Pt/Co_(x)Al催化剂上乙酰丙酸甲酯加氢与甲醇水液相重整反应耦合制备γ-戊内酯  

Synthesis ofγ-valerolactone through coupling of methyl levulinate hydrogenation with aqueous phase reforming of methanol over Pt/Co_(x)Al catalyst

作　　者：吕泽祥 朱善辉 董梅[1] 秦张峰[1] 樊卫斌[1] 王建国 LU Zexiang;ZHU Shanhui;DONG Mei;QIN Zhangfeng;FAN Weibin;WANG Jianguo(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室,山西太原030001 [2]中国科学院大学,北京100049

出　　处：《燃料化学学报（中英文）》2024年第9期1266-1279,共14页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金(22278416);山西省基础研究计划(202203021212326);中国科学院山西煤炭化学研究所自主创新基金(SCIC-DT-2023-02)资助。

摘　　要：生物质衍生物乙酰丙酸甲酯(ML)加氢制备高值化学品γ-戊内酯(GVL)通常需要在高压氢气中进行,存在成本高和危险性大等问题。本研究采用Pt/Co_(x)Al催化剂,将ML加氢反应与甲醇水液相重整(APRM)相耦合制备GVL,甲醇重整所获得的氢气原位用于ML的加氢反应,避免了外部氢源的使用,并考察了催化剂组成、反应溶液浓度和反应温度等条件对催化反应性能的影响。结果表明,Pt/Co_(x)Al催化剂在该耦合反应体系中具有优异的催化性能,GVL收率高达98.2%,六次循环后性能仍保持稳定。多种表征手段证明,Pt^(0)是ARPM和ML加氢反应的活性中心,Bronsted酸位点则促进ML水解和中间体的内酯化反应,两者之间的协同作用推动了GVL的生成。Pt与CoxAl载体之间存在强相互作用,Co含量适宜时,Pt/Co_(x)Al催化剂具有较高的Pt分散度和丰富的Br?nsted酸位点,因而表现出优异的催化性能。这些结果对探索新型高效的生物质衍生物制备燃料和化学品反应过程具有重要的参考价值。The synthesis of high-valueγ-valerolactone(GVL)from biomass-derived methyl levulinate(ML)conventionally requires a high-pressure hydrogenation process,which incurs significant costs and safety concerns.This study proposes an innovative approach to produce GVL by integrating ML hydrogenation with aqueous phase reforming of methanol(APRM)using Pt/Co_(x)Al catalysts,thereby eliminating the need for an external hydrogen source.The influence of catalyst composition,methanol concentration,and reaction temperature on catalytic performance has been carefully examined.The results suggest that Pt/Co1Al demonstrated exceptional activity,yielding up to 98.2%GVL,and maintaining stable performance over multiple cycles.Characterization results revealed that Pt^(0) facilitates both APRM and ML hydrogenation,while Brønsted acid sites catalyze the hydrolysis of ML and lactonization of intermediates.The synergy between Pt^(0) and Brønsted acid sites is essential for GVL formation.The appropriate amount of Co not only enhances Pt dispersion but also increases Brønsted acid sites,thereby boosting catalytic efficiency.This work offers a sustainable and economically feasible strategy for transforming biomass derivatives into valuable fuels and chemicals.

关 键 词：甲醇液相重整 乙酰丙酸甲酯 γ-戊内酯 PT 加氢反应 

分 类 号：O643[理学—物理化学]