Solid catalyzed hydrogenation in a Si/glass microreactor using supercritical CO2 as the reaction solvent

Abstract We present the use of supercritical CO 2 (scCO 2 ) as reaction solvent in a packed bed silicon/glass microreactor in case of the hydrogenation of cyclohexene as a model reaction. In situ phase studies in the continuous flow of the reaction mixture, hydrodynamic characterization and the influence of pressure and temperature on the reaction performance are discussed. The results are compared with the same reaction conducted in three phase gas–liquid–solid state and larger scale reactors using scCO 2 as reaction solvent. The phase study experiments show a single phase flow behavior at 136 bar and 25 °C for a 90:5:5 molar mixture of CO 2 :C 6 H 10 :H 2 . At 50 °C compositions up to 87.8:2.4:9.8 show single phase flow. The reaction performance increases with increasing temperature where pressure variations show no significant change. The comparison with larger scale systems indicates an increase of about one order of magnitude in space time yield in the presented microreactor.

[1]  Hydrogenation reactions using scCO2 as a solvent in microchannel reactors. , 2005, Chemical communications.

[2]  D. Reinhoudt,et al.  Fabrication, mechanical testing and application of high-pressure glass microreactor chips , 2007 .

[3]  M. Poliakoff,et al.  Selective catalytic hydrogenation of organic compounds in supercritical fluids as a continuous process , 1998 .

[4]  Saif A. Khan,et al.  Transport and reaction in microscale segmented gas-liquid flow. , 2004, Lab on a chip.

[5]  Philipp Rudolf von Rohr,et al.  Transparent silicon/glass microreactor for high-pressure and high-temperature reactions , 2008 .

[6]  D. Reinhoudt,et al.  Substantial rate enhancements of the esterification reaction of phthalic anhydride with methanol at high pressure and using supercritical CO2 as a co-solvent in a glass microreactor. , 2007, Lab on a chip.

[7]  Klavs F. Jensen,et al.  Microfabricated multiphase packed-bed reactors : Characterization of mass transfer and reactions , 2001 .

[8]  M. Arai,et al.  Innovation in a chemical reaction process using a supercritical water microreaction system: environmentally friendly production of epsilon-caprolactam. , 2002, Chemical communications.

[9]  R. Freitag,et al.  Fabrication of a versatile microanalytical system without need for clean room conditions , 2004 .

[10]  O. Levenspiel Chemical Reaction Engineering , 1972 .

[11]  Alfons Baiker,et al.  Supercritical Fluids in Heterogeneous Catalysis. , 1999, Chemical reviews.

[12]  David R. Miller,et al.  Quartz capillary microreactor for studies of oxidation in supercritical water , 2001 .

[13]  H. Lüdemann,et al.  Transport properties of supercritical fluids and their binary mixtures , 2002 .

[14]  David R. Miller,et al.  A Direct Sampling Mass Spectrometer Investigation of Oxidation Mechanisms for Acetic Acid in Supercritical Water , 2001 .

[15]  J. Wisniak,et al.  Hydrogen solubility in organic liquids , 1983 .

[16]  Klavs F Jensen,et al.  Solder-based chip-to-tube and chip-to-chip packaging for microfluidic devices. , 2007, Lab on a chip.

[17]  B. Subramaniam,et al.  Fixed-bed hydrogenation of organic compounds in supercritical carbon dioxide , 2001 .

[18]  Fernando Benito-Lopez,et al.  Optical fiber-based on-line UV/Vis spectroscopic monitoring of chemical reaction kinetics under high pressure in a capillary microreactor. , 2005, Chemical communications.

[19]  Masahiro Sato,et al.  Rapid and highly selective copper-free sonogashira coupling in high-pressure, high-temperature water in a microfluidic system. , 2007, Angewandte Chemie.