葡萄糖催化热解制备左旋葡萄糖酮特性研究

doi:10.11949/0438-1157.20200345

摘要/Abstract

摘要：

催化热解制备左旋葡萄糖酮（LGO）是生物质制备高值化学品的重要方法。开发了一种新型的金属磺化炭催化剂用于高效制备LGO，并研究了热解温度、催化剂与生物质的比例以及金属盐类型对左旋葡萄糖酮生成的影响，研究表明：金属磺化炭明显促进了LGO的选择性，在Ce-SC催化剂作用下，催化热解温度为300℃、原料/催化剂比例为1∶1时，LGO的含量达到了82%；在Co-SC催化剂作用下，催化热解温度为400℃、原料/催化剂比例为1∶1时，LGO的含量达到了64%。

关键词: 左旋葡萄糖酮, 催化快速热解, 葡萄糖, 金属磺化炭

Abstract:

Preparation of levoglucosenone (LGO) by catalytic pyrolysis is an important method for biomass to prepare high-value chemicals. A new type of metal sulfonated carbon catalyst was developed for the efficient preparation of LGO. The effects of pyrolysis temperature, catalyst-to-biomass ratio, and the type of metal salt on LGO production were studied. The results indicate that the sulfonated carbon impregnated with metal significantly promoted the selectivity of LGO. Under the action of Ce-SC catalyst, when the catalytic pyrolysis temperature was 300℃ and the raw material/catalyst ratio was 1∶1, the LGO content reached 82%. Under the action of Co-SC catalyst, when the catalytic pyrolysis temperature was 400℃ and the raw material/catalyst ratio was 1∶1, the LGO content reached 64%.

Key words: levoglucosenone, catalytic fast pyrolysis, glucose, metal sulfonated carbon

中图分类号:

TK 6

徐坤, 方阳, 宫梦, 陈应泉, 陈旭, 王贤华, 杨海平, 陈汉平. 葡萄糖催化热解制备左旋葡萄糖酮特性研究[J]. 化工学报, 2020, 71(8): 3594-3601.

Kun XU, Yang FANG, Meng GONG, Yingquan CHEN, Xu CHEN, Xianhua WANG, Haiping YANG, Hanping CHEN. Study on the catalytic pyrolysis of glucose to prepare levoglucosenone[J]. CIESC Journal, 2020, 71(8): 3594-3601.

图/表 8

表1 金属磺化炭孔隙结构参数

Table 1 BET data of metal sulfonated carbon

催化剂	S_BET/ (m²/g)	S_Micro/ (m²/g)	(S_Micro/S_BET)/%	D_Average/nm	孔容/ (cm³/g)
SC	166.43	128.55	0.77	2.216	0.092
Ni-SC	137.07	116.50	0.85	2.084	0.071
Ce-SC	156.25	127.55	0.82	2.146	0.084
Cu-SC	142.31	121.58	0.85	2.034	0.072
Al-SC	141.86	124.67	0.88	1.946	0.069
Fe-SC	146.87	112.00	0.76	2.271	0.083
Co-SC	214.59	165.04	0.77	2.230	0.120

图1 磺化炭催化剂的红外光谱

Fig.1 FT-IR spectra of sulfonated carbon catalysts

表2 在催化热解温度为400℃、葡萄糖/催化剂比例为1∶1时热解产物的分布

Table 2 Distribution of pyrolysis products at the pyrolysis temperature of 400℃ and glucose / catalyst ratio of 1∶1

No.	RT/min	Compounds	Peak area/%
No.	RT/min	Compounds	Non-catalytic	SC
1	5.47	3(2H)-furanone	6.05	—
2	6.27	furfural	24.05	7.85
3	12.95	neopentyl 2-methylbutanoate	1.55	—
4	14.80	levoglucosenone	1.33	46.43
5	15.77	4H-pyran-4-one, 2,3-dihydro-3,5-dihydroxy-6-methyl-	1.95	—
6	17.87	1,4:3,6-dianhydro-α-D-glucopyranose	3.70	22.27
7	18.34	5-hydroxymethylfurfural	12.56	—
8	19.80	cyclopropanecarboxamide, N-2-methylpropyl	—	1.74
9	25.42	β-D-glucopyranose, 1,6-anhydro-	5.76	17.07

图2 葡萄糖/催化剂质量比为1∶1，在400℃热解的产物峰面积占比

Fig.2 Peak area ratio of products at glucose/catalyst mass ratio of 1∶1 and pyrolysis temperature of 400℃

图3 葡萄糖/催化剂质量比为1∶1，在400℃热解的产物峰面积

Fig.3 Peak area of products at glucose/catalyst mass ratio of 1∶1 and pyrolysis temperature of 400℃

图4 葡萄糖在300~600℃，Ce-SC作催化剂时热解产物峰面积占比及峰面积

Fig.4 Peak area ratio and peak area of pyrolysis products at 300—600℃ with Ce-SC as catalyst

图5 葡萄糖/催化剂比例为2∶1~1∶2，Ce-SC作催化剂时热解产物峰面积占比及峰面积

Fig.5 Peak area ratio and peak area of pyrolysis products when Ce-SC is used as the catalyst and the glucose / catalyst ratio is 2∶1—1∶2

图6 金属磺化炭催化热解葡萄糖制备LGO机理

Fig.6 Mechanism of preparing LGO by catalytic pyrolysis of glucose with metal sulfonated carbon

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