MicroReactor developments Cline GUERMEUR Corning SAS CPAC SATELLITE

Micro-Reactor developments Céline GUERMEUR Corning SAS CPAC SATELLITE WORKSHOPS 2007 Micro-reactors and Micro-Analytical – March 19 -21, 2007

Focus: The reactor and its integration into the production system R R’ C=O Chemistry Mass and heat transfer System engineering Reactor engineering Corning 2

Micro reactor for Industrial Production Throughput in metric tons per year per reactor Targeted product Metric tons/Year per reactor Reactants concentration (wt%) Assumptions Flow rate (Kg/hour) 1 2 3 5 10 12 10 1 2 2 4 8 10 20 2 3 5 8 17 20 30 2 5 7 12 25 30 50 4 8 12 21 42 50 70 6 12 17 29 58 70 100 8 17 25 42 83 100 Conversion 100 % Selectivity 95 % Corning 3

Reactor engineering process Reaction network and feed distribution Thermodynamic & Kinetics Feed boundaries CUSTOMER NEEDS Chemistry know-how Reactor fundament als Basic reactor engineer ing Detailed reactor engineeri ng Design and sizing Material selection REACTOR PRODUCT SYNTHESIS UNIT Translation into a mass and heat transfer problem Let’s go together through an example Corning 4

Customer needs • • Chemistry know-how Reactor fundament als Basic reactor engineer ing Detailed reactor engineeri ng Safe and smooth production of 40 kg / week / reactor Raw material cost > 500 €/kg More than 95% conversion Impurities below 2% Corning 5

Chemistry know-how The chemistry know-how • A+B C • C+D E • E + H 20 Product + H 2 • Exothermic • Highly reactive intermediate • No major side products • • Exothermic Maximum temperature 10°C Safety limit : 50 L batch vessel Excess of C = Selectivity issue • Exothermic • Hydrogen release Corning 6

Basic reactor engineer ing Product synthesis unit Internal volume : 200 Liters 5 loading / unloading Internal volume < 0. 1 Liter No loading / unloading A B C PRODUCT SYNTHESIS UNIT D Corning 7

Basic engineering Basic reactor engineer ing • Step 1 : – Mixing and heat exchange integrated – Single injection • Step 2 : – Mixing and heat exchange integrated – No excess of C • Step 3: – Mixing and heat exchange integrated – Single injection Corning 8

Data needed: Mass and heat balance Detailed reactor engineeri ng 19 ml/min 17 g/min 0. 5 c. P @ 20°C Feed 1 20°C Feed 2 29 ml/min 26 g/min 0. 5 c. P@20°C 15 W released 0°C 150 W released 480 W released Feed 3 65 ml/min 58 g/min 0. 7 Cp@0°C Feed 4 43 ml/min 39 g/min 1. 6 c. P@ 0°C Corning 9

Hydrodynamic Detailed reactor engineeri ng Corning 10

Chemistry know-how Reactor fundament als Basic reactor engineer ing Detailed reactor engineeri ng Throughput: 40 kg/week 99 % conversion Impurities < 1% Pressure: Up to 18 bars Temperature : -50°C to 40°C Internal volume : 70 ml Corning 11

MASS TRANSFER: SINGLE AND MULTI-INJECTION HEAT TRANSFER

Single-injection reactor Reactor fundamental s A FEED PREHEAT/COOL B FEED PREHEAT/COOL HE IN REACT HE OUT PRODUCT Corning 13

Multi-injection reactor Reactor fundamental s A B FEED PREHEAT/COOL SPLIT FEED PREHEAT/COOL REACT HE IN HE OUT PRODUCT Acknowledgement: Michael T. Klein, Dean School of Engineering Corning Rutgers, The State University of New Jersey 14

Multi-injection: Better temperature management along the flow path Heat removal Heat generation Single -injection Multi -injection Corning 15

Single and multi-injection Reactor fundamental s Examples B = 1/3 B=1 B = 1/3 A/B = 2 A/B = 1 A=1 A/B = 3 In both cases, the molar ratio target is reached Corning 16

Multi-injection: Only two pumps are required Reactor fundamental s A B Pressure drop management and fluid split within the micro-structures Product Corning 17

Reactor fundamental s Mass and heat transfer are combined Heat transfer Mass transfer Heat transfer Corning 18

Optimum heat exchange Reactor fundamental s Reaction circuit: Toluene Heat exchange circuit: Water 600 W/m 2. K Corning 19

Heat exchange performance Reactor fundamental s Corning glass micro-reactor Example of metal mixer (Internal testing) Reaction circuit: Toluene – Same flow rate Heat exchange fluid: Water Heat exchange: Integrated 600 W/m 2. K Heat exchange: Agitated bath 60 W/m 2. K Corning 20

Multi-phase mass transfer Feeds Mixing test Results L Mixing quality > 90% for flow rates > 1. 8 L/h Villermaux method Villermaux & all, AICh. E Symp. Ser. 88 (1991) 6, 286. L/L Polystyrene precipitation 50 -100 nm particle Chem. Eng. Technol. 2005, 28, 324 -330 size Proc. of the 10 th APCCh. E Congress, 2004, 4 B-02 L/G Measure of slug size Pressure drop in monolith reactors, P. Woehl, R. L. Cerro, Catalysis Today 69 (2001) 171 -174 Flow patterns in liquid slugs during bubble-train flow inside capillaries, Chem Eng Sci 52 (1997) 2947 -2962 Hydrodynamic visualization 0. 5 - 10 mm Hydrodynamic regime adapted to needs Corning 21

Module approach enable bridging Specific reaction(s) Synthesis unit kglab testing Dedicated production Standard modules Test applicability on reaction portfolio Multipurpose production Corning 22

Nitration Corning 23

Organometalic reaction Corning 24

Example of Multipurpose production PRODUCTION 1 CAMPAIGN 1 PRODUCTION 1 CAMPAIGN 2 Corning 25

Generate value in production, increase safety and product quality using micro-reactors Courtesy of Lonza Corning 26