in al innovative project for micro process analytical...
TRANSCRIPT
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