Engineering Laboratory for Energy System Process Conversion & Emission Control Technology of Jiangsu Province, School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing 210042, China; Key Laboratory of Energy Thermal Conversion and Control, Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, China.
Engineering Laboratory for Energy System Process Conversion & Emission Control Technology of Jiangsu Province, School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing 210042, China.
Bioresour Technol. 2019 May;279:228-233. doi: 10.1016/j.biortech.2019.01.132. Epub 2019 Jan 29.
Using isopropanol as an in situ hydrogen donor, catalytic transfer hydrogenolysis of lignin into monomeric phenols was studied at mild conditions. The performance of catalysts and the effects of H, temperature, and time on depolymerization of acid extracted birch lignin (ABL) were extensively examined. Platinum-rhenium supported on titanium dioxide (PtRe/TiO) exhibited much higher activity on disrupting CO bonds than Pd/C, HZSM-5, Pt/TiO, and Re/TiO. 18.71 wt% monophenols was achieved for depolymerization of ABL over PtRe/TiO at 240 °C for 12 h with He. 4-Propylsyringol had the highest yield of 7.48 wt%. 2D HSQC NMR analysis reveals that β-O-4 bonds have been fully disrupted during depolymerization. Addition of H led to less monophenols, likely due to the competitive adsorption of active sites on catalysts. Structure-reactivity analysis based on six representative lignins shows that the total yields of monophenols were highly linearly correlated with the β-O-4 contents (R = 0.97).
采用异丙醇作为原位氢供体，在温和条件下研究了木质素催化转移氢解为单体酚。考察了催化剂的性能以及 H、温度和时间对酸提取桦木木质素（ABL）解聚的影响。担载在二氧化钛上的铂铼（PtRe/TiO）在破坏 CO 键方面的活性明显高于 Pd/C、HZSM-5、Pt/TiO 和 Re/TiO。在 He 气氛中，PtRe/TiO 于 240°C 下反应 12 h 可使 ABL 解聚得到 18.71wt%的单酚，其中 4-丙基愈创木酚的收率最高，为 7.48wt%。2D HSQC NMR 分析表明，β-O-4 键在解聚过程中完全断裂。添加 H 会导致单酚产率降低，这可能是由于催化剂活性位的竞争吸附所致。基于 6 种代表性木质素的结构-反应性分析表明，单酚的总收率与β-O-4 含量呈高度线性相关（R=0.97）。
