乙烯焦油炭磺酸催化果糖脱水合成5-羟甲基糠醛

doi:10.11944/j.issn.1000-0518.2020.03.190278

摘要/Abstract

摘要：

以蒸馏后的乙烯焦油重组分为原料,采用交联-磺化法制备了乙烯焦油炭磺酸。利用红外光谱(FT-IR)、X射线衍射(XRD)、拉曼光谱(Raman)、热重分析(TGA-DTG)、扫描电子显微镜(SEM)等手段对该催化剂进行结构和性能表征。结果表明,该催化剂呈现无定形石墨碳结构,且具有较高的酸量(4.20 mmol/g),表面的磺酸官能团是其关键活性中心。并将该催化剂用于果糖脱水合成5-羟甲基糠醛(5-HMF)的反应,在130 ℃反应140 min,催化剂用量0.3 g、溶剂用量8 mL及助剂用量0.3 g的条件下,果糖转化率和5-HMF产率分别为96.2%和52.1%,分离得到的5-HMF纯度可达97.0%。催化剂循环使用5次后,果糖的转化率和5-HMF的产率分别保持在85.1%和40.8%以上。

关键词: 果糖, 5-羟甲基糠醛, 乙烯焦油, 炭磺酸

Abstract:

Ethylene tar char sulfonic acid was prepared by crosslinking and sulfonating method with the heavy components of ethylene tar after distillation as the raw material. The structure and properties of the catalyst were characterized by Flourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA-DTG), and scanning electron microscopy (SEM). The results showed that the catalyst presented an amorphous graphite carbon structure and high acid content (4.20 mmol/g). The sulfonic acid functional group on the surface was the key active center. The catalyst was used for the dehydration of fructose into 5-hydroxymethylfurfural (5-HMF). At the reaction time of 140 min, temperatureat of 130 ℃, the catalyst dosage of 0.3 g, the solvent dosage of 8 mL and the additive dosage of 0.3 g, the conversion of fructose and the yield of 5-HMF were 96.2% and 52.1%, respectively. The purity of 5-HMF obtained by separation was 97.0%. The conversion of fructose and the yield of 5-HMF remained above 85.1% and 40.8% after the catalyst was recycled five times.

Key words: fructose, 5-hydroxymethylfurfural, ethylene tar, char sulfonic acid

张爽, 张龙. 乙烯焦油炭磺酸催化果糖脱水合成5-羟甲基糠醛[J]. 应用化学, 2020, 37(3): 314-321.

ZHANG Shuang, ZHANG Long. Dehydration of Fructose into 5-Hydroxymethylfurfural Catalyzed by Ethylene Tar Char Sulfonic Acid[J]. Chinese Journal of Applied Chemistry, 2020, 37(3): 314-321.

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