Direct conversion of bio-ethanol to isobutene on nanosized Zn(x)Zr(y)O(z) mixed oxides with balanced acid-base sites.

We report the design and synthesis of nanosized Zn(x)Zr(y)O(z) mixed oxides for direct and high-yield conversion of bio-ethanol to isobutene (~83%). ZnO is addded to ZrO(2) to selectively passivate zirconia's strong Lewis acidic sites and weaken Brönsted acidic sites, while simultaneously introducing basicity. As a result, the undesired reactions of bio-ethanol dehydration and acetone polymerization/coking are suppressed. Instead, a surface basic site-catalyzed ethanol dehydrogenation to acetaldehyde, acetaldehyde to acetone conversion via a complex pathway including aldol-condensation/dehydrogenation, and a Brönsted acidic site-catalyzed acetone-to-isobutene reaction pathway dominates on the nanosized Zn(x)Zr(y)O(z) mixed oxide catalyst, leading to a highly selective process for direct conversion of bio-ethanol to isobutene.

[1]  T. Yamaguchi,et al.  Acid-base bifunctional catalysis by ZrO2 and its mixed oxides , 1994 .

[2]  H. Hattori,et al.  Surface properties of zirconium oxide and its catalytic activity for isomerization of 1-butene , 1979 .

[3]  James A. Dumesic,et al.  An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates , 2007 .

[4]  Clarence Dayton Chang,et al.  The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts: II. Pressure effects , 1977 .

[5]  C. Jacobsen,et al.  Mesoporous Zeolite Single Crystals , 2000 .

[6]  T. Nakajima,et al.  A highly active and highly selective oxide catalyst for the conversion of ethanol to acetone in the presence of water vapour , 1994 .

[7]  Francesco Ancillotti,et al.  Oxygenate fuels: Market expansion and catalytic aspect of synthesis , 1998 .

[8]  A. Guerrero-Ruíz,et al.  Interaction of Carbon Dioxide with the Surface of Zirconia Polymorphs , 1998 .

[9]  J. Nováková,et al.  Reaction of ammonia with surface species formed from acetone on a HZSM-5 zeolite , 1991 .

[10]  T. Nakajima,et al.  Efficient synthesis of acetone from ethanol over ZnO–CaO catalyst , 1987 .

[11]  A. Corma,et al.  Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. , 2006, Chemical reviews.

[12]  J. Kitagawa,et al.  Acidic properties of Binary Metal Oxides , 1973 .

[13]  M. Girolamo,et al.  Light olefins dimerization to high quality gasoline components , 2001 .

[14]  M. A. Hasan,et al.  Surface Reactions of Acetone on Al2O3, TiO2, ZrO2, and CeO2: IR Spectroscopic Assessment of Impacts of the Surface Acid−Base Properties , 2001 .

[15]  K. Murata,et al.  Dehydration of Ethanol into Ethylene over Solid Acid Catalysts , 2005 .

[16]  H. Zou,et al.  Ultrafast enzyme immobilization over large-pore nanoscale mesoporous silica particles. , 2006, Chemical communications.

[17]  M. Bochmann,et al.  Zirconocenes as initiators for carbocationic isobutene homo- and copolymerizations , 1998 .

[18]  G. Hutchings,et al.  Acetone conversion to isobutene in high selectivity using zeolite β catalyst , 1993 .

[19]  Mark E. Davis,et al.  Studies on the Catalytic Activity of Zirconia Promoted with Sulfate, Iron, and Manganese , 1996 .

[20]  X. Verykios,et al.  Renewable Hydrogen from Ethanol by Autothermal Reforming , 2004, Science.

[21]  Jong‐San Chang,et al.  Trimerization of isobutene over a zeolite beta catalyst , 2007 .

[22]  J. Goldemberg Ethanol for a Sustainable Energy Future , 2007, Science.

[23]  C. P. Nicolaides,et al.  Catalytic skeletal isomerization of linear butenes to isobutene , 1993 .