Catalytic Transfer Hydrogenation of Ethyl Levulinate to gamma-Valerolactone Over Ni Supported on Equilibrium Fluid-Catalytic-Cracking Catalysts
Catalytic Transfer Hydrogenation of Ethyl Levulinate to gamma-Valerolactone Over Ni Supported on Equilibrium Fluid-Catalytic-Cracking Catalysts
复制标题
平衡流体催化裂化催化剂负载 Ni 上乙酰丙酸乙酯催化转移加氢生成 γ-戊内酯
DOI：
10.1007/s10562-020-03326-5
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发表时间：
2021
影响因子：
2.8
通讯作者：
Yin Dulin
中科院分区：
文献类型：
--
作者：
Chen Han;Xu Qiong;Li Hui;Liu Jian;Liu Xianxiang;Huang Geng;Yin Dulin
采用简单的研磨-裂解法制备了平衡催化裂化催化剂负载镍催化剂(Ni/E-CAT)，并将其用于乙酰丙酸乙酯(EL)的转移加氢制γ-戊内酯(GVL)。在180℃下反应6h，30-Ni/E-CAT的GVL选择性为96.2%，EL转化率为90.3%。通过X射线衍射、氮气吸附-脱附、NH3-TPD和扫描电子显微镜分析表明，30-Ni/E-CAT催化剂的高活性归因于其分散的镍金属活性中心和有效的酸性中心。催化探针测试表明，Ni/E-CAT的金属中心和酸中心对异丙醇中GVL的合成起协同催化作用，其中Ni金属中心促进EL中酮的加氢反应，E-CAT的酸中心促进中间体4-羟基戊酸乙酯或异丙酯的内酯化反应。提出了该催化体系的两条反应途径和协同机理。此外，Ni/E-CAT催化剂在四个循环中表现出良好的稳定性，没有明显的催化活性损失。
Nickel supported on equilibrium fluid-catalytic-cracking catalysts (Ni/E-cats) were prepared by a simple grinding-pyrolysis method and employed for the transfer hydrogenation of ethyl levulinate (EL) to γ-valerolactone (GVL). 96.2% selectivity of GVL and 90.3% conversion of EL were obtained at 180 °C for 6 h over 30-Ni/E-cat. Through XRD, N2adsorption–desorption, NH3-TPD and SEM analysis, the high activity of the 30-Ni/E-cat catalyst was attributed to its dispersed Ni metal active centers and available acidic sites. Catalytic probe test revealed that metal and acid sites of Ni/E-cat played a synergistic catalytic role in the synthesis of GVL in 2-propanol, where Ni metal sites contribute to the hydrogenation of ketone group in EL, and acid sites of E-cat promoted the lactonization of intermediate ethyl- or isopropyl 4-hydroxyvalerate. Two reaction pathways and synergistic mechanism were proposed in this catalytic system. Moreover, Ni/E-cat catalyst exhibited good stability up to four cycles without obvious loss of catalytic activity.Graphic Abstract