A review: research progress in production of 5-ethoxymethylfurfural

doi:10.16085/j.issn.1000-6613.2018-1053

Abstract

Abstract:

5-Ethoxymethylfurfural (EMF), a high value chemical which has high energy density and excellent combustion performance, is a new biofuel or fuel additive. The preparation of EMF by alcoholysis is one of the important approaches for the utilization of biomass, especially agricultural wastes. The characteristics of raw materials, catalysts and catalytic systems for EMF production are introduced in this paper. The research status, existing problems and developing trends of EMF production from different raw materials are investigated and studied. Though the yield of EMF from agricultural wastes is not high, it has the advantage of cheap and abundant raw material. The research advantages, disadvantages and developing trends of EMF production catalyzed by different catalysts, such as mineral acids, solid acids and ionic liquids are also analyzed. Mineral acids are corrosive to reactors and difficult to be reused and ionic liquids are expensive at present, whereas solid acids are efficient and recyclable. It has been suggested that EMF produced directly from cheap and abundant biomass is the most important research direction in the future, and highly effective, environmentally friendly and economical EMF production process is the basis of the industrial production.

Key words: 5-ethoxymethylfurfural, biomass, alcoholysis, catalyst

摘要：

5-乙氧基甲基糠醛（5-ethoxymethylfurfural，简称EMF）是一种具有成为新一代生物燃料或者燃料添加剂潜力的高附加值化学品，具有优良的能量密度和燃烧性能。通过醇解制备EMF是生物质资源化利用的重要途径之一，也是农业废弃物生物质资源化利用的重要方式。本文介绍了EMF制取原料、催化剂及催化体系的特性，综述了糖类、农林废弃生物质等不同种类原料制取EMF的研究现状，虽然农林废弃生物质转化率较低，但具有原料成本低、来源丰富的优势。在此基础上，分类综述了无机酸、固体酸、离子液体等不同催化体系制取EMF的现状、优势和不足，无机酸存在易腐蚀、不易回收等问题；离子液体目前成本较高，固体酸则催化效率较高、易回收，极具发展潜力。提出开发以低廉生物质资源为原料直接合成EMF的技术将是未来研究的重要方向，反应高效、环境友好、经济可行的EMF生产路径是实现工业化生产的基础。

关键词: 5-乙氧基甲基糠醛, 生物质, 醇解, 催化剂

CLC Number:

S216.2

Guizhuan XU,Binglin CHEN,Shaohao ZHANG,Zhangbin ZHENG,Yuqing YANG,Chen WANG. A review: research progress in production of 5-ethoxymethylfurfural[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1259-1268.

徐桂转,陈炳霖,张少浩,郑张斌,杨雨青,王晨. 生物质转化制备5-乙氧基甲基糠醛液体燃料研究进展[J]. 化工进展, 2019, 38(03): 1259-1268.

Figures/Tables 6

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序号	底物	催化剂	反应介质	温度/℃	时间	产率/%	文献
1	菊粉	7.7%H₂SO₄	乙醇	130	30min	29	[10]
2	果糖	0.1%H₂SO₄	乙醇	120	1h	79.33	[25]
3	葡萄糖	0.1%H₂SO₄	乙醇	210	14min	21.78	[25]
4	纤维素	0.1%H₂SO₄	乙醇	200	80min	14.35	[25]
5	木薯	0.52%H₂SO₄	乙醇	200	6h	2.05	[27]
6	HMF	0.14%H₃PO₄	乙醇	90	2h	1.7	[31]
7	HMF	0.18%H₂SO₄	乙醇	90	2h	79	[31]
8	果糖	0.1%H₂SO₄	乙醇	120	3h	66.29	[32]
9	HMF	10.9%H₂SO₄	乙醇	70	18h	79.8	[33]

序号	底物	催化剂	反应介质	温度/℃	时间	产率/%	文献
1	菊粉	7.7%H₂SO₄	乙醇	130	30min	29	[10]
2	果糖	0.1%H₂SO₄	乙醇	120	1h	79.33	[25]
3	葡萄糖	0.1%H₂SO₄	乙醇	210	14min	21.78	[25]
4	纤维素	0.1%H₂SO₄	乙醇	200	80min	14.35	[25]
5	木薯	0.52%H₂SO₄	乙醇	200	6h	2.05	[27]
6	HMF	0.14%H₃PO₄	乙醇	90	2h	1.7	[31]
7	HMF	0.18%H₂SO₄	乙醇	90	2h	79	[31]
8	果糖	0.1%H₂SO₄	乙醇	120	3h	66.29	[32]
9	HMF	10.9%H₂SO₄	乙醇	70	18h	79.8	[33]

