1. Review of Microreactors Radmila Jevtic (graduate student) and Professors Muthanna Al-Dahhan and Milorad P. Dudukovic

2. Outline Background and features Review of gas-liquid microreactors Scale-up methodology Conclusions

3. Background and Features Micro-structured reactor channel diameters: sub mm to mm range Surface/Volume area: 1,000-50,000 m 2 /m 3 Sources: 1) A. Günther at al., Langmuir, 21, 1547 (2005); 2) www.imm-mainz.de/;www.imm-mainz.de/ 3) http://www.mikroglas.com/

4. Features: Advantages  High surface-to-volume area; enhanced mass and heat transfer  Laminar flow conditions  Uniform residence time, backmixing minimized (increased precision and accuracy)  High-throughput and use of very small amounts of materials  Low manufacturing, operating, and maintenance costs (if mass produced), and low power consumption  Minimal environmental hazards and increased safety  “Scaling-out” or “numbering-up” instead of scaling-up

5. Type of conventional reactor Specific interface area [m 2 /m 3 ] Type of microreactorSpecific interface area [m 2 /m 3 ] Packed column Countercurrent flow Co-current flow 10-350 10-1700 Micro bubble column (1100μm x 170 μm) 5,100 Bubble columns50-600Micro bubble column (300 μm x 100 μm) 9,800 Spray columns10-100Micro bubble column (50 μm x 50 μm) 14,800 Mechanically stirred bubble columns 100-2000Falling film microreactor (300 μm x 100 μm) 27,000 Impinging jets90-2050 Features: Advantages  Specific interfacial area (S/V) Source: Oroskar, A. R et al. Proceedings of the IMRET-5: 5th International Conference on Microreaction Technology, 27.-30. 5. 2001, Strasbourg, (Berlin, Heidelberg, New York: Springer, 2002), 153.

6. Features: Advantages  Mass and heat transfer Source: J.C. Schouten, Symposium on Micro Process Engineering for Catalysis & Multiphases, Eindhoven University of Technology, February 2006

7. Features: Advantages  Mass transfer Source: Klavs Jensen’s Group, MIT. Reference: M.W. Losey, et al., I&EC Research, 40, 2555 (2001) Cyclohexane hydrogenation was performed in micro packed bed reactor. The catalyst was standard platinum supported on alumina powder. It was determined that overall mass transfer coefficient (KLa) was 5-15 s-1 as opposed to 0.01-0.08 s-1 for laboratory trickle bed reactors

8. Features: Drawbacks  Fast reaction rates are required due to the short residence times  Fouling and clogging  Maintenance, ageing, regeneration  Lack of experience with commercial processes  Catalyst deactivation, life on stream unknown  Only few technology providers

9. Potential application for microreactors Synthesis of hazardous gases: chlorine, iso-cyanates, hydrogen cyanide, phosgene… Hydrogen production via steam reforming, partial oxidation of methane, from higher alkanes and alcohol to syngas Synthesis of ethylene oxide, propylene to acrolein, oxidative dehydrogenation of alcohols to aldehydes Oxidation of ammonia Source: Dupont et al, Minisymposium on Micro Process Engineering for Catalysis & Multiphases, Eindhoven University of Technology, February 2006

10. Potential application for microreactors  Type A are very fast reactions with a reaction half time of less than 1 s.  Type B are also fast reactions with reaction times between 1s and 10 min.  Type C reactions are slow (reaction times greater than 10min). 63% are not well suited due to solids present as reactant, catalyst, or products. Almost 50% of reactions could benefit from a continuous process in microreactors: Source: Roberge, D. et al Chem. Eng. Tech. 2005, 28, 318.

11. Review on G-L microreactors: Falling Film Microreactor (FFM) Cross-section of a microchannel: 100micronx300micron Reaction used: direct fluorination of aromatic compound using elemental fluorine Specific interfacial area: 33,000m 2 /m 3 and 27,000m 2 /m 3 corresponding to film thickness of 30 and 37 microns Source: 1) Jähnisch, K. et al. Fluorine Chem. 2000, 105, 117. 2) Zanfir, M. et al. Ind. Eng. Chem. Res. 2005, 44, 1742. 3) www.imm-mainz.de/

12. Review of G-L microreactors: Micro-bubble Column (MBC) Dimensions: 50 μm x50 μm (narrow rectangular channels) and 300 μm x150 μm x50 μm (wide channels) Measured interfacial area: 9,000m2/m3; calculated: 14,000m2/m3 Taylor flow Reaction of direct fluorination of aromatics used Source: 1) Jähnisch, K. et al. Fluorine Chem. 2000, 105, 117. 2) www.imm-mainz.de/

13. Review of G-L microreactors: MMB and FFR Performance Selectivity: LBC- laboratory reactor MBC (I) 300μmx100μm MBC (II) 50μmx50μm Source: 1) Jähnisch, K. et al. Fluorine Chem. 2000, 105, 117.

