脱铝分子筛固体酸催化葡萄糖制备5-羟甲基糠醛

doi:10.16085/j.issn.1000-6613.2024-0836

化工进展 ›› 2024, Vol. 43 ›› Issue (S1): 374-381.DOI: 10.16085/j.issn.1000-6613.2024-0836

脱铝分子筛固体酸催化葡萄糖制备5-羟甲基糠醛

何世坤¹(), 张荣花¹, 李昊阳¹, 潘晖¹^,², 冯君锋¹^,²()

^1.南京林业大学化学工程学院，江苏南京 210037
^2.南京林业大学江苏省林业资源高效加工利用协同创新中心；江苏省高校农林生物质化学与利用国家重点实验室培育建设点，江苏南京 210037

收稿日期:2024-05-22 修回日期:2024-09-12 出版日期:2024-11-20 发布日期:2024-12-06
通讯作者: 冯君锋
作者简介:何世坤（1997—），男，硕士研究生，研究方向为生物质催化转化。E-mail：1502125563@qq.com。
基金资助:
国家自然科学基金(32101469);广西林产化学与工程重点实验室（国家民委重点实验室）开放基金(GXFK2204);江苏省生物质能源与材料重点实验室自主科研项目(JSBEN-S-202202)

Preparation of 5-hydroxymethylfurfural from glucose catalyzed by dealuminized molecular sieve solid acids

HE Shikun¹(), ZHANG Ronghua¹, LI Haoyang¹, PAN Hui¹^,², FENG Junfeng¹^,²()

^1.College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
^2.Jiangsu Co-Innovation Centre of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University; Jiangsu Provincial Key Lab. For the Chemistry and Utilization of Agro-Forest Biomass, Nanjing 210037, Jiangsu, China

Received:2024-05-22 Revised:2024-09-12 Online:2024-11-20 Published:2024-12-06
Contact: FENG Junfeng

摘要/Abstract

摘要：

利用不同浓度的硝酸对HY分子筛进行脱铝处理，脱铝后的HY分子筛具有不同的比表面积和孔径。以脱铝后的分子筛作为载体，利用浸渍法制备了Sn掺杂的双功能催化剂，并将其用于葡萄糖转化为5-HMF的反应。通过X射线衍射（XRD）、扫描电镜（SEM）、N₂吸附/解吸、X射线光电子能谱（XPS）和酸碱滴定等手段对催化剂进行表征。结果表明：合成的0.5mol/L-10%Sn-HY具有介孔结构、八面体形貌和适宜的B/L酸位比等。以甲基异丁基酮（MIBK）和NaCl-H₂O作为反应体系，在0.2g催化剂、165℃、60min的优化条件下，5-羟甲基糠醛的得率为67.3%。经过5次循环后，5-HMF得率仍旧可以达到49%，说明催化剂具有良好的稳定性。同时，初步探究葡萄糖转化为5-HMF的反应机理。总的来说，这项工作建立了一个高效的多相催化系统，展示了将生物质转化为平台化合物的巨大潜力。

关键词: 催化剂, 分子筛, 生物质, 双相体系, 5-羟甲基糠醛

Abstract:

HY molecular sieves were dealuminized with nitric acid of different concentrations. The dealuminized HY molecular sieves had different specific surface areas and pore sizes. The Sn-doped bifunctional catalyst for the conversion of glucose to 5-HMF was prepared by impregnation method using the dealuminized molecular sieve as the carrier. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N₂ adsorption/desorption, X-ray photoelectron spectroscopy (XPS) and acid-base titration. The results showed that the synthesized 0.5mol/L-10% Sn-HY had mesoporous structure, octahedral morphology and suitable B/L acid site ratio. In the reaction system of methyl isobutyl ketone (MIBK) and NaCl-H₂O, the yield of 5-hydroxymethylfurfural was 67.3% under the optimized conditions of 0.2g catalyst, 165℃ and 60min. After five cycles, the 5-HMF yield could still reach 49%, indicating that the catalyst had good stability. Meanwhile, the reaction mechanism for the conversion of glucose to 5-HMF was preliminarily investigated. Overall, this work established an efficient multiphase catalytic system that demonstrated the great potential of converting biomass into platform compounds.

Key words: catalyst, molecular sieves, biomass, biphasic system, 5-hydroxymethylfurfural

中图分类号:

TQ032

何世坤, 张荣花, 李昊阳, 潘晖, 冯君锋. 脱铝分子筛固体酸催化葡萄糖制备5-羟甲基糠醛[J]. 化工进展, 2024, 43(S1): 374-381.

HE Shikun, ZHANG Ronghua, LI Haoyang, PAN Hui, FENG Junfeng. Preparation of 5-hydroxymethylfurfural from glucose catalyzed by dealuminized molecular sieve solid acids[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 374-381.

图/表 12

图1 不同催化剂的XRD谱图

图2 不同催化剂的SEM图

图3 不同催化剂的红外光谱

表1 催化剂的物性参数

催化剂	比表面积 /m²·g^-1	总体积 /m³·g^-1	孔径/nm	酸强度 /mmol·g^-1
10%Sn-HY	545	281	2.1	0.89
0.2mol/L-10%Sn-HY	236	138	2.3	0.61
0.5mol/L-10%Sn-HY	47	60.2	5.2	0.42
1.0mol/L-10%Sn-HY	32	43.2	5.4	0.18

图4 不同催化剂的总谱图及Sn 3d的XPS光谱图

图5 不同催化剂的Py-IR光谱图

表2 不同催化剂对葡萄糖转化为5-HMF的影响

催化剂	转化率/%	乙酰丙酸得率/%	5-羟甲基糠醛得率/%
10%Sn-HY	100	5.0	29.9
0.2mol/L-10%Sn-HY	100	7.5	44.3
0.5mol/L-10%Sn-HY	100	6.6	65.4
1.0mol/L-10%Sn-HY	100	5.9	57.3

图6 反应性能对5-HMF得率的影响

图7 葡萄糖转化为5-HMF的反应机理

图8 催化剂的循环稳定性

表3 催化剂使用前后Sn含量与比表面积的变化情况

催化剂	Sn质量分数/%	比表面积/m²·g^-1
使用前	6.0892	47
使用后	3.8036	13

图9 回收催化剂的XRD和FTIR表征

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脱铝分子筛固体酸催化葡萄糖制备5-羟甲基糠醛

Preparation of 5-hydroxymethylfurfural from glucose catalyzed by dealuminized molecular sieve solid acids

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