFPAC 2012 - Baltimore MD

University of Lyon : Our contribution in the INnovAL Project: Development of liquid sampling-vaporization system for μGC Development of a μGC for on line analysis of liquid (available only

for gas analysis because of the temperature limit of the injector: < 100°C)

Optimization of micro-sensors

Density, particles ...

Page 5: Liquid Injection valve testing for Micro-GC adaptation - University … · 2012-11-27 · • Injection of alkane mixture in Fast GC configuration HPLIS • Direct connection of the

Comparison of the performance of the two online sampling/injection systems

• Heated Pressurized Liquid Injection System HPLIS (from SRA) • Rapid On Line Sampling Injector ROLSI (from EIF)

The comparison between the 2 valves is carried out using a synthetic mixture of n-alkanes and by studying:

• Chromatographic Repeatability • Existence of discrimination between the alkanes

Advantages and limitation of each sampling system

Function of : • Temperature • Pressure

LSA/TAP - IFPAC 2012 - Baltimore MD

The aim of the study : Find the most suitable liquid valve , optimize and couple to the micro-GC

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Moving partCarrier gaz inlet

Cappillary

Vaporisation chamber

Carrier gaz outlet Cooling fan

Spring

Electromagnet

Soft iron Core

ROLSI valve

Specification : • Maximum operating pressure 300 bar • Maximum operating temperature 250 °C • Transfer line upstream the GC, 300°C • Adjustable injection volume

LSA/TAP - IFPAC 2012 - Baltimore MD

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HPLIS

Specification : • Maximum operating pressure 80 bar • Maximum operating temperature 220 °C • Sample volume 0.06 μL • HStem 350 °C

LSA/TAP - IFPAC 2012 - Baltimore MD

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Operating System

LSA/TAP - IFPAC 2012 - Baltimore MD

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HPLIS Valve Response of the HPLIS valve as a function of the temperature of the valve chamber

(at constant injection pressure = 6 bar )

Oven

Initial temperature

Final temperature

Time

50 oC 1 min 40 oC/min 320 oC 30 min

Carrier flow 1.1 ml/min FID temperature 320 oC

Injector temperature 280 °C

LSA/TAP - IFPAC 2012 - Baltimore MD

Conclusion: discrimination between the alkanes due to the low t°C max of the valve chamber (joint)

PTFE joint were replaced by glass-PTFE joint

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HPLIS Valve

Conclusion:

*Pressure dependence was observed

*increase of 1.7% of the peak area

per 1 bar of pressure increase (PTFE)

*no dependence when using

glass-PTFE

LSA/TAP - IFPAC 2012 - Baltimore MD

Response of the HPLIS valve as a function of the upstream liquid pressure: 15 to 40 bars

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HPLIS and fast-GC HPLIS has been tested in fast-GC configuration in order to simulate the Micro-GC conditions

A synthetic mixture of n-alkanes is used at atmospheric pressure

Column DB-1 : L=20m, I.D=0.1mm, 0.1μm Carrier gas : Hydrogen

Conclusion: shorter time of analysis (12 minutes gain) but same discrimination phenomenon than with normal GC

LSA/TAP - IFPAC 2012 - Baltimore MD

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ROLSI valve n-alkane mixture between n-C8 and n-C16 at different injection pressures

valve chamber : 230 °C Transfer Line : 240°C

Pressures : 16 – 25 – 38 – 75 – 100 bar

LSA/TAP - IFPAC 2012 - Baltimore MD Conclusion: Discrimination between the alkanes independent from liquid pressure

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ROLSI valve Discrimination study versus the valve chamber temperature

Three temperatures were tested 180, 220, 250°C using a synthetic mixture of n-alkanes

LSA/TAP - IFPAC 2012 - Baltimore MD Conclusion: the temperature of the valve has no effect on the discrimination

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ROLSI Vs HPLIS A synthetic mixture of n-alkanes between n-C8 and n-C38 is used to evaluate the

performance of HPLIS and ROLSI at different pressures and temperatures

LSA/TAP - IFPAC 2012 - Baltimore MD

HPLIS • Discrimination independent from injection pressure • Temperature limitation to 220°C (normal PTFE joints) • Temperature limitation to 300°C (PTFE-glass joints) • Contamination of the core

ROLSI • Discrimination independent from injection pressure • Temperature up to 250°C • Long transfer line • Adjustable sampling volume

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Perspectives ROLSI

• Installation of the ROLSI valve directly on the GC injector, elimination of the transfer line

• Increase the temperature of the ROLSI’s injection chamber, isolation of the valve chamber from the core

• Injection of alkane mixture in Fast GC configuration HPLIS

• Direct connection of the valve to the column (bypassing the GC split injector) • Test of new gasket (based on Vespel) to increase pressure and heat of the valve:

decrease discrimination • Injection of high boiling point mixture (efficiency of the flash heating)

LSA/TAP - IFPAC 2012 - Baltimore MD

In the frame work of a PhD thesis : • Improvements of Rolsi and HPLIS valves • conception, built and trial of a new liquid injection valve and adaptation to μGC

How ?

Page 16: Liquid Injection valve testing for Micro-GC adaptation - University … · 2012-11-27 · • Injection of alkane mixture in Fast GC configuration HPLIS • Direct connection of the

Perspectives

LSA/TAP - IFPAC 2012 - Baltimore MD

Liquid injection

Valve

Micro GC

Micro G

C SRA

Moving partCarrier gaz inlet

Cappillary

Vaporisation chamber

Carrier gaz outlet Cooling fan

Spring

Electromagnet

Soft iron Core

Objective : Place the injection valve and the Micro GC on the ASTUTE platform from EIF

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INNOVation pour l’Analyse en Ligne

Analysis in the heart of the process

CONFIDENTIEL

Acknowledgment

Page 18: Liquid Injection valve testing for Micro-GC adaptation - University … · 2012-11-27 · • Injection of alkane mixture in Fast GC configuration HPLIS • Direct connection of the

Instrumentalists

Laboratories

Industries

LSA/TAP - IFPAC 2012 - Baltimore MD

INDUSTRIES (IFPEN, Arkema, Rhodia, Bluestar, Perstrop) Request – Validation - Optimization

LABORATORIES (University Lyon) Ecole des Mines (St Etienne)

Research

INSTRUMENTALISTS (SRA, EIF) Development & Industrialization

Thank you for your attention


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