Hydrogenation of levulinic acid to γ-valerolactone over anatase-supported Ru catalysts: Effect of catalyst synthesis protocols on activity

被引:76
作者
Piskun, A. S. [1 ]
Ftouni, J. [2 ]
Tang, Z. [1 ]
Weckhuysen, B. M. [2 ]
Bruijnincx, P. C. A. [2 ]
Heeres, H. J. [1 ]
机构
[1] Univ Groningen, ENTEG, Dept Chem Engn, Nijenborgh 4, NL-9747 AG Groningen, Netherlands
[2] Univ Utrecht, Debye Inst Nanomat Sci, Inorgan Chem & Catalysis, Univ Weg 99, NL-3584 CG Utrecht, Netherlands
关键词
Biobased chemicals; Hydrogenation; Ru catalysts; Titania; PHASE HYDROGENATION; RUTHENIUM; BIOMASS; CONVERSION; LIQUID; SELECTIVITY; SOLVENT; ESTERS; SITES; YIELD;
D O I
10.1016/j.apcata.2017.09.032
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
gamma-Valerolactone (GVL) is a value-added renewable chemical with great potential and can be obtained from biomass by the hydrogenation of levulinic acid (LA) using metal-based catalysts, such as Ru/TiO2. We here report an in depth study of the effect of catalyst synthesis parameters on the performance of Ru/TiO2 (anatase), varying the nature of the Ru-precursor and the conditions of the calcination and/or reduction step. Catalyst performance was evaluated under batch conditions at a hydrogen pressure of 45 bar and using either water (90 degrees C) or dioxane (150 degrees C) as solvent. The experiments showed that catalyst activity depends greatly on the Ru precursor used (RuCl3, RuNO(NO3)(3), Ru(NH3)(6)Cl-3). Best results when considering the turn-over frequencies(TOF) of the catalysts were obtained using the RuNO(NO3)(3) precursor, whereas RuCl3 performed better when considering the initial rate based on Ru intake. An intermediate calcination step and the use of a hydrogen-rich sweep gas during the fmal reduction step were shown to have a negative impact on catalyst activity. Characterization of the fresh catalysts by BET and TEM provided valuable insight in the relation between the catalyst structure and its activity.
引用
收藏
页码:197 / 206
页数:10
相关论文
共 52 条
[1]   Toward rational design of stable, supported metal catalysts for aqueous-phase processing: Insights from the hydrogenation of levulinic acid [J].
Abdelrahman, Omar Ali ;
Luo, Helen Y. ;
Heyden, Andreas ;
Roman-Leshkov, Yuriy ;
Bond, Jesse Q. .
JOURNAL OF CATALYSIS, 2015, 329 :10-21
[2]  
AI-Shaal M. G., 2014, GREEN CHEM, V16, P1358
[3]   Exploring the ruthenium catalysed synthesis of γ-valerolactone in alcohols and utilisation of mild solvent-free reaction conditions [J].
Al-Shaal, Mohammad G. ;
Wright, William R. H. ;
Palkovits, Regina .
GREEN CHEMISTRY, 2012, 14 (05) :1260-1263
[4]   Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass [J].
Alonso, David Martin ;
Wettstein, Stephanie G. ;
Dumesic, James A. .
GREEN CHEMISTRY, 2013, 15 (03) :584-595
[5]   Rational nanoparticle synthesis to determine the effects of size, support, and K dopant on Ru activity for levulinic acid hydrogenation to γ-valerolactone [J].
Cao, Shuo ;
Monnier, John R. ;
Williams, Christopher T. ;
Diao, Weijian ;
Regalbuto, John R. .
JOURNAL OF CATALYSIS, 2015, 326 :69-81
[6]   Experimental and kinetic modeling studies on the biphasic hydrogenation of levulinic acid to γ-valerolactone using a homogeneous water-soluble Ru-(TPPTS) catalyst [J].
Chalid, M. ;
Broekhuis, A. A. ;
Heeres, H. J. .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2011, 341 (1-2) :14-21
[7]  
Chalid M., 2012, THESIS
[8]   Integrated Catalytic Process to Directly Convert Furfural to Levulinate Ester with High Selectivity [J].
Chen, Bingfeng ;
Li, Fengbo ;
Huang, Zhijun ;
Lu, Tao ;
Yuan, Yin ;
Yuan, Guoqing .
CHEMSUSCHEM, 2014, 7 (01) :202-209
[9]  
Ding DQ, 2014, GREEN CHEM, V16, P3846, DOI [10.1039/C4GC00737A, 10.1039/c4gc00737a]
[10]  
Fogler H.S., 2016, Elements of Chemical Reaction Engineering, VFifth