Highly efficient synthesis of gamma-valerolactone by catalytic conversion of biomass-derived levulinate esters over support-free mesoporous Ni
Highly efficient synthesis of gamma-valerolactone by catalytic conversion of biomass-derived levulinate esters over support-free mesoporous Ni
复制标题
无载体介孔镍上催化转化生物质衍生的乙酰丙酸酯高效合成γ-戊内酯
DOI：
10.1016/j.renene.2020.09.023
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发表时间：
2021
期刊：
影响因子：
8.7
通讯作者：
Yin Dulin
中科院分区：
文献类型：
--
作者：
Chen Han;Xu Qiong;Zhang Du;Liu Wenzhu;Liu Xianxiang;Yin Dulin
采用简单的固相研磨和原位还原两步法合成了不同摩尔比的柠檬酸和硝酸镍的一系列介孔镍催化剂；这些催化剂进一步用于以2-丙醇作为氢供体将乙酰丙酸酯催化转移加氢生成γ-戊内酯（GVL）。考察了C6H8O7/Ni摩尔比、催化剂用量、反应温度和时间对催化性能的影响。在 C6H8O7/Ni 比例为 1.0:1 M 的 Ni-1.0 催化剂上，在 180°C 6 小时内可实现 99.1% 的优异 GVL 选择性和 100% 的乙酰丙酸乙酯 (EL) 转化率。表征结果表明，Ni-1.0催化剂由介孔金属Ni块体和表面Ni-NiO复合物组成，NiO的酸性位点在EL生产GVL过程中发挥协同催化作用。 Ni-1.0优异的介孔结构和大表面积提高了镍金属活性中心的原子利用率。此外，Ni-1.0催化剂可以很容易地分离并重复使用十次，每次循环时EL转化率仍保持在95%以上。这项工作为将生物质转化为 GVL（一种燃料添加剂化合物）提供了一种高效且环保的催化程序。
A series of mesoporous nickel catalysts with different molar ratios of citric acid and nickel nitrate were synthesized via a simple two-step method by solid-state grinding and in-situ reduction; these catalysts were further employed for the catalytic transfer hydrogenation of levulinate esters to γ-valerolactone (GVL) with 2-propanol as the hydrogen donor. The effects of C6H8O7/Ni molar ratios, catalyst dosage, reaction temperature and time on the catalytic performance were investigated. An excellent GVL selectivity of 99.1% and an ethyl levulinate (EL) conversion of 100% could be achieved at 180 °C in 6 h over Ni-1.0 catalyst with a 1.0:1 M ratio of C6H8O7/Ni. The characterization results showed that the Ni-1.0 catalyst was composed of mesoporous metallic Ni bulk and a surface Ni–NiO composite, and the acid sites of NiO played a synergistic catalytic role in producing GVL from EL. The superior mesoporous structure and large surface area of Ni-1.0 increased the atomic utilization rate of nickel metallic active centers. Moreover, Ni-1.0 catalyst could be easily separated and reused ten times, with an EL conversion above 95% remaining in each recycle. This work provids a highly efficient and environmentally friendly catalytic procedure for the conversion of biomass into GVL, a fuel additive compound.