Microtechnologies dans les industries de procédésD.Hendershot, CEP 2000) ‘smaller is...

ENKI Innovation (www.enki2.com) Microtechnologies dans les industries de procédés SFGP St-Etienne, 11 octobre 2007

Microtechnologiesdans les industries de procédés :

quelques exemples récentsd’avancées technologiques

Jean JENCK (ENKI Innovation)

Thème 1 "Génie des procédés et microtechnologies"


Le Génie des Procédés et les microtechnologies

1.1. Outils industriels dans diverses industries de procédésOutils industriels dans diverses industries de procédés

2. Le contexte global de l’Intensification des Procédés

3. Exemples

– en synthèse chimique

– en polymères, matériaux

– en formulation

4. Perspectives :

– en séparations

– en commodités

5. Conclusion : opportunités et défis

Intensificationdes Procédés

DéveloppementRapide

Outils de Outils de production industrielleproduction industrielle

« Lab forthe Future »

Acquisition de données

de base

Miniaturisation etMicrotechnologies

Qualité des Produits

SFGP Cathala-Letort

novembre 2002


des centaines d’excellents travaux et ‘papiers’ sur :

• micro-fluidique• micro-actionneurs• micro-usinage• micro-analytique• expérimentation à haut débit• etc.

Bien que précurseurs de nouvelles technologies :pas traités dans cet exposé.


La dure réalité :- équipement 22 Cytos ? un seul exemplaire connu- 20 t/an ? tonnage en baisse à chaque communication- équipement ? pas de réelle intégration « système »- CPC ? ...est en faillite

Following the acquisition of CPC on July 1, 2007 by private investors, the board of CPC has chartered MRSP exclusively to build global Sales and reassess Distribution Channels.


“Nippoh Chemicals : commercial-scale manufacture of a fine chemical using its newly installed microreactor”

Nippoh first in the world to use MRT for production of > 1 000 ton/yr

trimethyl-orthoacetate in continuous microreactor at Chimachi factory

microreactor so small that it can be operated on a desk

only 200 seconds, compared with ~30 hours in a large reactor

application to compounds based on hydrogen cyanate and ortho-esters

same quality as that synthesized with the 10 m3 reactor

Japan Chemical Week, 22 Feb 2007, p. 1

Bien que lent, il y a néanmoins un profond mouvement vers ces microtechnologies, en

chimie, formulation, polymères, matériaux, etc.


FinTech™

Microstructures Microstructures

GP et microtechnologies : un point sémantique

mméésoso--technologiestechnologies::

macro-équipementstructuré à l’échelle millimétriquemeilleur compromis performance/opérabilité

AlfaLaval


1. Introduction: des Outils industriels dans diverses industries deprocédés

2.2. Le contexte global de l’Intensification des ProcédésLe contexte global de l’Intensification des Procédés

3. Exemples



– en formulation

4. Perspectives :

– en séparations

– en commodités

5. Conclusion : quels défis ?



PI, a new strategystrategy:

Instead of adapting the physico-chemical transformation to existing, known, depreciated

but often inadapted equipment…

Process Intensification is a design strategy to adapt the process to the chemical reaction

“ Doing more with less ”adapting the size of equipment to the reaction replacing large, expensive, inefficient equipment

by smaller, more efficient and cheaperchoosing the technology best suiting each stepsometimes combining multiple operations in fewer

apparatuses.

DSM Urea Plus


«« Reengineering the Chemical Processing PlantReengineering the Chemical Processing Plant »»R.Bakker, Marcel Dekker ed. 2003

Reach intrinsic kinetics of phenomena

maximize transfer rateFick law: flux = coefficient x interface x gradient


Mass

Tra

nsf

er

Mass

Tra

nsf

er

Heat TransferHeat Transfer

Courtesy BRITEST

Courtesy BRITEST

JacketedStirred Tank

Pulsed Column

Loop Reactor

Rotating Packed Bed

Educter

Static Mixer

Static Mixer/Plate Exchanger

PlateExchanger

Spinning DiscReactor

Equipment characterized by E & m transfer performances

Microreactor


Microtechs for PI:why is ‘smaller beautiful’ ?

0.66sizecost ≈


UCC, Bhopal 3 Dec 1984:cloud of 41 tons MIC

>2 500 killed

An inventory of 10 kg MICwould have been sufficient

(D.Hendershot, CEP 2000)

‘smaller is beautiful’ becausesmaller is safer !

1 ppm COCl2


ref: Merck

Batch 5m3

-20°C 5h Yield 72%

5 MINI-reactors0°C < 1 mn

continuousyield >92%

‘smaller is beautiful’ becausecontinuous mode performs better

Many cryo batchcryo batch processes are now replaced by meso-techs for continuous (quasi) room T processes


Delocalized productions, close to customer, with much lower inventories… but also delocalized risk !