序号	底物	催化剂	反应介质	温度/℃	时间	产物	产率/%	文献
1	HMF	AlCl₃	乙醇	100	5h	EMF	92.9	[17]
2	果糖	AlCl₃	乙醇	100	11h	EMF	71.2	[17]
3	葡萄糖	AlCl₃	乙醇	100	11h	EMF	38.4	[17]
4	菊粉	AlCl₃	乙醇	100	11h	EMF	58.2	[17]
5	淀粉	AlCl₃	乙醇	100	11h	EMF	27.2	[17]
6	木薯	Al₂(SO₄)₃	乙醇	200	6h	EMF	0.36	[27]
7	木薯	Fe₂(SO₄)₃	乙醇	200	6h	EMF	3.01	[27]
8	木薯	NaHSO₄	乙醇	200	6h	EMF	4.43	[27]
9	木薯	MgSO₄	乙醇	200	6h	EMF	0.09	[27]
10	木薯	ZnSO₄	乙醇	200	6h	EMF	3.25	[27]
11	木薯	NiSO₄	乙醇	200	6h	EMF	11.4	[27]
12	葡萄糖	AlCl₃	乙醇/水	160	15min	HMF和EMF	57	[41]
13	果糖	FeCl₃	乙醇/[Bmim]Cl	100	4h	EMF	30.1	[42]

序号	底物	催化剂	反应介质	温度/℃	时间	产物	产率/%	文献
1	HMF	AlCl₃	乙醇	100	5h	EMF	92.9	[17]
2	果糖	AlCl₃	乙醇	100	11h	EMF	71.2	[17]
3	葡萄糖	AlCl₃	乙醇	100	11h	EMF	38.4	[17]
4	菊粉	AlCl₃	乙醇	100	11h	EMF	58.2	[17]
5	淀粉	AlCl₃	乙醇	100	11h	EMF	27.2	[17]
6	木薯	Al₂(SO₄)₃	乙醇	200	6h	EMF	0.36	[27]
7	木薯	Fe₂(SO₄)₃	乙醇	200	6h	EMF	3.01	[27]
8	木薯	NaHSO₄	乙醇	200	6h	EMF	4.43	[27]
9	木薯	MgSO₄	乙醇	200	6h	EMF	0.09	[27]
10	木薯	ZnSO₄	乙醇	200	6h	EMF	3.25	[27]
11	木薯	NiSO₄	乙醇	200	6h	EMF	11.4	[27]
12	葡萄糖	AlCl₃	乙醇/水	160	15min	HMF和EMF	57	[41]
13	果糖	FeCl₃	乙醇/[Bmim]Cl	100	4h	EMF	30.1	[42]

序号	底物	催化剂	催化剂性质	反应介质	温度/℃	时间	产率/%	文献
1	HMF	30% K-10 clay-HPW	比表面积117m²/g	乙醇	100	10h	91.5	[12]
2	果糖	30% K-10 clay-HPW		乙醇	100	10h	61.5	[12]
3	HMF	HPW		乙醇	100	6h	83.1	[12]
4	HMF	HPW(0.051mmol H⁺)	比表面积926m²/g；总孔容1.47cm³/g	乙醇	90	2h	80.9	[31]
5	HMF	HSiW(0.051mmol H⁺)		乙醇	90	2h	85.3	[31]
6	HMF	HSiW(0.028mmol H⁺)		乙醇	90	2h	86.5	[31]
7	HMF	20%HSiW/M-Ns		乙醇	90	2h	82.7	[31]
8	HMF	40%HSiW/M-Ns		乙醇	90	2h	85.8	[31]
9	HMF	40%HSiW/M-Ns		乙醇	90	4h	84.1	[31]
10	HMF	60%HSiW/M-Ns		乙醇	90	2h	83.2	[31]
11	HMF	[MIMBS]₃PW₁₂O₄₀		乙醇	70	24h	90.7	[33]
12	果糖	[MIMBS]₃PW₁₂O₄₀		乙醇	90	24h	90.5	[33]
13	果糖	HPW		乙醇/DMSO^①	140	130min	64	[43]
14	蔗糖	HPW		乙醇/DMSO	140	130min	28	[43]
15	菊粉	HPW		乙醇/DMSO	140	130min	54	[43]
16	HMF	Fe₃O₄@SiO₂-HPW	比表面积27.6m²/g；孔容0.064cm³/g；平均孔径1.85 nm	乙醇	100	11h	84	[44]
17	HMF	Fe₃O₄@SiO₂-HPW		乙醇	100	24h	55	[44]
18	HMF	Ag₁H₂PW		乙醇	100	10h	88.7	[45]
19	HMF	40%MCM-41-HPW	比表面积998.2m²/g；总孔容0.87cm³/g	乙醇	100	12h	83.4	[45]
20	果糖	40%MCM-41-HPW		乙醇	100	12h	42.9	[45]
21	果糖	H₃PW₁₂O₄₀		乙醇/THF^②	130	30min	76	[46]
22	蔗糖	H₃PW₁₂O₄₀		乙醇/THF	130	30min	33	[47]
23	菊粉	H₃PW₁₂O₄₀		乙醇/THF	130	30min	62	[47]