Double-protective strategy enabling high-efficiency production of levulinic acid from high-loading cellulose

IF 13.1 1区 化学 Q1 Energy
Hang Lv , Ping Hu , Chenyu Ge, Fengyi Lu, Hui Li, Di Wu, Zhidan Xue, Yimeng Guo, Xixi Liu, Liangfang Zhu, Changwei Hu
{"title":"Double-protective strategy enabling high-efficiency production of levulinic acid from high-loading cellulose","authors":"Hang Lv ,&nbsp;Ping Hu ,&nbsp;Chenyu Ge,&nbsp;Fengyi Lu,&nbsp;Hui Li,&nbsp;Di Wu,&nbsp;Zhidan Xue,&nbsp;Yimeng Guo,&nbsp;Xixi Liu,&nbsp;Liangfang Zhu,&nbsp;Changwei Hu","doi":"10.1016/j.jechem.2025.03.013","DOIUrl":null,"url":null,"abstract":"<div><div>Valorization of renewable cellulose into initial platform chemicals (IPCs) generally suffers from low process efficiency owing to difficult depolymerization of recalcitrant cellulose and troublesome repolymerization of high-reactive intermediates to undesired humins. Herein, we report a double-protective strategy for cellulose depolymerization and orientated conversion to levulinic acid (LA), one of the important IPCs, by in-situ adding protective formaldehyde (HCHO). This approach initiates from the (hemi)acetalation of hydroxyl groups in cellulose with HCHO, causing controllable depolymerization to (hemi)acetalized glucose with increased rate kinetically and a new mechanism of its catalytic conversion to LA via (hemi)acetal-driven direct C1–C2 cleavage. As such, the cellulose-to-LA conversion is protectively proceeded with the repolymerization of reactive intermediates prevented remarkably, leading to an excellent LA yield of 87.3 mol% from high-loading microcrystalline cellulose (15.0 wt% in aqueous phase) in a biphasic solvent containing 2-methyltetrahydrofuran and water. The process efficiency, expressed as space-time yield, is improved by 3.6 fold when compared with a non-protective approach. This work highlights an advance in maximizing the utilization of biomass-derived carbons for high-efficiency production of important IPCs directly from cellulose for future biorefinery.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"106 ","pages":"Pages 577-586"},"PeriodicalIF":13.1000,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Energy Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2095495625002220","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"Energy","Score":null,"Total":0}
引用次数: 0

Abstract

Valorization of renewable cellulose into initial platform chemicals (IPCs) generally suffers from low process efficiency owing to difficult depolymerization of recalcitrant cellulose and troublesome repolymerization of high-reactive intermediates to undesired humins. Herein, we report a double-protective strategy for cellulose depolymerization and orientated conversion to levulinic acid (LA), one of the important IPCs, by in-situ adding protective formaldehyde (HCHO). This approach initiates from the (hemi)acetalation of hydroxyl groups in cellulose with HCHO, causing controllable depolymerization to (hemi)acetalized glucose with increased rate kinetically and a new mechanism of its catalytic conversion to LA via (hemi)acetal-driven direct C1–C2 cleavage. As such, the cellulose-to-LA conversion is protectively proceeded with the repolymerization of reactive intermediates prevented remarkably, leading to an excellent LA yield of 87.3 mol% from high-loading microcrystalline cellulose (15.0 wt% in aqueous phase) in a biphasic solvent containing 2-methyltetrahydrofuran and water. The process efficiency, expressed as space-time yield, is improved by 3.6 fold when compared with a non-protective approach. This work highlights an advance in maximizing the utilization of biomass-derived carbons for high-efficiency production of important IPCs directly from cellulose for future biorefinery.

Abstract Image

双保护策略使高负荷纤维素高效生产乙酰丙酸
可再生纤维素转化为初始平台化学品(IPCs)的过程效率较低,这主要是由于难降解纤维素的解聚和高活性中间体重新聚合到不需要的人类物质的麻烦。本文报道了通过原位添加保护性甲醛(HCHO)对纤维素解聚和定向转化为乙酰丙酸(LA)的双重保护策略。该方法从纤维素中羟基与HCHO的(半)乙酰化反应开始,在动力学上引起可控解聚以加快(半)乙酰化葡萄糖的速率,并通过(半)乙酰化驱动的直接C1-C2裂解催化转化为LA的新机制。因此,在含有2-甲基四氢呋喃和水的双相溶剂中,高负荷微晶纤维素(水相中为15.0 wt%)的LA产率达到87.3 mol%。以空时产率表示的工艺效率,与非保护方法相比提高了3.6倍。这项工作强调了最大限度地利用生物质衍生碳,直接从纤维素中高效生产重要的ipc,用于未来的生物炼制。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Journal of Energy Chemistry
Journal of Energy Chemistry CHEMISTRY, APPLIED-CHEMISTRY, PHYSICAL
CiteScore
19.10
自引率
8.40%
发文量
3631
审稿时长
15 days
期刊介绍: The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies. This journal focuses on original research papers covering various topics within energy chemistry worldwide, including: Optimized utilization of fossil energy Hydrogen energy Conversion and storage of electrochemical energy Capture, storage, and chemical conversion of carbon dioxide Materials and nanotechnologies for energy conversion and storage Chemistry in biomass conversion Chemistry in the utilization of solar energy
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信