糠酸制备生物质基2, 5-呋喃二甲酸的研究进展

doi:10.3969/j.issn.0253-2417.2023.02.001

摘要/Abstract

摘要：

2, 5-呋喃二甲酸(FDCA)作为一种绿色的生物基平台化合物，可广泛应用于聚酯、塑化剂、消防及医药等领域。目前，根据合成FDCA的原料区分，FDCA合成路线分为5-羟甲基糠醛(HMF)路线、糠酸路线和其他原料路线。其中糠酸可由大宗生物质基化学品糠醛氧化制备，糠醛工业化生产使得糠酸制备FDCA路线具有绿色、经济性高的优势。据此，综述了糠酸制备FDCA的4种方法：歧化法、羰基化法、C—H羧基化法以及生物催化法的研究现状，对比分析了各方法的优劣及研究进展。通过对比分析表明：C—H羧基化法是一种反应条件温和、绿色环保的工艺，具有实现规模化生产的潜力。

关键词: 糠酸, 2, 5-呋喃二甲酸, 生物质, 平台化合物, 羧基化

Abstract:

As a green bio-based platform chemical, 2, 5-furan dicarboxylic acid(FDCA) was widely used in polyester, plasticizer, fire protection, medicine, etc. At present, according to the distinction of raw materials for the synthesis of FDCA, the synthetic routes of FDCA could be divided into 5-hydroxymethylfurfural(HMF) route, furoic acid route and other raw material routes. Among them, furfural acid could be prepared from the oxidation of bulk bio-based chemical furfural, and the industrial production of furfural made the preparation of FDCA from furfural acid had the potential advantages of green and economical. Based on this, this paper reviews the research status of four methods for preparing FDCA from furoic acid, including: disproportionation, carbonylation, carboxylation and biocatalysis methods. The paper also summarizes a comparative analysis of the advantages and disadvantages of each method and highlights the progress made in their respective research fields. A comparative analysis indicates that the C-H carboxylation method is a gentle and environmentally friendly process, demonstrating significant potential for large-scale production.

Key words: furoic acid, 2, 5-furandicarboxylic acid, biomass, platform compound, carboxylation

中图分类号:

TQ35
TQ251.1

常春, 毋晋生, 陈志勇. 糠酸制备生物质基2, 5-呋喃二甲酸的研究进展[J]. 林产化学与工业, 2023, 43(2): 1-11.

Chun CHANG, Jinsheng WU, Zhiyong CHEN. Research Progress in Preparation of Biomass Based 2, 5-Furan Dicarboxylic Acid from Furoic Acid[J]. Chemistry and Industry of Forest Products, 2023, 43(2): 1-11.

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反应类型 reaction type	反应物¹⁾ reactant	催化剂 catalyzer	温度/℃ temperature	时间/h time	转化率/% conversion rate	产率²⁾/% yield	文献reference
歧化反应 disproportionation reaction	PF	ZnCl₂	250	3	61	52	[27]
	PF	CdI₂	260	5.5	92	64	[28]
	PF	ZnI₂	260	5.5	48	41	[28]
	PF	ZnCl₂	260	5.5	39	33	[28]
	PF	Ag/SiO₂/CdI₂	200	20	51	264^*	[29]
	PF	Ag/SiO₂	200	20	20	1 203^*	[29]
羰基化反应carbonylation reaction	BrFA	Xantphos/PPh₃/PdCl₂	90	24	>99	>99	[31]
	BrFA	TPPTS/Pd(dba)₂	90	8	>99	98	[32]
	BrFA	Pd(Xantphos)Cl₂/AC	90	16	>99	95	[33]
羧基化反应carboxylation reaction	糠酸铯cesium furoate	Cs₂CO₃	200	5	94	89	[38]
	糠酸铯/糠酸钾cesium furoate/PF	Cs₂CO₃/K₂CO₃	260-285	24	98	89	[40]
	Cu(FC)₂	Cs₂CO₃	220	20	—	99	[41]
	糠酸furoic acid	Cs₂CO₃	220	20	—	76	[41]
	糠酸钠sodium furoate	K₂CO₃/HCOONa	280	6	84	79	[43]
生物催化反应biocatalytic reaction	糠酸furoic acid	HmfF	50	8	—	4	[50]

合成途径 synthetic route	原料来源 material source	反应介质 reaction medium	转化路线特点 characteristic of conversion path	副产物 by-product	工业化实现程度 implementation of industrialization	经济性 economy
歧化法 disproportionation	广泛 abroad	固相solid, 熔融相molten	歧化 disproportionation	较多 more	难 difficult	成本较高 high cost
羰基化法 carbonylation	较少 less	有机相organic, 水相aqueous	C—Br羰基化 carbonylation	较少 less	难 difficult	成本较高 high cost
羧基化法 barboxylation	广泛 abroad	固相solid, 熔融相molten	C—H羧基化 carboxylation	较少 less	难 difficult	成本较低 low cost
生物催化法 biocatalysis	较少 less	液相 liquid	可逆(脱)羧 reversible(de) carboxylation	较少 less	难 difficult	成本较高 high cost

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