生物质资源合成烷氧基甲基呋喃醚的研究进展

doi:10.3969/j.issn.1673-5854.2021.04.007

摘要/Abstract

摘要：

生物质资源是自然界中唯一的有机碳资源，能用于合成多种高附加值的燃料和化学品。生物质醚类化合物是其中重要的一类衍生物，烷氧基甲基呋喃醚已经应用于柴油和柴油添加剂中，特别是5-乙氧基甲基糠醛（EMF）因其具有能量密度高、毒性低、稳定性好、流动性好等特点而受到广泛关注。本文综述了近年来以5-羟甲基糠醛（HMF）为基本结构的不同生物质原料来源合成烷氧基甲基呋喃醚的研究进展情况，讨论了催化剂的Lewis酸和Brønsted酸对醚化产物选择性的影响。在总结烷氧基甲基呋喃醚合成方法的基础上，对其催化体系的未来发展方向进行了探讨。

关键词: 有机碳资源, 烷氧基甲基呋喃醚, 5-羟甲基糠醛, 醚化

Abstract:

Biomass resources are the only organic carbon resources in nature, which can synthesize a variety of high value-added fuels and chemicals. Biomass ethers compounds are one of the most important biomass derivatives. Among them, alkoxymethylfuran ether has been applied to diesel and diesel additives. Especially, 5-(ethoxymethyl)furfural (EMF) has attracted much attention due to its high energy density, low toxicity, good stability and good fluidity. Recent advances in the synthesis of alkoxymethylfuran ether from different biomass materials with 5-(hydroxymethyl)furfural (HMF) as the basic structure were reviewed. The effects of Lewis acid and Brønsted acid on the selectivity of etherification products were discussed. On the basis of summarizing the synthesis methods of alkoxymethylfuran ether, the future development direction of the catalytic system was discussed.

Key words: organic carbon resources, alkoxymethylfuran ether, 5-(hydroxymethyl) furfural (HMF), etherification

中图分类号:

TQ35

沈鸿波, 李兴龙, 傅尧. 生物质资源合成烷氧基甲基呋喃醚的研究进展[J]. 生物质化学工程, 2021, 55(4): 43-58.

Hongbo SHEN, Xinglong LI, Yao FU. Recent Advances in Synthesis of Alkoxymethylfuran Ether from Biomass Resources[J]. Biomass Chemical Engineering, 2021, 55(4): 43-58.

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序号 No.	催化剂 catalyst	温度/℃ temperature	反应时间/h reaction time	转化率/% conversion	EMF收率/% yield of EMF	EL收率/% yield of EL	文献 ref.
1	HY沸石HY zeolite	70	24	—	8.5	—	[26]
2	Al-MCM-41(Si/Al=75)	140	5	61	—	—	[27]
3	Al-MCM-41(Si/Al=50)	140	5	100	68	10	[27]
4	Al-MCM-41(Si/Al=25)	140	5	100	37	47	[27]
5	SBA-15	140	5	75	—	—	[26]
6	ZrO₂-SBA-15	140	5	100	76	23	[26]
7	Al-TUD-1	140	4	88	81	—	[28]
8	Amberlyst-15	75	24	—	55	8	[29]
9	Amberlite IR 120	75	24	—	33	7	[29]
10	Dowex50WX8	75	24	—	45	9	[29]
11	Dowex DR2030	75	24	—	57	8	[29]
12	硅硫酸silica sulfuric acid	75	24	—	36	7	[29]
13	HPW-K-10	100	10	—	91.5	—	[30]
14	H₄SiW₁₂O₄₀	90	2	81.3	86.5	4.6	[31]
15	20%H₄SiW₁₂O₄₀/MCM-41	90	2	84.8	82.7	4.3	[31]
16	40%H₄SiW₁₂O₄₀/MCM-41	90	2	80.1	85.8	4.6	[31]
17	40%H₄SiW₁₂O₄₀/MCM-41	90	4	92	84.1	5.8	[31]
18	60%H₄SiW₁₂O₄₀/MCM-41	90	2	78.9	83.2	4.4	[31]
19	[MIMBS]₃PW₁₂O₄₀	100	10	—	91.5	—	[32]
20	硫酸化纤维素cellulose sulfates	100	10	—	84.4	—	[33]
21	SiO₂-SO₃H	100	12	—	83.3	—	[34]
22	Fe₃O₄@SiO₂-SO₃H	100	10	—	89.3	—	[34]
23	Fe₃O₄@C-SO₃H	100	12	—	88.4	—	[35]
24	[BmimSO₃H]₃PW₁₂O₄₀	70	24	98.7	90.7	—	[32]
25	AlCl₃	100	5	—	92.9	—	[36]