- Interox: 1 ton/day peroxysulfuric acid (1s in a 20 cm3 tubular reactor)

- Kvaerner: phosgene COCl2 modular generator, point-of-use, skid-mounted

- hydrogen cyanide, chlorine dioxide, ethylene oxide, …

‘smaller is beautiful’ becausemore flexible

for on-siteon-demandproduction

ref: A.Green BHRG


‘smaller is beautiful’ because‘dream reactions’ are now possible

High T and P processing:T not limited by solvent boiling point

operation in liquid phase at elevated pressure (100 bar is easy)

Use of dangerous reagents:ex: fluorination by F2 takes a few milli-seconds in a

miniature falling film

Explosive regimes:ex: even in detonating mode, ie. with mixtures of

pure hydrogen and oxygen

ref: IMM


Challenges for microprocessing

Cost issuesthe cost of equipment must be offset by savings on- direct cost (raw material, energy) ex: non-cryo

- maintenance / effluents / indirect costs

Rush-to-be-second ?!?

Technical difficulties

example of corrosion





3.3. ExemplesExemples

–– en synthèse chimiqueen synthèse chimique


– en formulation

4. Perspectives :

– en séparations

– en commodités



Mobile multipurpose microreactor unit• feed : 3 liquids, 2 gases• ATEX EEx zone II• -80°C to +250°C• data collection

• production up to 50 tpa

Glass microstructured reactors


Alfa-Laval plate reactor

Capacities ranging from 1 l/h to 2000 l/h


Alfa-Laval plate reactor

Based on the promising results achieved, ARKEMA and Alfa Laval have initiated preparations

activities in order to perform installation, demonstration and evaluation of a Pilot Scale Plate Reactor, PR Pilot during 2006 and 2007. These activities are scheduled to be

performed before June 2007. The ART-project will be finalized in October 2007.

nous attendons donc avec curiosité une nouvelle annonce

R&D Arkema Pierre-Bénite


CHART compact heat exchange reactor


www.chart-ind.com ShimTech®

Liquid-phase oxidation of organic feedstockIEC Res. 2005, 44, 9683-9690:

consuming O2 = safety !T +- 1°C

CHART compact reactor : liquid phase


CHART compact reactor : gas phase


SiProcess for lab and pre-prod


www.siemens.com/siprocess

SIPROCESS

Combination of modularity with integrated automation. Each module has its own electronics and sensors to control the internal module functions.The electronics are connected to the higher-level automation system based on SIMATIC PCS 7 via a bus system, to which they are linked by plugging the module into a rack.


For chemical companies, an alternative is still to integrate microdevices from suppliers into home-made systems.Here are 2 examples (Schering, Merck) among many.





3.3.ExemplesExemples


–– en polymères, en matériauxen polymères, en matériaux

– en formulation

4. Perspectives :

– en séparations

– en commodités



Industrial microtechnology: polymer synthesis


SFTR: segmented flow tubular reactorAIChE Spring 2006, Orlando USA, paper 84a

Industrial microtechnology: ceramic powders


Mixing plate

Fluid A

Fluid B

Product

Mixing

Mixing plate:

The fluids divided into each channel and encountered each other at the center under high shear rate.

Inlet plate: to feed materials uniformly to the micro channel

H. Nagasawa , N. Aoki, K. Mae Design of a New Micromixer for Instant Mixing Based on Collision of Micro SegmentChem. Eng. Techn. 28(3), 324-330 (2005)

Fuji

Industrial microtechnology: organic pigments


Water with dispersant

K-M mixer 12 l/h

H. Maeta, T. Sato, H. Nagasawa, K. MaeProc. AIChE Spring National Meeting 2006 Orlando, Topical 1, paper 98a

Transparent Yellow 15 nm


Water with dispersant

K-M mixer 12 l/h

H. Maeta, T. Sato, H. Nagasawa, K. MaeProc. AIChE Spring National Meeting 2006 Orlando, Topical 1, paper 98a

70 t/year with only one K-M mixer

Fuji

Transparent Yellow 15 nm


K. Tahara, J. Mizuya and M. SatoArakawa Chemical Industries &Osaka Prefecture University(AIChE Spring 2007, Houston)

Industrial microtechnology: polyimide beads





3.3.ExemplesExemples



–– en formulationen formulation

4. Perspectives :

– en séparations

– en commodités



Inline color change of plastics:

caterpillar micromixersfilled with color componentscontinuous feed to extruder

POLYTREND Color Infusion PlusTM: production interrupted for just a few minutes.

Industrial microtechnology: polymer processing


0.2-5 mm

not micro:milli !

0.2-5 mm

Transmembrane pressure drop: one phase is dispersed thru pores (principle known since early 1990s), fine droplets are directly generated by build-up and detachment at the surface of the membrane.

