纤维素低氧环境下热解特性和糖类生成机制

doi:10.11949/0438-1157.20211355

摘要/Abstract

摘要：

在最小化二次反应的金属网反应器下对微晶纤维素进行低氧热解实验。采用带有脉冲安培检测的高性能阴离子交换色谱法(HPAEC-PAD)的Dionex ICS-6000离子色谱(IC)对热解后的产物水溶性中间态活性纤维素(WSIAC)和水溶性初生焦油(WSPT)的组成和分布进行分析。重点关注纤维素热解过程中几种脱水糖和糖聚物的生成转化规律。实验发现氧气通过促进中间态纤维素的生成来提前纤维素的分解。氧化气氛下，聚合度越高的脱水糖稳定性越差。氧气的存在一方面促进纤维二聚糖和纤维三聚糖生成，另一方面，它们的破碎或其他分解反应也在一定程度下受到氧气影响。

关键词: 生物质, 氧化, 热解, 中间态活性纤维素, 脱水糖

Abstract:

Low oxygen pyrolysis of microcrystalline cellulose was carried out in a metal mesh reactor (WMR) with minimal secondary reaction. The composition and distribution of water-soluble intermediate active cellulose (WSIAC) and water-soluble primary tar (WSPT) were analyzed by Dionex ICS-6000 ion chromatography (IC) using high-performance anion exchange chromatography (HPAEC-PAD) with pulsed amperometric detection. The formation and transformation of several dehydrated sugars and glycopolymers during cellulose pyrolysis was emphasized. It was found that oxygen predates the decomposition of cellulose by promoting the formation of intermediate cellulose. In oxidizing atmosphere, the higher degree of polymerization, the worse the stability of dehydrated sugar. The presence of oxygen promotes the production of cellobiose and cellotrian. On the other hand, their fragmentation or other decomposition reactions are also affected by oxygen to a certain extent.

Key words: biomass, oxidation, pyrolysis, intermediate active cellulose, dehydration of sugar

中图分类号:

TK 6

欧阳志鹏, 刘庭峰, 冷尔唯, 冯天毅, 曾建辉, 龚勋. 纤维素低氧环境下热解特性和糖类生成机制[J]. 化工学报, 2022, 73(3): 1351-1358.

Zhipeng OUYANG, Tingfeng LIU, Erwei LENG, Tianyi FENG, Jianhui ZENG, Xun GONG. Pyrolysis characteristics and mechanism of carbohydrate formation of cellulose in low oxygen environment[J]. CIESC Journal, 2022, 73(3): 1351-1358.

图/表 9

图1 金属网反应器结构图

Fig.1 Schematic diagram of the wire-mesh reactor

图2 纤维素在金属网和热重实验中低氧热解的焦产率

Fig.2 Coke yield from low oxygen pyrolysis of cellulose on WMR and TG

图3 不同气氛下纤维素在金属网反应器上焦油产率

Fig.3 Tar yield of cellulose in metal mesh reactor under different atmosphere

图4 不同气氛下纤维素在金属网反应器上热解焦产率

Fig.4 Pyrolysis coke yield of cellulose in metal mesh reactor under different atmosphere

图5 纤维素热解的固态产物FT-IR谱图

Fig.5 FT-IR diagram of solid pyrolysis products of cellulose

图6 纤维素热解的固态产物中水溶性中间态纤维素产率

Fig.6 Yields of water-soluble intermediates in solid residues at various temperatures

图7 纤维素热解产生的水溶性中间态纤维素中脱水糖和糖聚物选择性

Fig.7 Selectivity of dehydrated sugars and glycopolymers in water-soluble intermediate cellulose produced by pyrolysis of cellulose

图8 纤维素不同温度下热解水溶性初生焦油产率

Fig.8 Yields of water-soluble liquids at various temperatures

图9 纤维素热解产生的水溶性初生焦油中脱水糖和糖聚物选择性

Fig.9 Selectivity of dehydrated sugars and glycopolymers in water-soluble primary tar produced from cellulose pyrolysis

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