载体对钼基催化剂催化解聚硫酸盐木质素制备液体燃料和酚类单体的影响研究  

Catalytic depolymerization of kraft lignin for liquid fuels and phenolic monomers over molybdenum-based catalysts:The effect of supports

作　　者：王一双 陈明强[1,2] 史经经 张进辉 李唱 王君[1] WANG Yi-shuang;CHEN Ming-qiang;SHI Jing-jing;ZHANG Jin-hui;LI Chang;WANG Jun(School of Chemical Engineering,Anhui University of Science and Technology,Huainan 232001,China;Analytical and Testing Center,Anhui University of Science and Technology,Huainan 232001,China)

机构地区：[1]安徽理工大学化学工程学院,安徽淮南232001 [2]安徽理工大学分析测试中心,安徽淮南232001

出　　处：《燃料化学学报》2021年第12期1922-1935,共14页Journal of Fuel Chemistry and Technology

基　　金：supported by the Key Research and Development Projects of Anhui Province (202004a06020053);National Natural Science Foundation of China (51876001, 51906001)

摘　　要：本文研究了不同载体(黏土(海泡石(SEP)、凹凸棒石(ATP)、蒙脱土(MTM))和氧化物(Al_(2)O_(3)和SiO_(2))及其负载的Mo基催化剂对超临界乙醇体系中催化解聚木质素制备液体燃料和酚类单体的影响。催化剂表征结果证明,不同结构性质的载体会影响Mo基催化剂结构、表面Mo^(5+)含量和酸性位分布。与Al_(2)O_(3)和SiO_(2)相比,黏土基载体具有更多的强酸位,不利于木质素油(LO)的生成,形成更多的固体产物。仅使用载体获得的LO中得到的石油醚溶性产物(PEsp)主要为烷基/烷氧基取代苯酚,而Mo基催化剂中Mo物种(尤其是Mo^(5+))显著提高了LO和PEsp的产量。Mo/SiO_(2)表面Mo^(5+)物种最多,LO产率最高,为85.2%,其中生成的烷基/烷氧基取代苯酚达450.3 mg/glignin。在黏土负载的Mo催化剂中,Mo/SEP的LO产率(82.3%)和PEsp产率(70.8%)较高,所获得取代酚达到398.8 mg/glignin。本研究系统地报道了绿色环保型黏土基材料在木质素转化中的应用,为黏土基材料在生物质转化中的应用提供了关键信息。Catalytic lignin depolymerization(CCLD)for liquid fuels and phenolic monomers was investigated over various supports including clays(e.g.,sepiolite(SEP),attapulgite(ATP),and montmorillonite(MTM)),and oxides(e.g.,Al_(2)O_(3)and SiO_(2))as well as their supported Mo-based catalysts under supercritical ethanol.The characterization results demonstrated that different supports with diverse structural properties could affect the textural structures,surface Mo^(5+)content,and acid sites distribution.Clay-based supports had more strong acid sites as compared with Al_(2)O_(3)and SiO_(2),which went against the production of lignin oil(LO)and led to form more solid products during CLD experiments.Meanwhile,the obtained petroleum ether-soluble product(PEsp)in LO catalyzed by sole supports was mainly alkyl/alkoxy substituted phenols.Additionally,Mo species(especially Mo^(5+))significantly increased the yields of LO and PEsp.Mo/SiO_(2)had the highest surface Mo^(5+)species,showing the highest LO yield of 85.2%,in which the produced alkyl/alkoxy substituted phenols reached 450.3 mg/glignin.Among the clay-supported Mo catalysts,Mo/SEP presented superior LO(82.3%)and PEsp(70.8%)yields and the generated substituted phenols reached 398.8 mg/glignin.This paper systematically reported the application of green and environmentally friendly clay-based materials in lignin conversion,which provides some key information for the development of clay catalysts for biomass conversion.

关 键 词：硫酸盐木质素 催化解聚 木质素油 钼基催化剂 黏土材料 酚类单体 

分 类 号：TK6[动力工程及工程热物理—生物能]