Renewable energies | Eco-friendly production | Innovative transport | Eco-efficient processes | Sustainable resources

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Trends and needs for online micro analysis for R&D

Dr. Noémie CAILLOL IFP Energies nouvelles BP3, 69360 Solaize, FRANCE

Dr. Franck BACO-ANTONIALI IDEEL BP3, 69360 Solaize, FRANCE Dr. Hervé THIEBAUD ARKEMA, Centre de Recherche Rhône Alpes, BP63, 69493, Pierre Bénite, FRANCE

INNOVAL INNOVATIVE PROJECT FOR MICRO PROCESS ANALYTICAL TECHNOLOGY

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L’analyse des procédés: un enjeu pour l'industrie chimique

PRODUCTION

Products Quality

Safety of employees

and neighborhood

Environment protection (pollution)

R&D

Reduction of costs

Process intensification

ANALYSIS + PROCESS CONDITIONS CONTROLS

Objective

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> Quality of the analysis > Sampling safety > Wastes management > ↘ Installation cost ($ € ) > ↘ Energy consuming systems

Analysis at the "heart of process"

Sampling loop

The future for industrial online analysis : in situ analysis

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Evolution of needs in term of analyzers in R&D

µ Pilots HTE Pilots Process Intensification

Reduction of sample volume

"Classical" analyzers

µ Analyzers

µSensors

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•More compact analyzers to be able to analyze at the heart of process "bring the analyzer to the sample" • Reduce time of experimentation and Increase the number of tests at the same time we need Smart analyzers to follow process stabilization, product quality, process control , ...

+ Excellent repeatability, accurate systems, good agreement with

standard methods, ...

Needs for R&D and Process Intensification

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New generation of analyzers: - compact (micro analyzers, micro sensors) - coupled with sampling microsystems - directly integrated to the process

>> Analysis at the closest of the reaction New Standard (SP76) NeSSI TM New Sampling and Sensor Initiative from CPAC

Issue

> Difficulties of direct implementation on industrial sites and R&D laboratories

- Unsatisfactory agreement between analyzers and industrials/R&D needs

- Laboratory techniques are not always available for in-situ applications

Difficulties

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Need

Need for more compact analyzers to be able to analyze

“at the heart of process"

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How to answer the needs for Micro Analysis?

Micro Analysis Needs Collaborative project

USERS Request - Validation

LABORATORIES Research

INSTRUMENTALISTS Development & Industrialization

INNovAL Project

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INnovAL – Main Actors

USERS Request - Validation

LABORATORIES Research

INSTRUMENTALISTS Development & Industrialization

(LIBS)

(GC)

(TDL)

(sampling)

(sensors)

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Targets: -Development of new in situ on-line analyzers in agreement with industrial and R&D needs -Optimization of technologies available on the market -Development of new and innovative solutions

INnovAL Project (AXELERA) "L'Analyse en Ligne au cœur du procédé"

Properties Molecular Properties Molecular

Analysis in liquids Analysis in gases Elemental analysis

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Elemental Analysis

In situ analysis of elements in industrial liquids traces of S, Ni & V in petroleum products contaminants analysis in ex-biomass and chemical products, ... traces analysis of contaminants in water monitoring of corrosion (traces of metals) ...

Laser Induced Breakdown Spectroscopy

Main Objectif: Develop a online LIBS analyser (LinLIBS)

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Elemental Analysis

1st year results: Lab evaluation of feasibility of industrial applications

IFPEN’s : S, Ni & V in petroleum products 2nd year results:

Definitions of optimal measurement conditions (Wavelength, sampling mode…) Equipment development compatible with NeSSI standard

3rd year results: Prototype assembly, lab spectrometer evaluations and analysing protocol

optimisation Final year:

On-line evaluation on a semi-industrial pilot unit at IFPEN

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Analysis in liquids - Properties

In situ analysis of elements in industrial liquids

in situ density, viscosity analysis of liquids with µsystems in situ refractive index analysis with µsystems particles analysis in liquid (solid, catalyst, macromolecules, ...) calculation of other properties using µspectrometers

Adaptation in function of specific needs Specific developments

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Analysis in liquids - Properties Example of In situ density with Excalibur µdensimeter Repeatability

Densité en ligne - Gazole

P=Patm, Qv = 2 ml/min

22

22.5

23

23.5

24

24.5

25

28/1/08 23:16 29/1/08 0:28 29/1/08 1:40 29/1/08 2:52 29/1/08 4:04 29/1/08 5:16 29/1/08 6:28 29/1/08 7:40

Time

Tem

pera

ture

(°C)

