ZrOCl2催化琼脂糖制备5-羟甲基糠醛和乙酰丙酸

doi:10.3969/j.issn.1673-5854.2019.05.003

生物质化学工程 ›› 2019, Vol. 53 ›› Issue (5): 15-20.doi: 10.3969/j.issn.1673-5854.2019.05.003

ZrOCl₂催化琼脂糖制备5-羟甲基糠醛和乙酰丙酸

何欣骏¹,马娇¹,王康军¹,许占威²,贾松岩^1,^3,*()

1. 沈阳化工大学化学工程学院, 辽宁沈阳 110142
2. 中国科学院大连化学物理研究所, 辽宁大连 116023
3. 大连理工大学精细化工国家重点实验室, 辽宁大连 116024

收稿日期:2018-10-17 出版日期:2019-09-30 发布日期:2019-09-27
通讯作者: 贾松岩 E-mail:jiasongyan@126.com
作者简介:何欣骏(1991-),男,广西合浦人,硕士生,主要从事生物质催化转化研究工作
基金资助:
辽宁省自然科学基金资助项目(2015020633);辽宁省教育厅科学研究项目(L2015421);大连理工大学精细化工国家重点实验室开放基金资助项目(KF1812)

Catalytic Synthesis of 5-Hydroxymethylfurfural and Levulinic Acid from Agarose with ZrOCl₂ as Catalyst

Xinjun HE¹,Jiao MA¹,Kangjun WANG¹,Zhanwei XU²,Songyan JIA^1,^3,*()

1. College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
2. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
3. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China

Received:2018-10-17 Online:2019-09-30 Published:2019-09-27
Contact: Songyan JIA E-mail:jiasongyan@126.com
Supported by:
辽宁省自然科学基金资助项目(2015020633);辽宁省教育厅科学研究项目(L2015421);大连理工大学精细化工国家重点实验室开放基金资助项目(KF1812)

摘要/Abstract

摘要：

以琼脂糖为原料，分别采用CuCl₂、NiCl₂、MnCl₂、MgCl₂、FeCl₃、AlCl₃、ZrOCl₂、SnCl₄为催化剂催化转化制备5-羟甲基糠醛（5-HMF）和乙酰丙酸（LA），筛选适用于琼脂糖转化的优选催化剂，并对制备条件如溶剂含水量、催化剂用量、反应温度以及反应时间等影响因素进行了考察。研究结果表明：以50mg琼脂糖为原料，ZrOCl₂为催化剂，二甲基亚砜（DMSO）为反应溶剂，在1 mL DMSO/H₂O（体积比为8:2）混合溶剂中，ZrOCl₂用量为琼脂糖中单糖物质的量的10%，140℃下反应60 min，5-羟甲基糠醛（5-HMF）的得率为26.9%，乙酰丙酸（LA）的得率为24.7%。对制备机理分析表明：反应过程中琼脂糖首先水解为醛型单糖，然后在催化剂作用下醛型单糖异构化再脱水转化为5-HMF，部分5-HMF在酸的作用下进一步转化为LA。

关键词: 琼脂糖, 5-羟甲基糠醛, 乙酰丙酸, ZrOCl₂

Abstract:

Agarose was used as the starting material, and CuCl₂, NiCl₂, MnCl₂, MgCl₂, FeCl₃, AlCl₃, ZrOCl₂ and SnCl₄ were respectively used as catalysts to convert agarose into 5-hydroxymethylfurfural(5-HMF) and levulinic acid(LA). Preferred catalysts were screened out for the conversion of agarose. The effects of reaction parameters such as water content, catalyst loading, reaction temperature and reaction time on the reaction were investigated in detail. The results demonstrated that when 50 mg of agarose was used as the feedstock with ZrOCl₂ as the catalyst and DMSO as the solvent, 5-HMF yield of 26.9% and LA yield of 24.7% could be achieved in 1 mL DMSO/H₂O mixed solvent with a volume ratio of 8:2 and ZrOCl₂ loading of 10% to the amount of substance of monosaccharide in agarose at 140℃ for 60 min. Mechanism analyses indicated that agarose was hydrolyzed into aldose, which underwent subsequent isomerization and dehydration to produce 5-HMF. 5-HMF could be further converted into LA catalyzed by acid catalyst.

Key words: agarose, 5-hydroxymethylfurfural, levulinic acid, ZrOCl₂

中图分类号:

TQ35

何欣骏,马娇,王康军,许占威,贾松岩. ZrOCl₂催化琼脂糖制备5-羟甲基糠醛和乙酰丙酸[J]. 生物质化学工程, 2019, 53(5): 15-20.

Xinjun HE,Jiao MA,Kangjun WANG,Zhanwei XU,Songyan JIA. Catalytic Synthesis of 5-Hydroxymethylfurfural and Levulinic Acid from Agarose with ZrOCl₂ as Catalyst[J]. Biomass Chemical Engineering, 2019, 53(5): 15-20.

图/表 6

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参考文献 19

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催化剂catalyst	5-HMF/%		LA/%
催化剂catalyst	DMSO	V(DMSO)/ V(H₂O)=8:2	DMSO	V(DMSO)/ V(H₂O)=8:2
CuCl₂	14.2	23.4	1.4	4.7
AlCl₃	16	17.1	0.3	15.2
FeCl₃	15.6	25.4	0.6	3.9
SnCl₄	12.1	24.3	0.5	3.5
ZrOCl₂	16.6	26.9	10.6	24.7

V(DMSO)/ V(H₂O)	5-HMF/%	LA/%
10:0	16.6	10.6
9:1	24.4	20.9
8:2	26.9	24.7
7:3	23.7	19
6:4	23.1	18.3
4:6	22.1	17.2
2:8	19.5	15.5
0:10	16.7	14.3

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ZrOCl₂催化琼脂糖制备5-羟甲基糠醛和乙酰丙酸

Catalytic Synthesis of 5-Hydroxymethylfurfural and Levulinic Acid from Agarose with ZrOCl₂ as Catalyst

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