废海绵衍生碳基固体酸催化热解木薯渣制备左旋葡萄糖酮

doi:10.11949/0438-1157.20230997

摘要/Abstract

摘要：

以废弃海绵作为碳材料前体，通过惰性气氛碳化和接枝磺酸基团，合成了系列磺酸功能化碳基固体酸，用于木薯渣快速热解制备左旋葡萄糖酮（LGO）。研究采用多种物理化学表征手段，如X射线衍射、红外光谱、液氮吸脱附、扫描电镜等，系统分析了制备的废弃海绵衍生碳基固体酸物化特性。结果表明，废弃海绵衍生碳基固体酸具有较丰富的孔道结构，其表面接枝了丰富的磺酸基团，因而有利于木薯渣选择性热解转化获得LGO。其中，在碳化温度500℃、碳/酸比1 g∶0.5 ml时，废弃海绵衍生碳基固体酸展现出较优的催化热解性能，产物中LGO质量收率可达12.93%。本文研究将为废弃海绵资源化利用提供新的思路，同时又能够促进固废衍生碳材料在农林废弃物高值转化方面应用。

关键词: 生物质, 催化剂, 热解, 有机化合物, 化学分析

Abstract:

In this paper, waste sponges were used as carbon material precursors, and a series of sulfonic acid functionalized carbon-based solid acids were synthesized through inert atmosphere carbonization and grafting of sulfonic acid groups, which were used for rapid pyrolysis of cassava residue to prepare LGO. The as-prepared waste sponge derived carbon-based solid acids were systematically analyzed by using various physicochemical characterizations, including X-ray diffraction (XRD), infrared spectroscopy (FT-IR), liquid nitrogen adsorption and desorption, and scanning electron microscopy (SEM), and so on, so as to identify the structural characteristics. The experimental results indicated that waste sponge derived carbon-based solid acid prepared at 500℃ and carbon-to-acid ratio of 1 g∶0.5 ml had rich porous structures and sulfonic acid groups, thus facilitating the selective pyrolysis of cassava residue into LGO. Under the catalysis of above mentioned carbon-based solid acid, the mass yield of LGO achieved 12.93% from cassava residue pyrolysis. This study presents a new idea for the resource utilization of waste sponges, which also promoted the application of solid wastes derived carbon materials for high-value transformation of agricultural and forestry wastes.

Key words: biomass, catalyst, pyrolysis, organic compounds, chemical analysis

中图分类号:

TQ 352.4

钟声亮, 张军, 单锐, 孙勇. 废海绵衍生碳基固体酸催化热解木薯渣制备左旋葡萄糖酮[J]. 化工学报, 2023, 74(11): 4559-4569.

Shengliang ZHONG, Jun ZHANG, Rui SHAN, Yong SUN. Waste sponge derived carbon-based solid acids for levoglucosanone production via cassava residue pyrolysis[J]. CIESC Journal, 2023, 74(11): 4559-4569.

图/表 12

图1 不同氯磺酸添加量碳基固体酸催化剂XRD谱图

Fig.1 XRD patterns of as-prepared carbon-based solid acid catalysts

图2 制备的碳基固体酸的氮气吸附-脱附等温曲线

Fig.2 N2 adsorption-desorption curves of carbon-based solid acids

表1 不同碳化温度的碳基固体酸催化剂孔隙结构参数

Table 1 Pore structure parameters of catalysts with different carbonization temperatures

碳化温度/℃	比表面积/ (m²/g)	孔体积/ (cm³/g)	孔径/nm
300	4.99	0.02	18.94
500	13.93	0.07	16.55
700	23.13	0.10	13.67

图3 不同氯磺酸添加量碳基固体酸催化剂SEM图

Fig. 3 SEM images of carbon-based solid acid catalysts

表2 不同氯磺酸添加量对应的磺酸基团负载量

Table 2 Sulfonic acid group loading for different chlorosulfonic acid additions

催化剂	磺酸基团负载量/(mmol/g)
500WS-S0.1	0.24
500WS-S0.25	2.73
500WS-S0.5	3.87
500WS-S1	4.19
500WS-S2	3.39

图4 500WS-S0.5的XPS谱图

Fig. 4 XPS spectra of 500WS-S0.5

图5 不同碳/酸比的碳基固体酸催化剂FT-IR透射光谱

Fig. 5 FT-IR spectra of carbon-based solid acid catalysts

图6 木薯渣催化热解的TG-DTG曲线

Fig. 6 TG-DTG curves of catalytic pyrolysis of cassava residues

图7 木薯渣催化热解的 TG/MS曲线

Fig. 7 TG/MS curves of catalytic pyrolysis of cassava residues

图8 Py-GC/MS实验结果

Fig. 8 The results of Py-GC/MS experiments

图9 500WS-S0.5参与木薯渣热解产物色谱图

Fig. 9 GC-MS spectra for pyrolytic products in the case of using 500WS-S0.5 as catalyst

图10 木薯渣催化热解制备LGO可能反应途径

Fig. 10 Possible pathway for CR pyrolysis over carbon-based solid acids

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