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通过磷-31核磁共振对热解油中含氧官能团的作用进行深入研究。

In-depth study on the effect of oxygen-containing functional groups in pyrolysis oil by P-31 NMR.

作者信息

Wu Zhihong, Ben Haoxi, Yang Yunyi, Luo Ying, Nie Kai, Jiang Wei, Han Guangting

机构信息

Southeast University Nanjing 210096 China

Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment Nanjing 210096 China.

出版信息

RSC Adv. 2019 Aug 29;9(47):27157-27166. doi: 10.1039/c9ra04099d.

Abstract

One of the major obstacles to the widespread use of pyrolysis oil is its high oxygen content, with oxygen atoms being mainly present in the hydroxyl and the carboxyl groups. Therefore, quantitative and accurate characterization of oxygen-containing functional groups is of great significance. This study employed P NMR to conduct in-depth studies on several model compounds including four kinds of alcohols and carboxylic acids. The model compounds have been investigated for stability in P NMR solution for both short storage (4 hours) and long storage (14 days), namely by and monitoring. The experimental phenomena indicates that carboxylic hydroxyl has poor stability compared to alcohols hydroxyl group, which is reflected in the amount of alcohol compounds remaining over 90% after long-term storage. Among the carboxylic acids used in the study, aromatic acids are relatively stable. Interestingly, oxalic acid is extremely unstable and completely decomposed in the first hour, while formic acid had only a small amount left after one day of storage. Therefore, the optimum time for the preparation, storage and upgrading of the pyrolysis oil can be determined by analysis of the stability of the oxygen-containing functional groups in P NMR solution to ensure accuracy. Moreover, according to the results of the P NMR and other characterization methods, it can been seen that water was formed during the decomposition of all the model compounds. This is a report on the quantitative characterization of different oxygen-containing functional groups representing pyrolysis oil and the first study on the similarities and differences of the decomposition of carboxylic acids and alcohols in P NMR solution. The results of this in-depth investigation can provide important assistance in research that will further upgrade and apply pyrolysis oil.

摘要

热解油广泛应用的主要障碍之一是其高含氧量,氧原子主要存在于羟基和羧基中。因此,对含氧官能团进行定量准确的表征具有重要意义。本研究采用磷核磁共振(³¹P NMR)对包括四种醇类和羧酸类在内的几种模型化合物进行深入研究。通过³¹P NMR监测,研究了模型化合物在³¹P NMR溶液中短期储存(4小时)和长期储存(14天)的稳定性。实验现象表明,羧酸羟基的稳定性比醇羟基差,这体现在长期储存后醇类化合物的剩余量超过90%。在本研究使用的羧酸中,芳香酸相对稳定。有趣的是,草酸极其不稳定,在第一小时就完全分解,而甲酸在储存一天后只剩下少量。因此,通过分析³¹P NMR溶液中含氧官能团的稳定性,可以确定热解油制备、储存和提质的最佳时间,以确保准确性。此外,根据³¹P NMR和其他表征方法的结果,可以看出所有模型化合物分解过程中都生成了水。这是一篇关于代表热解油的不同含氧官能团定量表征的报告,也是首次关于羧酸和醇在³¹P NMR溶液中分解异同的研究。这一深入研究结果可为热解油进一步提质和应用的研究提供重要帮助。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00dc/9070637/d1d0bc9484c3/c9ra04099d-f1.jpg

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