负载金属型固体酸催化木质纤维生物质定向转化为乙酰丙酸甲酯

doi:10.16085/j.issn.1000-6613.2023-0836

化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3042-3050.DOI: 10.16085/j.issn.1000-6613.2023-0836

• 能源加工与技术 • 上一篇

负载金属型固体酸催化木质纤维生物质定向转化为乙酰丙酸甲酯

何世坤¹(), 张文豪¹, 冯君锋¹^,²(), 潘晖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:2023-05-19 修回日期:2023-09-25 出版日期:2024-06-15 发布日期:2024-07-02
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）开放基金课题(GXFK2204)

Directional conversion of lignocellulosic biomass to methyl levulinate over supported metal solid acid

HE Shikun¹(), ZHANG Wenhao¹, FENG Junfeng¹^,²(), PAN Hui¹^,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, Jiangsu Provincial Key Lab for the Chemistry and Utilization of Agro-forest Biomass, Nanjing Forestry University, Nanjing 210037, Jiangsu, China

Received:2023-05-19 Revised:2023-09-25 Online:2024-06-15 Published:2024-07-02
Contact: FENG Junfeng

摘要/Abstract

摘要：

木质纤维生物质是一种存量丰富、绿色的资源，通过利用木质纤维生物质制备高值化的液体燃料和化学品，不但可以缓解社会对化石燃料需求的压力，而且可以改善生态环境，助力“双碳”目标。本研究制备了多种金属负载型固体酸催化剂，用于催化生物质碳水化合物高效转化为乙酰丙酸甲酯。通过表征手段研究所制备催化剂的特性，发现其具备双功能特性（B酸和L酸活性中心）。其中，AlCl₃作为L酸供应体，负载到催化剂表面，催化性能最佳。研究反应温度和时间等因素对葡萄糖、木糖同步定向转化为乙酰丙酸甲酯的影响发现：在复合溶剂二甲氧基甲烷/甲醇的质量比1∶1、反应温度200℃、反应时间120min的条件下性能最好，原料的转化率达到了100%，乙酰丙酸/酯的最大收率达到了24.96%。

关键词: 木质纤维生物质, 催化剂, 复合溶剂, 生物燃料, 酯化

Abstract:

Lignocellulosic biomass is an abundant and green resources. Preparation of high added-value liquid fuels and chemicals from lignocellulosic biomass can alleviate society's demand for fossil fuels and improve the ecological environment, and thus contribute to the "dual-carbon" objective. In this study, a variety of metal-supported solid acid catalysts were prepared for conversion of biomass carbohydrates to methyl levulinate. The prepared catalysts were characterized and were found to possess bifunctional properties(B- and L-acid active centers). The catalyst with AlCl₃ loaded on surface to provide L-acid showed the best catalytic performance. The effects of different factors such as reaction temperature and time on the simultaneous directional conversion of glucose and xylose to methyl levulinate were investigated in detail. A raw material conversion of 100% and levulinic acid/ester yield of 24.96% could be obtained with the co-solvent of dimethoxy-methane/methanol (1∶1 mass ratio) at 200℃ for 2h.

Key words: lignocellulosic biomass, catalyst, compounded solvent, biofuel, esterification

中图分类号:

TQ032

何世坤, 张文豪, 冯君锋, 潘晖. 负载金属型固体酸催化木质纤维生物质定向转化为乙酰丙酸甲酯[J]. 化工进展, 2024, 43(6): 3042-3050.

HE Shikun, ZHANG Wenhao, FENG Junfeng, PAN Hui. Directional conversion of lignocellulosic biomass to methyl levulinate over supported metal solid acid[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3042-3050.

