Energy Technology Research Group, School of Engineering Science, University of Southampton, Highfield, Southampton SO17 1BJ, United Kingdom.
Bioresour Technol. 2010 Aug;101(15):6136-46. doi: 10.1016/j.biortech.2010.02.078. Epub 2010 Mar 21.
Lignin is a key component in the biomass with a complex polymeric structure of the phenyl-C(3) alkyl units. The kraft lignin from the wood pulping process is tested in TG-FTIR and Py-GC-MS. The samples are pyrolyzed in TGA coupled with FTIR from 30 to 900 degrees C at the heating rate of 20 and 40K/min. The evolution of phenolic compounds in the initial pyrolysis stage of lignin is determined by FTIR, while the second stage is mainly attributed to the production of the low molecular weight species. A bench-scale fast pyrolysis unit is employed to investigate the effect of temperature on the product yield and composition. It is found that the guaiacol-type and syringol-type compounds as the primary products of lignin pyrolysis are predominant in bio-oil, acting as the significant precursors for the formation of the derivatives such as the phenol-, cresol- and catechol-types. A series of free-radical chain-reactions, concerning the cracking of different side-chain structures and the methoxy groups on aromatic ring, are proposed to demonstrate the formation pathways for the typical compounds in bio-oil by closely relating lignin structure to the pyrolytic mechanisms. The methoxy group (-OCH(3)) is suggested to work as an important source for the formation of the small volatile species (CO, CO(2) and CH(4)) through the relevant free radical coupling reactions.
木质素是生物质中一种复杂的苯丙烷结构的主要成分。对木材制浆过程中的 kraft 木质素进行了 TG-FTIR 和 Py-GC-MS 测试。样品在 TGA 中以 20 和 40K/min 的加热速率从 30 到 900°C 进行热重-傅里叶变换红外光谱分析。FTIR 确定了木质素初始热解阶段酚类化合物的演变,而第二阶段主要归因于低分子量物质的产生。采用台式快速热解装置研究了温度对产物产率和组成的影响。结果表明,愈创木酚型和丁香酚型化合物作为木质素热解的主要产物在生物油中占优势,作为酚型、甲酚型和邻苯二酚型等衍生物形成的重要前体。通过将木质素结构与热解机制紧密联系起来,提出了一系列涉及不同侧链结构和芳环上甲氧基断裂的自由基链式反应,以说明生物油中典型化合物的形成途径。建议通过相关自由基偶联反应,将甲氧基(-OCH(3))作为形成小分子挥发性物质(CO、CO(2)和 CH(4))的重要来源。