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可再生醇类在白杨有机溶剂木质素自催化生产中的应用。

Use of Renewable Alcohols in Autocatalytic Production of Aspen Organosolv Lignins.

作者信息

Bujanovic Biljana M, Hirth Kolby, Ralph Sally, Reiner Richard S, Dongre Prajakta, Mickles Clayton, Karlen Steven D, Baez Carlos, Clemons Craig

机构信息

US Department of Agriculture-Forest Service-Forest Products Laboratory, Madison, Wisconsin 53726, United States.

Department of Biological Systems Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.

出版信息

ACS Omega. 2024 Aug 23;9(36):38227-38247. doi: 10.1021/acsomega.4c05981. eCollection 2024 Sep 10.

Abstract

This study aimed to investigate the intrinsic efficiency of renewable alcohols, applied under autocatalytic conditions, for removing lignin from aspen and hot-water-extracted aspen while substantially preserving the lignin structure so as to facilitate various valorization strategies. Ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol (BDO), ethanol (EtOH), and tetrahydrofurfuryl alcohol (THFA) were evaluated based on their lignin solubilization ability, expressed as the relative energy difference (RED) following the principles of the Hansen solubility theory. The findings indicate that alcohols with a higher lignin solubilization potential lead to increased delignification, almost 90%, and produce a lignin with a higher content of β-O-4 bonds, up to 68% of those found in aspen milled wood lignin, thereby indicating their potential for valorization through depolymerization. However, these alcohols also produce lignin with a higher content of β-β and β-5 bonds, resulting in a higher molecular weight and polydispersity, due to readily occurring homolytic reactions. Hot-water extraction (HWE) conducted prior to alcohol treatment reduced the delignification efficiency and resulted in a lignin with a lower β-O-4 bond content. The lignins produced in these experiments exhibited a superior UV-A absorption capacity compared with synthetic benzophenone, as well as a greater radical quenching ability than synthetic butylated hydroxytoluene, indicating their potential for use in the protection of polymers against degradation.

摘要

本研究旨在考察在自催化条件下应用可再生醇从白杨木和热水抽提白杨木中去除木质素的内在效率,同时大幅保留木质素结构,以促进各种增值策略。基于它们的木质素溶解能力对乙二醇(EG)、丙二醇(PG)、1,4-丁二醇(BDO)、乙醇(EtOH)和四氢糠醇(THFA)进行了评估,按照汉森溶解度理论的原理,以相对能量差(RED)表示。研究结果表明,具有较高木质素溶解潜力的醇会使脱木质素率提高,几乎达到90%,并产生β-O-4键含量更高的木质素,高达白杨木磨木木素中β-O-4键含量的68%,从而表明它们通过解聚进行增值的潜力。然而,由于容易发生均裂反应,这些醇也会产生β-β键和β-5键含量更高的木质素,导致分子量和多分散性更高。在醇处理之前进行的热水抽提(HWE)降低了脱木质素效率,并产生了β-O-4键含量较低的木质素。与合成二苯甲酮相比,这些实验中产生的木质素表现出优异的紫外-A吸收能力,并且比合成丁基化羟基甲苯具有更强的自由基猝灭能力,表明它们在保护聚合物免受降解方面具有应用潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c824/11391562/5760f7b2a4b6/ao4c05981_0019.jpg

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