Transformation of γ-valerolactone into 1,4-pentanediol and 2-methyltetrahydrofuran over Zn-promoted Cu/Al2O3 catalysts

The transformation of γ-valerolactone (GVL) into 1,4-pentanediol (1,4-PDO) and 2-methyltetra-hydrofuran (2-MTHF) in the presence of H2, one of the useful biomass conversion and utilization processes, was investigated with monometallic Cu/Al2O3 and bimetallic ZnCu/Al2O3 catalysts. A 10 wt% Cu-loaded monometallic catalyst produced 1,4-PDO and 2-MTHF in comparable quantities at a medium conversion (∼50%). When Zn was added in a range of Zn/Cu molar ratios of up to 2, in contrast, the catalysts yielded 1,4-PDO in a high selectivity of about 97% at low and high conversion levels. In addition, the 1,4-PDO selectivity over the ZnCu/Al2O3 catalysts remained almost unchanged during recycled runs. That is, the addition of Zn to Cu/Al2O3 switched the product selectivity and improved the catalyst stability and reusability. Furthermore, the physicochemical properties of the catalysts were characterized by several methods including XRD, TEM, TPR, XPS, FTIR of adsorbed pyridine, and so on. On the basis of those results, the relationships between the catalytic performance (activity, selectivity, and reusability) and the catalyst structural features were discussed.

[1]  Osman G. Mamun,et al.  Investigation of solvent effects in the hydrodeoxygenation of levulinic acid to γ-valerolactone over Ru catalysts , 2019, Journal of Catalysis.

[2]  Shu Zhang,et al.  Copper-based catalysts with tunable acidic and basic sites for the selective conversion of levulinic acid/ester to γ-valerolactone or 1,4-pentanediol , 2019, Green Chemistry.

[3]  Yong Li,et al.  Highly chemoselective hydrogenation of lactone to diol over efficient copper-based bifunctional nanocatalysts , 2019, Applied Catalysis B: Environmental.

[4]  Fangming Jin,et al.  Catalytic transfer hydrogenation of levulinate ester into γ-valerolactone over ternary Cu/ZnO/Al2O3 catalyst , 2019, Journal of Energy Chemistry.

[5]  Binglian Liang,et al.  Investigation on Deactivation of Cu/ZnO/Al2O3 Catalyst for CO2 Hydrogenation to Methanol , 2019, Industrial & Engineering Chemistry Research.

[6]  Ning Zhang,et al.  Efficient and sustainable hydrogenation of levulinic-acid to gamma-valerolactone in aqueous solution over acid-resistant CePO4/Co2P catalysts , 2019, Green Chemistry.

[7]  Changhai Liang,et al.  Transfer Hydrogenation of Biomass-Derived Furfural to 2-Methylfuran over CuZnAl Catalysts , 2019, Industrial & Engineering Chemistry Research.

[8]  B. Han,et al.  Highly efficient hydrogenation of levulinic acid into 2-methyltetrahydrofuran over Ni–Cu/Al2O3–ZrO2bifunctional catalysts , 2019, Green Chemistry.

[9]  C. Shin,et al.  Roles of Structural Promoters for Direct CO2 Hydrogenation to Dimethyl Ether over Ordered Mesoporous Bifunctional Cu/M–Al2O3 (M = Ga or Zn) , 2018, ACS Catalysis.

[10]  Jiajun Wang,et al.  Effect of carbon support on the catalytic performance of Cu-based nanoparticles for oxidative carbonylation of methanol , 2018, Applied Surface Science.

[11]  Yulong Zhang,et al.  Effect of Al-containing precursors on Cu/ZnO/Al2O3 catalyst for methanol production , 2018, Fuel Processing Technology.

[12]  Jeehoon Han,et al.  Catalytic production of 1,4-pentanediol from corn stover. , 2017, Bioresource technology.

[13]  Peng Sun,et al.  Synergetic Catalysis of Bimetallic CuCo Nanocomposites for Selective Hydrogenation of Bioderived Esters , 2017 .

[14]  P. Arias,et al.  Structure-activity relationships of Ni-Cu/Al2O3 catalysts for γ-valerolactone conversion to 2-methyltetrahydrofuran , 2017 .

[15]  Xin Chen,et al.  Hydrogenation of γ-valerolactone to 1,4-pentanediol in a continuous flow reactor , 2017 .

[16]  Chongqi Chen,et al.  Characterization and Catalytic Performance of Cu/ZnO/Al2O3 Water–Gas Shift Catalysts Derived from Cu–Zn–Al Layered Double Hydroxides , 2017 .

[17]  C. Mota,et al.  Hydrogenation of Levulinic Acid (LA) to γ-Valerolactone (GVL) over Ni–Mo/C Catalysts and Water-Soluble Solvent Systems , 2017, Catalysis Letters.

[18]  R. Palkovits,et al.  The Role of the Hydrogen Source on the Selective Production of γ-Valerolactone and 2-Methyltetrahydrofuran from Levulinic Acid. , 2016, ChemSusChem.

[19]  A. Bhaumik,et al.  Towards rational design of core–shell catalytic nanoreactor with high performance catalytic hydrogenation of levulinic acid , 2016 .

[20]  I. Chorkendorff,et al.  Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis , 2016, Science.

[21]  Liang Zeng,et al.  Platinum-Modified ZnO/Al2O3 for Propane Dehydrogenation: Minimized Platinum Usage and Improved Catalytic Stability , 2016 .