Industrial microtechnology: micro-membrane emulsification


lab facilities for customers tests

www.velocys.com

• High shear at wall, lower shear in bulk• Small droplet sizes, uniform distribution• Rapid, in-line heating & cooling• Overcome scale-up challenges• Small, compact units


Institute Mikrotechnik Mainz

Industrial microtechnology: micro-mixer emulsification


Static Mixer Reactor (static mixing elements made of heat-transfer tubes): adapted for processes in which simultaneous mixing and intensive cooling (or heating) are necessary (ex. PS polymerization)

Philippe Tanguy

Colloque PID Lyon, 27-28mar07

Industrial microtechnology: micro-static mixer emulsification


Industrial microtechnology: pasteurization of food

(NIZO Food Research)


Industrial microtechnology: sterilization of food


FZKultra-fast heating / cooling

residence: a few milliseconds

rates: up to 1000 K/s

400 kg/h in 1 cm3

exchangerpressure drop 0.5 MPa





3. Exemples



– en formulation

4.4. Perspectives :Perspectives :

–– en séparationsen séparations

– en commodités/énergie



VelocysFractionator

Industrial microtechnology: distillation

Pioneered at Pacific Northwest National Laboratory

Microchannels enable ultra-Short HETP (potential for 10-100x reduction)


Velocys , US DoE, ABB Lummus

HEPT ~1.5 cm





3. Exemples



– en formulation

4.4. Perspectives :Perspectives :

– en séparations

–– en commodités, énergieen commodités, énergie



“changing the way the world produces energy, chemicals and biofuels with revolutionary microchannel technology”

In November of 2005, Total S.A. and Velocys formed a multi-year alliance to apply microchannel process technology and highly active, nano-scale catalyst to produce synthetic fuel from abundant natural gas.

Industrial microtechnology: Fischer-Tropsch synthesis


Emerging Commercial Applications

Steam Methane Reformer

Advantages

90% size reduction

33% capital cost reduction

7% improvement in feedstock utilization

Reduced NOx emission

Status

2006 – Manufacturing scale-up, catalyst adaptation

2007 – Pilot plant demonstration

2008 – Commercial demonstration


U.S. Army National Automotive Center

Design Basis:• gasoline ~20 000 m3/year• compact facility• natural gas feed

Fischer-Tropsch delocalized process





3. Exemples



– en formulation

4. Perspectives :

– en séparations

– en commodités

5.5.Conclusion : opportunités et défisConclusion : opportunités et défis


Technology validation still to be assessed.

Validated by its economical benefit ? A ‘rush-to-be-second’ and not so many excuses anymore not to use it ?

Decisive for sustainable chemistry, new routes reconsidered.Also emerging in the pharmaceutical industry.

Useful for on-site applications (cosmetics, drugs, testing).

Engineering methodologies required !

Microtechs and Process Intensification:a global conclusion


ColmatageAbrasion

Matériaux

NettoyageStérilisation

Alimentation

Investissements lourdsDurées longues

Commodités, énergie

Manque de ressourcesRésistance au changement

Chimie fine

FlexibilitéCoût

Chimie pharma

Défi majeurMarché


SFGP2007, thSFGP2007, thèème 1me 1 : Le G: Le Géénie des Procnie des Procééddéés et les microtechnologiess et les microtechnologies

1- CFD simulation of hydrodynamic and thermal performance of micro heat exchangerJ. JONQUILLE, W. NASTOLL, C. BOYER, L. NOUGIER

2- Caractérisation du mélange et de la dégradation énergétique dans des installations miniaturisées

Florian HUCHET ; Hayet BENNADJI ; Jacques COMITI ; Patrick LEGENTILHOMME (GEPEA)

3- Conception et caractérisation d’échangeur-réacteur à structure multi-échelleMeryem SABER ; Jean Marc COMMENGE ; Laurent FALK (LSGC)

4- Développement d’un pré-concentrateur pour la détection de substances chimiques àl’état de traces

PIJOLAT Christophe, CAMARA Malik, VIRICELLE Jean-Paul, TOURNIER Guy, BREUIL Philippe / Centre SPIN EMSE St-EtienneCOURBAT Jérôme, BRIAND Danick, IMT Neuchatel (CH)

5- Etude d'un microréacteur conçu pour l'électrosynthèse organiqueAnis ATTOUR ; François LAPICQUE ; Athanassios ZIOGAS (IMM) ; Sabine RODE ; Michael MATLOSZ (LSGC)

6- Utilisation de systèmes microfluidiques pour la synthèse de copolymères à blocs : influence du mélange et des conditions opératoires sur le contrôle de la distribution des masses molaires

Carine ROSENFELD ; Christophe SERRA ; Cyril BROCHON ; Georges HADZIIOANNOU (LIPHT - CNRS UMR 7165)

Microtechnologies dans les industries de procédésD.Hendershot, CEP 2000) ‘smaller is...

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