Novel synthesis of thick wall coatings of titania supported Bi poisoned Pd catalysts and application in selective hydrogenation of acetylene alcohols in capillary microreactors.

Catalysis in microreactors allows reactions to be performed in a very small volume, reducing the environmental problems and greatly intensifying the processes through easy pressure control and the elimination of heat- and mass-transfer limitations. In this study, we report a novel method for the controlled synthesis of micrometre-thick mesoporous TiO2 catalytic coatings on the walls of long channels (>1 m) of capillary microreactors in a single deposition step. The method uses elevated temperature and introduces a convenient control parameter of the deposition rate (displacement speed controlled by a stepper motor), which allows deposition from concentrated and viscous sols without channel clogging. A capillary microreactor wall-coated with titania supported Bi-poisoned Pd catalyst was obtained using the method and used for the semihydrogenation of 2-methyl-3-butyn-2-ol providing 93 ± 1.5% alkene yield for 100 h without deactivation. Although the coating method was applied only for TiO2 deposition, it is nonetheless suitable for the deposition of volatile sols.

[1]  Rafael Luque,et al.  Supported metal nanoparticles on porous materials. Methods and applications. , 2009, Chemical Society reviews.

[2]  R. Sacks,et al.  High-performance, static-coated silicon microfabricated columns for gas chromatography. , 2006, Analytical chemistry.

[3]  H. Löwe,et al.  Chemistry in microstructured reactors. , 2004, Angewandte Chemie.

[4]  N. López,et al.  Molecular understanding of alkyne hydrogenation for the design of selective catalysts. , 2010, Dalton transactions.

[5]  Marco Faustini,et al.  Preparation of Sol−Gel Films by Dip-Coating in Extreme Conditions , 2010 .

[6]  Nele De Belie,et al.  Titanium dioxide coated cementitious materials for air purifying purposes: Preparation, characterization and toluene removal potential , 2010 .

[7]  W. Marsden I and J , 2012 .

[8]  K. Grob,et al.  Capillary columns with very thick coatings , 1983 .

[9]  J. Burns,et al.  The intensification of rapid reactions in multiphase systems using slug flow in capillaries. , 2001, Lab on a chip.

[10]  Neil Genzlinger A. and Q , 2006 .

[11]  Andrew G. Glen,et al.  APPL , 2001 .

[12]  Masoud Agah,et al.  Design, fabrication, and evaluation of microfabricated columns for gas chromatography. , 2004, Analytical chemistry.

[13]  F. Liguori,et al.  Green semi-hydrogenation of alkynes by Pd@borate monolith catalysts under continuous flow , 2014 .

[14]  Bs Bhaskar Patil,et al.  Industrial applications of plasma, microwave and ultrasound techniques: Nitrogen-fixation and hydrogenation reactions , 2013 .

[15]  G. Chuah,et al.  A wall-coated catalytic capillary microreactor for the direct formation of hydrogen peroxide , 2010 .

[16]  G. Taylor Deposition of a viscous fluid on the wall of a tube , 1961, Journal of Fluid Mechanics.

[17]  G. L. Puma,et al.  Carbon nanotube/titanium dioxide (CNT/TiO2) core–shell nanocomposites with tailored shell thickness, CNT content and photocatalytic/photoelectrocatalytic properties , 2011 .

[18]  L. Kiwi-Minsker,et al.  Kinetics of the solvent-free hydrogenation of 2-methyl-3-butyn-2-ol over a structured Pd-based catalyst , 2009 .

[19]  Á. Berenguer-Murcia,et al.  Capillary microreactors wall-coated with mesoporous titania thin film catalyst supports. , 2009, Lab on a chip.

[20]  M. Wohlfahrt‐Mehrens,et al.  High surface area crystalline titanium dioxide: potential and limits in electrochemical energy storage and catalysis. , 2012, Chemical Society reviews.

[21]  Asterios Gavriilidis,et al.  Flow regimes for adiabatic gas–liquid flow in microchannels , 2009 .

[22]  Jeremy L. Steinbacher,et al.  Greener approaches to organic synthesis using microreactor technology. , 2007, Chemical reviews.

[23]  Quan Yuan,et al.  Gas-Liquid Microreaction Technology: Recent Developments and Future Challenges , 2008 .

[24]  L. Luo,et al.  Hydrodynamics and mass transfer characteristics in gas–liquid flow through a rectangular microchannel , 2007 .

[25]  R. Kobayashi,et al.  Vapor pressure of normal paraffins ethane through n-decane from their triple points to about 10 mm mercury , 1973 .

[26]  David Reay,et al.  Process Intensification: Engineering for Efficiency, Sustainability and Flexibility , 2008 .