14. Review of G-L microreactors: CO 2 absorption in Falling Film Microreactor (FFM) Source: Zanfir, M. et al. Ind. Eng. Chem. Res. 2005, 44, 1742.  Performance of the reactor for CO2 absorption in sodium hydroxide solution compared with the model  Model gives good agreement for low concentration of NaOH but poor for higher concentrations due to model simplification and possible liquid maldistribution Schematic of the single channel in the model

15. Review of G-L microreactors: Microreactor for direct fluorination of aromatics (MIT)  Experiments were carried out at room temperature in annular dry flow regime Flow visualization Performance Source: 1) Klavs Jensen group, MIT 2) N. de Mas, et al., Ind. Eng. Chem Research, 42(4); 698-710 (2003)

16. G L Review of G-L microreactors: Using Inert gas to Mix Miscible Liquids Source: 1) Klavs Jensen group, MIT 2) A. Günther et al., Langmuir, 21, 1547 (2005).

17. L1L1 L2L2 t t Review of G-L microreactors: RTD in  Fluidic Channels Source: 1) Klavs Jensen group, MIT 2) F. Trachsel, et al., Chem. Eng. Sci., 60 (2005), 5729 Segmented flow can be understood as sequence of small batch reactors passing through plug flow reactor with very narrow residence time distribution (RTD) curve

18. Review of G-L microreactors: Colloidal particle synthesis Narrow RTD characteristic of segmented flow in microchannels can be employed in the synthesis of colloidal particles where size distribution is important. Example: colloidal silica (SiO 2 ) Alkoxide groups (OR) are first replaced by hydroxyl group (OH)- HYDROLISIS. Siloxane bonds are formed and either alcohol (ROH) or water (H2O) are formed-CONDENSATION As alkoxide, which can be view as weak ester of silicic acid (Si(OH)4), TOES (tetraehyl orthosilicate) is often used Source: Stöber, W. et al.J. Colloid Interface Sci. 1968, 26, 62.

19. Review on G-L microreactors: Colloidal particle synthesis 1 µm Gas SFR enables continuous synthesis with results that mirror those obtained from batch synthesis  Wide particle size distribution at low residence times Laminar Flow Reactor Segmented Flow Reactor Source: 1) Klavs Jensen group, MIT 2) S.A. Khan, et al.,” Langmuir 20, 8604-8611(2004 )

20. Scale up Methodology Number of channels increases, size of the single channel does not  The concept of scale-up by replication of microreactor units (scale-out) appears to be simple but the areas of reactor monitoring and control become increasingly complex as the parallel array size grows to a large number of reactors. Source: Lerou, CREL Annual Meeting, St. Louis, MO, November, 2005

21. Scale up Methodology Source: Lerou, CREL Annual Meeting, St. Louis, MO, November, 2005 30 ft 100 ft

22. Scale up Methodology  Reaction: Direct fluorination of ethyl acetoacetate in formic acid by fluorine (10-50% in nitrogen)  Cooling and heating is provided by the coils that pass through the steel base of the reactor  Production rate: cca 300g of product per day  10 reactors - 3 kg (which is the range of the pilot-plant operation) Source: Chambers, R. D. et al. Lab Chip. 2005, 5, 191.

23. Scale up Methodology-Integration  Idea: to standardize interfaces of various microdevices (microreactors, micromixers, etc) available from different manufacturers so that they can be incorporated in a “microplant”  Test reaction: the sulfonation of toluene with gaseous SO3.  Result: A selectivity of 82% of the target product, toluenesulfonic acid, is achieved at nearly complete conversion (last step, hydration, not performed) Source: Müller, A. et al. Chem. Eng. J. 2005, 107, 205.

24. Conclusions Promising technology:  enhanced mass and heat transfer  efficient process intensification  inherently safe operation  uniform residence time Some issues still remain:  integration with sensors, actuators, and other associated equipment, such as pumps;  reactor monitoring and control;  high activity stable catalysts needed.