图/表 17

参考文献 31

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催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/Å
A15	385.94	0.63	65.70
2%AlCl₃-A15	37.65	0.24	106.00
4%AlCl₃-A15	77.60	0.36	184.22
6%AlCl₃-A15	55.70	0.34	242.49

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/Å
A15	385.94	0.63	65.70
2%AlCl₃-A15	37.65	0.24	106.00
4%AlCl₃-A15	77.60	0.36	184.22
6%AlCl₃-A15	55.70	0.34	242.49

催化剂	B酸/mmol·g^-1	L酸/mmol·g^-1	L酸/B酸
2%AlCl₃-A15	0.037	0.047	1.27
4%AlCl₃-A15	0.058	0.068	1.17
6%AlCl₃-A15	0.049	0.051	1.04

催化剂	B酸/mmol·g^-1	L酸/mmol·g^-1	L酸/B酸
2%AlCl₃-A15	0.037	0.047	1.27
4%AlCl₃-A15	0.058	0.068	1.17
6%AlCl₃-A15	0.049	0.051	1.04

催化剂	原料转化率/%	糠醛得率/%	5-羟甲基糠醛得率/%	糖苷类得率/%	乙酰丙酸得率/%	乙酰丙酸甲酯得率/%	乙酰丙酸/酯得率/%
6%LiCl/乙醇-A15	100	0.08	1.90	1.09	3.62	14.35	17.97
6%LiCl/水-A15	100	0.10	3.02	0.79	8.36	15.20	23.56
6%LiCl/甲醇-A15	100	0.06	1.07	0.89	1.14	13.23	14.37

负载金属型固体酸催化木质纤维生物质定向转化为乙酰丙酸甲酯

Directional conversion of lignocellulosic biomass to methyl levulinate over supported metal solid acid

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催化剂	原料转化率/%	糠醛得率/%	5-羟甲基糠醛得率/%	糖苷类得率/%	乙酰丙酸得率/%	乙酰丙酸甲酯得率/%	乙酰丙酸/酯得率/%
2%Al(NO₃)₃-A15	99.90	—	4.09	0.016	1.34	7.07	8.41
4%Al(NO₃)₃-A15	99.90	0.08	2.64	0.69	3.58	13.91	17.49
6%Al(NO₃)₃-A15	99.90	0.07	1.85	0.43	5.95	13.47	19.42
2%AlCl₃-A15	100	—	1.83	—	3.61	11.84	15.45
4%AlCl₃-A15	100	0.09	1. 88	0.76	7.36	17.59	24.96
6%AlCl₃-A15	100	0.08	1.82	0.36	5.09	18.07	23.17

催化剂	原料转化率/%	糠醛得率/%	5-羟甲基糠醛得率/%	糖苷类得率/%	乙酰丙酸得率/%	乙酰丙酸甲酯得率/%	乙酰丙酸/酯得率/%
A15	100	—	—	—	—	1.65	1.65
2%LiCl-A15	100	—	2.89	—	2.88	3.32	6.20
4%LiCl-A15	100	—	3.16	—	7.20	10.58	17.78
6%LiCl-A15	100	0.10	3.02	0.79	8.36	14.35	22.71
2%CrCl₃-A15	100	—	3.44	—	2.68	5.18	7.86
4%CrCl₃-A15	100	0.06	1.68	0.21	5.29	16.00	21.29
6%CrCl₃-A15	100	0.05	1.64	0.47	5.17	16.78	21.95
2%AlCl₃-A15	100	—	1.83	—	3.61	11.84	15.45
4%AlCl₃-A15	100	0.09	1.88	0.76	7.36	17.59	24.96
6%AlCl₃-A15	100	0.08	1.82	0.36	5.09	18.07	23.17

催化剂	反应溶剂	原料转化率 /%	糠醛得率 /%	5-羟甲基糠醛得率 /%	糖苷类得率 /%	乙酰丙酸得率 /%	乙酰丙酸甲酯得率 /%	乙酰丙酸/酯得率 /%
6%CrCl₃-A15	水	100	—	1.04	2.33	16.90	—	16.90
6%CrCl₃-A15	甲醇	100	0.05	1.64	0.47	5.17	16.78	21.95
A15	水	100	—	0.65	0.54	9.33	—	9.33
A15	甲醇	100	0.08	—	—	—	1.65	1.65

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