NMR of Facility of Research (SGIker), University of the Basque Country (UPV/EHU), Avenida Tolosa 72, 20018 Donostia-San Sebastián, Spain.
INIA-CIFOR, Forestry Products Department, Ctra. de la Coruña, Km 7.5, Madrid 28040, Spain.
Int J Biol Macromol. 2017 Dec;105(Pt 1):238-251. doi: 10.1016/j.ijbiomac.2017.07.030. Epub 2017 Jul 6.
In modern lignocellulosic-based biorefineries, carbohydrates can be transformed into biofuels and pulp and paper, whereas lignin is burned to obtain energy. However, a part of lignin could be converted into value-added products including bio-based aromatic chemicals, as well as building blocks for materials. Then, a good knowledge of lignin is necessary to define its valorisation procedure. This study characterized different lignins from side-streams produced from olive tree pruning bioethanol production (lignins collected from steam explosion pretreatment with water or phosphoric acid as catalysts, followed by simultaneous saccharification and fermentation process) and alkaline pulping (lignins recovered from kraft and soda-AQ black liquors). Together with the chemical composition, the structure of lignins was investigated by FTIR, C NMR, and 2D NMR. Bioethanol lignins had clearly distinct characteristics compared to pulping lignins; a certain number of side-chain linkages (mostly alkyl-aryl ether and resinol) accompanied with lower phenolic hydroxyls content. Bioethanol lignins also showed a significant amount of carbohydrates, mainly glucose and protein impurities. By contrast, pulping lignins revealed xylose together with a dramatical reduction of side-chains (some resinol linkages survive) and thereby higher phenol content, indicating rather severe lignin degradation during alkaline pulping processes. All lignins showed a predominance of syringyl units.
在现代以木质纤维素为基础的生物炼制厂中,碳水化合物可以转化为生物燃料和纸浆,而木质素则被燃烧以获取能量。然而,一部分木质素可以转化为附加值产品,包括生物基芳香化学品以及材料的构建块。因此,需要对木质素有很好的了解,才能确定其增值过程。本研究对来自橄榄树修剪生物乙醇生产过程中的侧流木质素(分别用蒸汽爆破预处理收集的木质素,催化剂为水或磷酸,然后进行同步糖化和发酵过程)和碱性制浆(从牛皮纸浆和苏打-AQ 黑液中回收的木质素)进行了不同木质素的特性描述。除了化学成分外,还通过傅里叶变换红外光谱(FTIR)、碳核磁共振(C NMR)和二维核磁共振(2D NMR)对木质素的结构进行了研究。与制浆木质素相比,生物乙醇木质素具有明显不同的特征;存在一定数量的侧链连接(主要是烷基-芳基醚和树脂醇),同时酚羟基含量较低。生物乙醇木质素还含有大量的碳水化合物,主要是葡萄糖和蛋白质杂质。相比之下,制浆木质素则显示出木糖,同时侧链大量减少(一些树脂醇连接仍然存在),因此酚含量较高,表明碱性制浆过程中木质素发生了严重降解。所有木质素均以愈创木基单元为主。