[22]  H. Ahouari,et al.  The Cu–ZnO synergy in methanol synthesis from CO2, Part 2: Origin of the methanol and CO selectivities explained by experimental studies and a sphere contact quantification model in randomly packed binary mixtures on Cu–ZnO coprecipitate catalysts , 2015 .

[23]  A. Riisager,et al.  Deactivation of solid catalysts in liquid media: the case of leaching of active sites in biomass conversion reactions , 2015 .

[24]  L. Pinard,et al.  The Cu–ZnO synergy in methanol synthesis from CO2, Part 1: Origin of active site explained by experimental studies and a sphere contact quantification model on Cu + ZnO mechanical mixtures , 2015 .

[25]  I. Chorkendorff,et al.  Quantification of zinc atoms in a surface alloy on copper in an industrial-type methanol synthesis catalyst. , 2014, Angewandte Chemie.

[26]  Avelino Corma,et al.  Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels , 2014 .

[27]  Catherine Pinel,et al.  Heterogeneous catalytic hydrogenation of biobased levulinic and succinic acids in aqueous solutions. , 2013, ChemSusChem.

[28]  James A. Dumesic,et al.  Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass , 2013 .

[29]  D. Duprez,et al.  High-surface-area zinc aluminate supported silver catalysts for low-temperature SCR of NO with ethanol , 2012 .

[30]  Qi‐Lin Zhou,et al.  Highly efficient hydrogenation of biomass-derived levulinic acid to γ-valerolactone catalyzed by iridium pincer complexes , 2012 .

[31]  A. Alcántara,et al.  2-Methyltetrahydrofuran (2-MeTHF): a biomass-derived solvent with broad application in organic chemistry. , 2012, ChemSusChem.

[32]  J. Nørskov,et al.  The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts , 2012, Science.

[33]  T. Borowiecki,et al.  The quantitative description of the effects of cesium doping on the activity and properties of Cu/ZnO/Al2O3 catalyst in low-temperature water–gas shift , 2012 .

[34]  Kangnian Fan,et al.  Tunable copper-catalyzed chemoselective hydrogenolysis of biomass-derived γ-valerolactone into 1,4-pentanediol or 2-methyltetrahydrofuran , 2012 .

[35]  S. B. Halligudi,et al.  Direct hydrocyclization of biomass-derived levulinic acid to 2-methyltetrahydrofuran over nanocomposite copper/silica catalysts. , 2011, ChemSusChem.

[36]  Kwan-Young Lee,et al.  Effect of Copper Precursors to the Activity for Dimethyl Ether Synthesis from Syngas over Cu–ZnO/γ-Al2O3 Bifunctional Catalysts , 2011 .

[37]  S. B. Halligudi,et al.  Selective hydrogenation of levulinic acid to γ-valerolactone over carbon-supported noble metal catalysts , 2011 .

[38]  Jean-Paul Lange,et al.  Valeric biofuels: a platform of cellulosic transportation fuels. , 2010, Angewandte Chemie.

[39]  N. Tsubaki,et al.  Effect of H2O on Cu-based catalyst in one-step slurry phase dimethyl ether synthesis , 2009 .

[40]  Luke M. Neal,et al.  Steam reforming of methanol using Cu-ZnO catalysts supported on nanoparticle alumina , 2008 .

[41]  Viktória Fábos,et al.  Integration of Homogeneous and Heterogeneous Catalytic Processes for a Multi-step Conversion of Biomass: From Sucrose to Levulinic Acid, γ-Valerolactone, 1,4-Pentanediol, 2-Methyl-tetrahydrofuran, and Alkanes , 2008 .

[42]  M. Pagliaro,et al.  From glycerol to value-added products. , 2007, Angewandte Chemie.

[43]  J. Suo,et al.  Deactivation and reactivation of copper-containing pentatomic hydrotalcite in catalytic hydroxylation of phenol , 2006 .

[44]  L. Arrúa,et al.  Cu/SiO2 catalysts for methanol to methyl formate dehydrogenation: A comparative study using different preparation techniques , 2000 .

[45]  Yong Wang,et al.  Production of levulinic acid and use as a platform chemical for derived products , 2000 .

[46]  J. Fierro,et al.  CO2 hydrogenation over Pd-modified methanol synthesis catalysts , 1998 .

[47]  J. Fierro,et al.  Structural and surface properties of CuO-ZnO-Cr2O3 catalysts and their relationship with selectivity to higher alcohol synthesis , 1995 .

[48]  T. Fujitani,et al.  Evidence for the migration of ZnOx in a Cu/ZnO methanol synthesis catalyst , 1994 .

[49]  L. Marrelli,et al.  Reduction kinetics of CuO-ZnO , 1993 .

[50]  R. L. Mieville,et al.  Studies on the chemical state of Cu during methanol synthesis , 1984 .

[51]  Á. Molnár,et al.  Studies on the conversions of diols and cyclic ethers—491: Stereochemistry of cyclodehydration of 1,4-diols on the action of brönsted and lewis acids: a comprehensive study , 1981 .

[52]  M. L. Mihailović,et al.  Stereochemistry of cyclic ether formation. Part I. Stereoselective intramolecular cyclisation of aliphatic disecondary 1,4-diols and their sulphonate esters to tetrahydrofurans , 1972 .

[53]  E. P. Parry,et al.  An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity , 1963 .

[54]  R. Hixon,et al.  Derivatives of γ-Valerolactone, 1,4-Pentanediol and 1,4-Di-(β-cyanoethoxy)-pentane1 , 1947 .