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Hydrogenation of levulinic acid to γ-valerolactone over anatase-supported Ru catalysts: Effect of catalyst synthesis protocols on activity
Applied Catalysis A: General ( IF 5.5 ) Pub Date : 2017-09-28 , DOI: 10.1016/j.apcata.2017.09.032
A.S. Piskun , J. Ftouni , Z. Tang , B.M. Weckhuysen , P.C.A. Bruijnincx , H.J. Heeres

γ-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 °C) or dioxane (150 °C) as solvent. The experiments showed that catalyst activity depends greatly on the Ru precursor used (RuCl3, RuNO(NO3)3, Ru(NH3)6Cl3). 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 final 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.



中文翻译:

锐钛矿型Ru催化剂上乙酰丙酸加氢成γ-戊内酯的研究:催化剂合成工艺对活性的影响

γ-戊内酯(GVL)是一种具有巨大潜力的增值可再生化学品,可以通过使用Ru / TiO 2等金属基催化剂将乙酰丙酸(LA)加氢从生物质中获得。我们在此报告了对催化剂合成参数对Ru / TiO 2(锐钛矿)性能,改变Ru前体的性质以及煅烧和/或还原步骤的条件的影响的深入研究。在间歇条件下,在45 bar的氢气压力下,使用水(90°C)或二恶烷(150°C)作为溶剂,评估催化剂的性能。实验表明,催化剂的活性很大程度上取决于所用的Ru前驱体(RuCl 3,RuNO(NO 33,Ru(NH 36 Cl 3)。当使用RuNO(NO 33前体获得最佳的催化剂周转频率(TOF)时,获得最佳结果,而考虑到基于Ru摄入的初始速率,RuCl 3表现更好。结果表明,中间煅烧步骤和在最终还原步骤中使用富氢吹扫气对催化剂活性具有负面影响。通过BET和TEM对新鲜催化剂进行表征,为催化剂结构与其活性之间的关系提供了有价值的见解。

更新日期:2017-09-28
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