0.8435

0.8445

0.8455

0.8465

0.8475

0.8485

0.8495

0.8505

0.8515

dens

ity

(g/c

m3 )

T captor (°C)direct densityCorrected density at 15°C

Products

Numbers of measures

MV average g/cm3

St. Deviation g/cm3

Reapitability g/cm3

Gasoil

740

0,8509

1,96.10-5

5,49 10-5

Repeatability for diesel

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Analysis in liquids - Properties Example of In situ density with Excalibur µdensimeter Response to a periodic feed change

less than 30s – Flow 2ml/min

23

23.5

24

24.5

25

25.5

26

26.5

27

31/1/08 11:15 31/1/08 11:18 31/1/08 11:21 31/1/08 11:24 31/1/08 11:26 31/1/08 11:29 31/1/08 11:32 31/1/08 11:35 31/1/08 11:38 31/1/08 11:41

Time

Tem

pera

ture

(°C)

0.8405

0.8415

0.8425

0.8435

0.8445

0.8455

0.8465

0.8475

0.8485

0.8495

0.8505

dens

ity

(g/c

m3 )

T captor (°C)

Raw density

Corrected density

Gasoil A Gasoil A Gasoil A

Gasoil B Gasoil B

difference (A-B) 0.0006 g/cm3

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Analysis in liquids - Properties Example of In situ density with Excalibur µdensimeter µpilot test : gasoline + dissolved gas

0.7105

0.7155

0.7205

0.7255

0.7305

0.7355

0.7405

0.7455

0.7505

3/9/08 0:00 5/9/08 0:00 7/9/08 0:00 9/9/08 0:00 11/9/08 0:00 13/9/08 0:00 15/9/08 0:00 17/9/08 0:00

Date & Hour

Den

sity

(g/

cm3)

15.00

25.00

35.00

45.00

55.00

65.00

75.00

Tem

pera

ture

(°C

)

Corrected density at 15°CLaboratory analysis 15°CTemperature Captor (°C)

Better results with online analysis

Loss of gas phase

We are able to follow the "real life" of a process Better knowledge for R&D development

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In situ analysis in different industrial liquids

with µspectrometric methods (miniaturized systems), using in situ probes Development and performance optimization for several

applications

in situ analysis of dissolved gases (traces) in hydrocarbons (H2, O2, ...)

Development of liquid injection systems for on line µGC analysis at the moment µGC is only used for gas analysis Development of a new injection system for liquides.

Analysis in liquids- Molecular Analysis

min0 20 40 60 80 100

pA

10

15

20

25

30

35

40

45

FID1 A, (D:\DOCUMENTS AND SETTINGS\JACQUINE\BUREAU\ETUDE HPLIS\DATA\P20BARS\001F0101.D)

PIC

1

PIC

2

PIC

3

PIC

4

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For IFPEN : For Bluestar:

For Arkema: For Solvay, Vencorex, …

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Spectroscopic applications evaluation : UV, ATR, IR, Raman

Analysis in liquids- Molecular Analysis

application Evaluation & adaptation Hydrogen content monitoring in diesel by NIR

Development of a transfer function from lab model to online analysis

Xylene Isomer quantification by Raman Models develop on miniaturized spectrometer

application Evaluation & adaptation commentary

hydrosilylation reaction by Raman and MIR

qualitative and quantitative analysis - Validation of lab model on fabrication unit

First online Raman Spectrometer installation on Process

application Evaluation & adaptation commentary

Monitoring of a mineral component in a Fluor environment by RAMAN A specific analysis cell developed by EIF Installation on industrial site at

Pierre Bénite

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In situ analysis in different industrial gases

in situ analysis with µspectrometric methods using in situ probes Evaluation of performances for Raman applications

Optimization of Tunable Diode Laser for specific applications TDL interface developed with EIF

Optimization of sensors

Density, moisture, H2, ... Analysis in corrosive environments (HF, HCl, ...)

Analysis in gases - Properties and Molecular Analysis

TDL

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Conclusion & outlooks For R&D we need µanalyzers to intensify and optimize research

productivity and results quality Increase the links between industrials, academic laboratories and

instrumentalists to adapt new analytical solutions in agreement with real industrial needs

INNOVAL project

Creation of a new research institute for ‘energetic transition’ to develop the factories of the future With a department dedicated to Industrial analysis

IDEEL

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Center of Excellence for "Industrial Analysis" in Lyon Region Reseach laboratories – Industrial laboratories - Training

Master degree

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NEXTLAB Conference, 2- 4 April 2014

Acknowledgements

Thank you