固体酸SO42-/Al-MCM-41催化木糖制糠醛的研究

doi:10.3969/j.issn.0253-2417.2021.03.014

摘要/Abstract

摘要：

采用硫酸对Al-MCM-41固体酸进行改性，制备木糖脱水制糠醛催化剂SO₄^2-/Al-MCM-41。借助傅里叶变换红外光谱（FT-IR）、氨气程序升温脱附（NH₃-TPD）、氮气等温吸附-脱附分析等表征技术对催化剂进行表征。结果表明，硫酸改性成功地在分子筛Al-MCM-41表面引入了SO₄^2-，提高了分子筛的酸性，并且未改变分子筛的介孔结构。考察了催化剂、溶剂、反应温度及反应时间等因素对糠醛收率的影响。结果表明，在水/正丁醇反应体系下（水和正丁醇体积比1：1，水相中NaCl质量分数2%），以木糖为原料，液固比（溶剂与固体原料比）20：1（mL：g），固体酸SO₄^2-/Al-MCM-41为催化剂，原料与催化剂质量比为2：1，在190℃反应温度下反应30 min时获得最大糠醛收率62.45%，与分子筛Al-MCM-41作为催化剂相比，糠醛收率同比提高了21.82个百分点。另外，固体酸SO₄^2-/Al-MCM-41对半纤维素制备糠醛也有较好的催化作用，在更加苛刻的反应条件下获得51.96%的糠醛收率（半纤维素基）。催化剂重复性研究结果表明，固体酸催化剂使用3次时，糠醛收率约为54%。随着催化剂使用次数的增加，催化剂催化能力有一定程度降低，可通过高温焙烧、硫酸浸渍的方式进行催化剂再生。

关键词: 固体酸, 木糖, 糠醛, 水解

Abstract:

The solid acid Al-MCM-41 was modified by sulfuric acid to prepare the catalyst SO₄^2-/Al-MCM-41 for furfural production from xylose dehydration. The catalyst was characterized by Fourier transform infrared(FT-IR) spectroscopy, temperature-programmed desorption of ammonia(NH₃-TPD), and N₂ adsorption-desorption anslysis.The results showed that SO₄^2- was successfully introduced into the surface of Al-MCM-41 by sulfuric acid modification, which improved the acidity of the molecular sieve without changing the mesoporous structure of the molecular sieve.The influence of factors such as catalyst, solvent, reaction temperature and reaction time on the yield of furfural were investigated. The results showed that the highest yield of furfural was 62.45% in water/n-butanol reaction system(volume ratio of water and n-butanol 1:1, NaCl mass fraction in water 2%) with xylose as the raw material, ratio of liquor to material 20:1(mL: g) solid acid SO₄^2-/Al-MCM-41 as catalyst and mass ratio of raw material and catalyst 2:1 at 190℃ for 30 min, compared with molecular sieve Al-MCM-41 as catalyst, the yield of furfural increased by 21.82 percentage points. In addition, solid acid SO₄^2-/Al-MCM-41 also had a good catalytic effect on the preparation of furfural from hemicellulose, and 51.96% furfural yield was obtained from hemicellulose under more severe condition. The results of catalyst recycling study showed that the yield of furfural was about 54% when the solid acid catalyst was used for three times. With the increase of the catalyst use times, the catalytic capacity of the catalyst decreased to a certain extent. The catalyst regeneration could be carried out by means of high temperature roasting and sulfuric acid impregnation.

Key words: solid acid, xylose, furfural, hydrolysis

中图分类号:

TQ35

刘秋梅, 胡汉文, 张素平. 固体酸SO₄^2-/Al-MCM-41催化木糖制糠醛的研究[J]. 林产化学与工业, 2021, 41(3): 103-111.

Qiumei LIU, Hanwen HU, Suping ZHANG. Synthesis of Furfural from Xylose Catalyzed by Solid Acid SO₄^2-/Al-MCM-41[J]. Chemistry and Industry of Forest Products, 2021, 41(3): 103-111.

图/表 10

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参考文献 25

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样品 samples	BET比表面积/(m²·g^-1) BET specific surface area	孔容/(cm³·g^-1) pore volume	平均孔径/nm pore size
Al-MCM-41	676.91	0.67	3.93
SO₄^2-/Al-MCM-41	734.02	0.74	4.01

催化剂 catalyst	催化剂用量/g catalyst dosage	糠醛收率/% furfural yield
SO₄^2-/Al-MCM-41	1.25	48.33
SO₄^2-/Al-MCM-41	2.5	62.45
SO₄^2-/Al-MCM-41	5	63.18
Al-MCM-41	2.5	40.63

溶剂体系 solvent system		糠醛收率/% furfural yield
溶剂种类 solvent type	水/正丁醇water/n-butanol	62.45
	水/甲苯water/toluene	56.27
	水/甲基异丁基酮water/MIBK	56.22
	水/环戊基甲醚water/CPME	53.09
	水water	35.04
溶剂组成(V_正丁醇∶V_水) solvent composition(V_n_-butanol∶V_water)	3∶7	52.57
	4∶6	54.75
	5∶5	62.45
	6∶4	53.72
	7∶3	41.24
NaCl用量 NaCl dosage	0%	57.08
	2%	62.45
	4%	61.53
	6%	62.05

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固体酸SO₄^2-/Al-MCM-41催化木糖制糠醛的研究

Synthesis of Furfural from Xylose Catalyzed by Solid Acid SO₄^2-/Al-MCM-41

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