茶多酚-铪催化剂的制备及催化乙酰丙酸乙酯转化为γ-戊内酯

doi:10.3969/j.issn.1673-5854.2023.05.003

摘要/Abstract

摘要：

以茶多酚为配体, 采用共沉淀法制备了催化剂茶多酚-铪, 对催化剂结构进行表征, 并将此催化剂用于乙酰丙酸乙酯(EL)转移加氢制备γ-戊内酯(GVL)的反应。对催化剂的制备条件如HfCl₄与茶多酚物质的量比、三乙胺用量、老化温度等进行考察, 探讨了不同反应条件对催化剂茶多酚-铪催化EL反应的活性影响以及催化剂的循环稳定性。结果表明: 茶多酚1 mmol, n(HfCl₄)∶n(茶多酚)=4∶1, 三乙胺用量50 mmol, 无老化处理, 此条件下制备的催化剂茶多酚-铪催化活性较好。在反应温度160 ℃、反应时间3 h条件下, 100 mg该催化剂可催化1 mmol EL制备GVL, 使EL转化率达到93.5%, GVL产率达到83.7%, GVL选择性为89.5%。催化剂茶多酚-铪具有良好的循环稳定性, 经过5次使用后, 还能使GVL产率和EL转化率基本保持不变。

关键词: 茶多酚, 铪, 催化剂, 乙酰丙酸乙酯, γ-戊内酯

Abstract:

Using tea polyphenols as ligands, tea polyphenols-hafnium catalyst was prepared by co-precipitation method. The structure of the catalyst was characterized, and the catalyst was used in transfer hydrogenation reaction of ethyl levulinate(EL) into γ-valerolactone(GVL). The preparation conditions of the catalyst, such as the molar ratio of HfCl₄ to tea polyphenols, the amount of triethylamine and the aging temperature, were investigated. Then, the effects of different reaction conditions on the activity of the tea polyphenols-hafnium catalysts for the ethyl levulinate reaction and the cycling stability of the catalyst were discussed. The results showed that the catalyst had better catalytic activity when the molar ratio of HfCl₄ to tea polyphenols was 4∶1, the amount of triethylamine was 50 mmol and no aging treatment was performed. When 100 mg catalyst could catalyse 1 mmol EL to prepare GVL at the reaction temperature of 160 ℃ and reaction time of 3 h, the EL conversion rate could reach 93.5%, the GVL yield could reach 83.7% and the GVL selectivity could reach 89.5%. The tea polyphenol-hafnium catalyst had good cycling stability after 5 cycles, which could keep the GVL yield and EL conversion basically unchanged.

Key words: tea polyphenols, hafnium, catalyst, ethyl levulinate, γ-valerolactone

中图分类号:

TQ35

王蒙, 丛思琦, 康琪, 王文博, 孔祥如, 林保东, 周华从. 茶多酚-铪催化剂的制备及催化乙酰丙酸乙酯转化为γ-戊内酯[J]. 生物质化学工程, 2023, 57(5): 17-24.

Meng WANG, Siqi CONG, Qi KANG, Wenbo WANG, Xiangru KONG, Baodong LIN, Huacong ZHOU. Preparation of Tea Polyphenol-hafnium Catalyst and Catalytic Conversion of Ethyl Levulonate to γ-Valentolactone[J]. Biomass Chemical Engineering, 2023, 57(5): 17-24.

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使用次数/次using times	EL转化率EL conversion	GVL产率GVL yield	GVL选择性GVL selectivity
1	56.6	51.3	90.6
2	84.0	44.9	53.3
3	88.1	46.5	52.8
4	84.3	44.1	52.3
5	81.8	46.3	56.5

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