[27]  James A. Anderson,et al.  Bi modified Pd/SnO2 catalysts for water denitration , 2007 .

[28]  M. Scheffler,et al.  First-principles kinetic Monte Carlo simulations for heterogeneous catalysis : Application to the Co oxidation at RuO2(110) , 2005, cond-mat/0510234.

[29]  G. Bond,et al.  Selective Hydrogenation of Ethyne in Ethene‐Rich Streams on Palladium Catalysts. Part 1. Effect of Changes to the Catalyst During Reaction , 2006 .

[30]  T. Netscher,et al.  Hydrogenation in the Vitamins and Fine Chemicals Industry – An Overview , 2012 .

[31]  James A. Schwarz,et al.  Methods for Preparation of Catalytic Materials , 1995 .

[32]  K. Jensen Microreaction engineering * is small better? , 2001 .

[33]  Shunsuke Tanaka,et al.  Platinum Nanoparticles Supported on Anatase Titanium Dioxide as Highly Active Catalysts for Aerobic Oxidation under Visible Light Irradiation , 2012 .

[34]  L. Scriven Physics and Applications of DIP Coating and Spin Coating , 1988 .

[35]  Gas–liquid–solid “slurry Taylor” flow: Experimental evaluation through the catalytic hydrogenation of 3-methyl-1-pentyn-3-ol , 2013 .

[36]  N. Krins,et al.  Thick and crack-free nanocrystalline mesoporous TiO2 films obtained by capillary coating from aqueous solutions , 2010 .

[37]  A. Po,et al.  BISMUTH TOXICITY—A REASSESSMENT * , 1989, Journal of clinical pharmacy and therapeutics.

[38]  Younan Xia,et al.  Structure sensitivity of alkynol hydrogenation on shape- and size-controlled palladium nanocrystals: which sites are most active and selective? , 2011, Journal of the American Chemical Society.

[39]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[40]  Jc Jaap Schouten,et al.  Selective Hydrogenation of 2-Methyl-3-butyne-2-ol in a Wall-Coated Capillary Microreactor with a Pd25Zn75/TiO2 Catalyst , 2009 .

[41]  V. Grassian,et al.  Titanium dioxide photocatalysis in atmospheric chemistry. , 2012, Chemical reviews.

[42]  Abhaya K. Datye,et al.  Wall coating of a CuO/ZnO/Al2O3 methanol steam reforming catalyst for micro-channel reformers , 2004 .

[43]  K. Grob Are we using the full range of film thickness in capillary-GLC? , 1977 .

[44]  M. Vannice Kinetics of Catalytic Reactions , 2005 .

[45]  J. Mellor,et al.  Pd catalysed hexyne hydrogenation modified by Bi and by Pb , 2009 .

[46]  D. Chisholm A theoretical basis for the Lockhart-Martinelli correlation for two-phase flow , 1967 .

[47]  K. Westerterp,et al.  Mechanism and kinetics of the selective hydrogenation of ethyne and ethene , 1993 .

[48]  E. Sulman,et al.  Palladium nanoparticles stabilized in block-copolymer micelles for highly selective 2-butyne-1,4-diol partial hydrogenation , 2005 .

[49]  Takehiko Kitamori,et al.  A Microfluidic Device for Conducting Gas-Liquid-Solid Hydrogenation Reactions , 2004, Science.

[50]  Xiaobo Chen,et al.  Titanium dioxide nanomaterials: self-structural modifications. , 2014, Chemical reviews.

[51]  J. A. Bennett,et al.  Improving selectivity in 2-butyne-1,4-diol hydrogenation using biogenic Pt catalysts , 2012 .

[52]  J. J. Kim,et al.  Method of catalyst coating in micro-reactors for methanol steam reforming , 2007 .

[53]  P. Alphonse,et al.  Nanoparticle Route for the Preparation in Aqueous Medium of Mesoporous TiO2 with Controlled Porosity and Crystalline Framework , 2010 .

[54]  C. Kappe,et al.  Heterogeneous catalytic hydrogenation reactions in continuous-flow reactors. , 2011, ChemSusChem.

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

[56]  Volker Hessel,et al.  Novel process windows for enabling, accelerating, and uplifting flow chemistry. , 2013, ChemSusChem.

[57]  Chris R. Kleijn,et al.  Velocity fluctuations of segmented flow in microchannels , 2008 .

[58]  P. Pfeifer,et al.  Investigations on a Pt/TiO2 catalyst coating for oxidation of SO2 in a microstructured reactor for operation with forced decreasing temperature profile , 2011 .

[59]  M. Ueno,et al.  Development of microchannel reactors using polysilane-supported palladium catalytic systems in capillaries. , 2008, Chemical communications.