Cen Youliang, Zhu Shanhui, Guo Jing, Chai Jiachun, Jiao Weiyong, Wang Jianguo, Fan Weibin
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences Taiyuan 030001 PR China
University of Chinese Academy of Sciences Beijing 100049 PR China.
RSC Adv. 2018 Mar 1;8(17):9152-9160. doi: 10.1039/c8ra01316k. eCollection 2018 Feb 28.
A highly active and selective cobalt catalyst was developed for the hydrogenation of biomass-derived ethyl levulinate (EL) to γ-valerolactone (GVL), ethyl 4-hydroxypentanoate (EHP), 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF), which are considered to be value-added chemicals and important biofuels. The effects of reaction time, reaction temperature, catalyst amount and solvent on its catalytic performance were investigated. In addition, the reaction pathway was studied as well. It was found that the selectivity of GVL, 1,4-PDO and 2-MTHF on Co/ZrO can be easily tuned by changing reaction conditions, and can reach as high as 94%, 78% and 77%, respectively. The product selectivity is also significantly affected by the catalyst support. With SBA-15 as the support, the selectivity of EHP can reach 90%. Moreover, Co/ZrO gave an extraordinarily high GVL productivity of 1.50 mol g h and displayed excellent stability and reusability. Interestingly, coke has a positive effect on the enhancement of GVL yield. AL dimers and trimers were identified as the coke species in the hydrogenation of EL. As far as we know, this is the first work conducting the flexible transformation of EL on cobalt catalysts.
开发了一种高活性和选择性的钴催化剂,用于将生物质衍生的乙酰丙酸乙酯(EL)氢化为γ-戊内酯(GVL)、4-羟基戊酸乙酯(EHP)、1,4-戊二醇(1,4-PDO)和2-甲基四氢呋喃(2-MTHF),这些被认为是增值化学品和重要生物燃料。研究了反应时间、反应温度、催化剂量和溶剂对其催化性能的影响。此外,还研究了反应途径。结果发现,通过改变反应条件,Co/ZrO上GVL、1,4-PDO和2-MTHF的选择性可以很容易地调节,分别可高达94%、78%和77%。产物选择性也受到催化剂载体的显著影响。以SBA-15为载体时,EHP的选择性可达90%。此外,Co/ZrO具有1.50 mol g h的极高GVL产率,并表现出优异的稳定性和可重复使用性。有趣的是,焦炭对提高GVL产率有积极作用。在EL的氢化反应中,AL二聚体和三聚体被确定为焦炭物种。据我们所知,这是首次在钴催化剂上进行EL的灵活转化工作。