序号 No.	催化剂 catalyst	溶剂体系 solvent system	反应条件 reaction condition	EMF收率/% yield of EMF	文献 ref.
1	H₂SO₄	EtOH	82.5 ℃，6 h	60	[56]
2	HCl	EtOH	120 ℃，2 h	40	[57]
3	MCM-41-HPW	EtOH	100 ℃，12 h	42.9	[58]
4	HPW-K-10	EtOH	100 ℃，24 h	61.5	[30]
5	硫酸化纤维素cellulose sulfates	EtOH	100 ℃，12 h	72.5	[33]
6	Glu-TsOH-Ti	EtOH	100 ℃，30 h	66	[59]
7	SiO₂-SO₃H	EtOH	100 ℃，12 h	63.1	[41]
8	Fe₃O₄@SiO₂-SO₃H	EtOH	100 ℃，10 h	72.5	[41]
9	BF₃·(Et)₂O/AlCl₃·6H₂O	EtOH	110 ℃，3 h	55	[61]
10	AlCl₃	EtOH	100 ℃，11 h	71.2	[36]
11	CrCl₃	EtOH	100 ℃，12 h	33	[36]
12	CuSO₄	EtOH	110 ℃，10 h	45.2	[36]
13	Fe₂(SO₄)₃	EtOH	120 ℃，10 h	47.7	[36]

序号 No.	树脂型催化剂 resin catalyst	EMF收率/% yield of EMF	EL收率/% yield of EL	EMFDA收率/% yield of EMFDA	HMF收率/% yield of HMF
1	Amberlyst-15	71	16	10	—
2	Amberlite IR120	32	9	5	16
3	Dowex50WX8	56	14	7	—
4	Dowex DR2030	68	16	6	—
5	硅硫酸silica sulfuric acid	69	17	9	—

序号 No.	底物 substrate	溶剂体系 solvent systems	催化剂 catalyst	反应条件 reaction condition	MMF收率/% yield of MMF	ML收率/% yield of ML	文献 ref.
1	纤维素cellulose	甲醇methanol	H₂SO₄	183 ℃，12 min	2.7	37.8	[67]
2	纤维素cellulose	甲醇methanol	CF₃SO₃H	193 ℃，10 min	1.5	22.3	[67]
3	纤维素cellulose	甲醇methanol	TsOH	210 ℃，30 min	0.5	34.8	[67]
4	纤维素cellulose	甲醇methanol	SO₂	210 ℃，75 min	0.6	18.2	[67]
5	纤维素cellulose	V(CH₃OH): V(H₂O)=7:3	H₂SO₄	189 ℃，8 min	1.1	18.1	[67]
6	纤维素cellulose	V(CH₃OH): V(CCl₄)=1:1	H₂SO₄	194 ℃，5 min	TR	45.5	[67]
7	纤维素cellulose	V(CH₃OH): V(PhMe)=1:1	H₂SO₄	195 ℃，7 min	1.8	39.8	[67]
8	纤维素cellulose	V(CH₃OH): V(CYH)=1:1	H₂SO₄	208 ℃，3 min	0.4	37.1	[67]
9	果糖fructose	甲醇methanol	H₂SO₄	180 ℃，30 s	38.7	—	[63]
10	果糖fructose	甲醇methanol	HCl	80 ℃，8 h	3	—	[63]
11	果糖fructose	V(CH₃OH): V(THF)=1:1	Amberlyst-15	120 ℃，180 min	47	14.4	[68]
12	果糖fructose	V(CH₃OH): V(Hex)=1:4.8	[MSPIM]Cl	100 ℃，20 min	57	9	[69]
13	果糖fructose	超临界甲醇supercritical methanol	H₂SO₄	240 ℃，30 s	79	—	[70]
14	5-羟甲基糠醛 5 -(hydroxymethyl)urfural	甲醇methanol	Al-NbP-pH₂	180 ℃，360 min	79.5	11.2	[71]

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