Zhang Yan, Qiao Wenpu, Gao Zhuangzhi, Guo Daliang
Key Laboratory of Recycling and Eco-Treatment of Waste Biomass of Zhejiang Province, Zhejiang University of Science and Technology, Hangzhou 310023, China.
Key Laboratory of Recycling and Eco-Treatment of Waste Biomass of Zhejiang Province, Zhejiang University of Science and Technology, Hangzhou 310023, China.
Int J Biol Macromol. 2024 Aug;275(Pt 2):133553. doi: 10.1016/j.ijbiomac.2024.133553. Epub 2024 Jul 19.
In this paper, the experiment of cellulose from corn stalk using 1, 2-propylene glycol (PG) and diethylene glycol (DEG) liquefaction catalyzed by phosphoric acid at atmosphere pressure was carried out. The effect of reaction time on the structural changes of cellulose in the liquefaction process of polyhydric alcohols was investigated, aiming at understanding the mechanism of cellulose liquefaction reaction under the action of acid catalyzed polyhydric alcohols. It was found that the liquefaction yield increased first and then decreased with the extension of reaction time, and reached the highest at 150 min (99.34 %). In the phase of increasing liquefaction yield, cellulose was degraded and translated into glucose, which was then converted into plenty of glycosides with PG/DEG. These glycosides were further converted into low molecular weight (LMW) substances such as hydrocarbons, acids, alcohols, esters, ketones, and ethers. At this time, the biofuel contained 70 %-85 % compounds with carbon number less than 25 and 5 %-10 % compounds with carbon number more than 25. As the prolongation of reaction time (after 150 min), quantities of unstable free radicals formed by cellulose degradation could combine with each other or with hydrogen atoms provided by PG/DEG to produce relatively stable macromolecular substances. That is, the polydispersity (M/M, abbreviated Ð = 1.28) of the generated biofuel at this stage no longer decreased. However, liquefaction residue produced at 240 min had changed essentially, which was completely different from the liquefaction residue produced in the early stage of liquefaction. In conclusion, this paper revealed the partial reaction process of cellulose by studying the structural changes in the liquefaction process of polyhydric alcohols, which laid a theoretical foundation for exploring the liquefaction mechanism of cellulose.
本文进行了在常压下以磷酸为催化剂,用1,2 - 丙二醇(PG)和二甘醇(DEG)对玉米秸秆纤维素进行液化的实验。研究了反应时间对多元醇液化过程中纤维素结构变化的影响,旨在了解酸催化多元醇作用下纤维素液化反应的机理。结果发现,随着反应时间的延长,液化产率先升高后降低,在150分钟时达到最高(99.34%)。在液化产率增加阶段,纤维素降解转化为葡萄糖,然后与PG/DEG转化为大量糖苷。这些糖苷进一步转化为碳氢化合物、酸、醇、酯、酮和醚等低分子量(LMW)物质。此时,生物燃料中碳数小于25的化合物占70% - 85%,碳数大于25的化合物占5% - 10%。随着反应时间的延长(150分钟后),纤维素降解形成的大量不稳定自由基会相互结合或与PG/DEG提供的氢原子结合,生成相对稳定的大分子物质。也就是说,此阶段生成的生物燃料的多分散性(M/M,简称为Ð = 1.28)不再降低。然而,240分钟时产生的液化残渣已发生本质变化,与液化初期产生的液化残渣完全不同。总之,本文通过研究多元醇液化过程中的结构变化揭示了纤维素的部分反应过程,为探索纤维素液化机理奠定了理论基础。