Reaction and Raman spectroscopic studies of alcohol oxidation on gold-palladium catalysts in microstructured reactors

Oxidation of benzyl alcohol in the absence of solvent on 1% (Au–Pd)/TiO2 catalyst with pure oxygen was performed in silicon-glass micropacked-bed reactors (MPBRs). The overall size of the microreactor chip was 23 mm × 23 mm with a reaction channel dimension of 0.6 mm (W) × 0.3 mm (H) × 190 mm (L). A pillar structure (small rectangular posts of 60 μm (W) × 1 mm (L) 40 μm apart) was incorporated near the outlet of the reaction channel to retain the catalyst. The reaction was studied in the temperature range of 80–120 °C and at inlet pressures up to 5 bar(a). Benzyl alcohol conversion and benzaldehyde selectivity at 80 and 120 °C obtained in MPBRs were very close to those from conventional glass stirred reactors (GSRs) apart from the selectivity at 120 °C. Toluene was formed in the absence of oxygen, and its production was enhanced in the presence of oxygen. Increasing pressure improved both conversion and benzaldehyde selectivity. Mass transfer resistance in MPBRs was evaluated experimentally. The external mass transfer resistance could be ignored at a volumetric flow ratio of gas (STP) to liquid above 100, at a given liquid flow rate (0.003 mL/min). The effect of catalyst particle size on the reaction was examined with two ranges of particle size: 53–63 μm and 90–125 μm. Lower conversion was obtained with particle sizes of 90–125 μm, indicating the presence of internal mass transfer resistances. In situ Raman measurements in MPBRs were performed using a specially designed microreactor stage with a different microreactor configuration. Raman spectra obtained from liquid pockets at different points along the reaction channel could be used to obtain the benzaldehyde concentration profile along the catalyst bed. Bands due to formation of highly disordered graphitic carbon were observed on the catalyst surface.

[1]  S. Haswell,et al.  Monitoring of chemical reactions within microreactors using an inverted Raman microscopic spectrometer , 2003, Electrophoresis.

[2]  M. Duduković,et al.  Comparison of Upflow and Downflow Two-Phase Flow Packed-Bed Reactors with and without Fines: Experimental Observations , 1996 .

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

[4]  Peter J. Miedziak,et al.  Oxidation of alcohols using supported gold and gold–palladium nanoparticles , 2010 .

[5]  Kangnian Fan,et al.  Aerobic oxidation of alcohols catalyzed by gold nanoparticles supported on gallia polymorphs , 2008 .

[6]  J. Moulijn,et al.  Catalyst testing in a multiple-parallel, gas–liquid, powder-packed bed microreactor , 2009 .

[7]  K. Ebitani,et al.  Hydroxyapatite-supported palladium nanoclusters: a highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen. , 2004, Journal of the American Chemical Society.

[8]  A. Gavriilidis,et al.  A microstructured reactor based in situ cell for the study of catalysts by X-ray absorption spectroscopy under operating conditions , 2007 .

[9]  Richard F Winkle,et al.  A method for rapid reaction optimisation in continuous-flow microfluidic reactors using online Raman spectroscopic detection. , 2005, In Analysis.

[10]  G. Hutchings,et al.  Solvent-free oxidation of benzyl alcohol using Au-Pd catalysts prepared by sol immobilisation. , 2009, Physical chemistry chemical physics : PCCP.

[11]  E. Stitt,et al.  Effect of Fines and Porous Catalyst on Hydrodynamics of Trickle Bed Reactors , 2005 .

[12]  Toshimitsu Suzuki,et al.  Palladium-loaded oxidized diamond catalysis for the selective oxidation of alcohols , 2009 .

[13]  Klavs F. Jensen,et al.  Silicon Micromixers with Infrared Detection for Studies of Liquid-Phase Reactions , 2005 .

[14]  J. Charpentier,et al.  Some liquid holdup experimental data in trickle-bed reactors for foaming and nonfoaming hydrocarbons , 1975 .

[15]  Eun Kyu Lee,et al.  Applicability of laser-induced Raman microscopy forin situ monitoring of imine formation in a glass microfluidic chip , 2003 .

[16]  J. van Klinken,et al.  Catalyst dilution for improved performance of laboratory trickle-flow reactors , 1980 .

[17]  K. Wiberg,et al.  Oxidation in organic chemistry , 1982 .

[18]  Peter J. Miedziak,et al.  Au-Pd supported nanocrystals prepared by a sol immobilisation technique as catalysts for selective chemical synthesis. , 2008, Physical chemistry chemical physics : PCCP.

[19]  Masatake Haruta,et al.  Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide , 1989 .

[20]  L. Goodman,et al.  Assignment of out-of-plane vibrational modes in benzaldehyde , 1971 .

[21]  D. Hickman,et al.  A comparison of a batch recycle reactor and an integral reactor with fines for scale-up of an industrial trickle bed reactor from laboratory data , 2004 .

[22]  Asterios Gavriilidis,et al.  Application of microfabricated reactors for operando Raman studies of catalytic oxidation of methanol to formaldehyde on silver , 2007 .

[23]  M. N. Vargaftik,et al.  Oxidative and anaerobic reactions of benzyl alcohol catalysed by a Pd-561 giant cluster , 2002 .

[24]  A. Corma,et al.  A collaborative effect between gold and a support induces the selective oxidation of alcohols. , 2005, Angewandte Chemie.

[25]  Yuanxin Wu,et al.  Reproducible Technique for Packing Laboratory-Scale Trickle-Bed Reactors with a Mixture of Catalyst and Fines , 1995 .

[26]  G. Hutchings,et al.  Oxidation of glycerol using gold-palladium alloy-supported nanocrystals. , 2009, Physical chemistry chemical physics : PCCP.

[27]  F. Kapteijn,et al.  Catalyst performance testing: bed dilution revisited , 2002 .

[28]  A. Baiker,et al.  Oxidation of alcohols with molecular oxygen on solid catalysts. , 2004, Chemical reviews.

[29]  G. Hutchings Vapor phase hydrochlorination of acetylene: Correlation of catalytic activity of supported metal chloride catalysts , 1985 .

[30]  G. Hutchings,et al.  Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO2 Catalysts , 2006, Science.

[31]  Robert J. Davis,et al.  Selective oxidation of glycerol over carbon-supported AuPd catalysts , 2007 .