果糖一步法制备5-甲氧基甲基-2-呋喃甲醛及树脂催化剂再生方法探究

doi:10.6023/A24080246

摘要/Abstract

5-甲氧基甲基-2-呋喃甲醛(MMF)是一种重要的生物基平台分子, 可作为燃料添加剂和用于制备多种化合物. 本工作利用一系列商业强酸性树脂催化剂, 以离子液体和甲醇为共溶剂, 实现了从果糖一步法向MMF的转化. 离子液体与中间产物5-羟甲基糠醛(HMF)之间具有强相互作用, 可以减少HMF自身缩合等副反应的发生, 提高MMF的产率. 在最佳反应条件下, 果糖的转化近乎完全, MMF的产率达到67.7%, HMF与MMF的总产率达到接近75%. 使用BET表面分析技术、红外光谱、元素分析及酸碱滴定技术对使用前后的催化剂进行表征, 证实了催化剂失活的可能机制是胡敏覆盖催化剂活性位点、树脂催化剂与离子液体之间的离子交换及催化剂酸性位点的微量脱落. 探索出合适的催化剂再生方案, 实现了催化剂的稳定循环. 此外, 本催化体系还可以将其它碳水化合物中的果糖组分高效转化为MMF, 为生物质转化制备MMF的产业化奠定了一定的研究基础.

关键词: 醚化反应, 树脂催化剂, 离子液体, 5-羟甲基糠醛, 5-甲氧基甲基-2-呋喃甲醛, 生物质能源

With the excessive use of fossil energy, energy and environmental problems have become increasingly prominent, and the search for new energy sources is imminent. Biomass is renewable, widely distributed, carbon neutral, and can be used to produce a variety of chemicals, so it has attracted wide attention from the scientific community and the business community. 5-Hydroxymethylfurfural (HMF) is an important biomass-based platform molecule that can be used to synthesize a variety of chemicals and fuels. It is a key intermediate for the synthesis of bio-based polyester monomer 2,5-Furandicarboxylic acid (FDCA). However, HMF is very active and heat-sensitive, and can self-polymerize at room temperature to form by-products such as humin. 5-(Methoxymethyl)-2-furaldehyde (MMF) is a new bio-based platform molecule. Its structure is similar with HMF, but its properties are more stable. It can be separated from the reaction system by simple distillation, and the separation cost is much lower than that of HMF, which is expected to replace HMF as a key platform compound for the product of bio-based furan chemicals. Therefore, the direct conversion of bio-based raw materials into MMF has very important research value and industrial significance. In this paper, a series of resin catalysts were used to realize the one-step conversion from fructose to MMF using ionic liquids and methanol as cosolvent. Under the best conditions, about 67.7% yield of MMF was obtained in the present of DA-330, which is higher than related research. However, the activity of DA-330 resin decreases very quickly in the reaction system. The yield of MMF was about 10% during the second experiment, which was much lower than that of the first time. After a series of characterizations, such as Brunner-Emmet-Teller measurements, Fourier transform infrared spectroscopy, acid base titration and elemental analysis, it was determined that the deactivation of the resin catalyst was due to the coverage of humin, ion exchange between the resin and ionic liquid, and the loss of acid sites of resin. After hydrogen peroxide oxidation, H⁺ ion exchange, the activity of the resin catalyst was restored to the level of the new catalyst, and the yield of MMF did not significantly decrease after recycled four times.

Key words: etherification reaction, resin catalyst, ionic liquid, 5-hydroxymethylfurfural, 5-(methoxymethyl)-2-furaldehyde, biomass energy

引用此文

鞠嘉浩, 徐吉磊, 王康军, 黄家辉. 果糖一步法制备5-甲氧基甲基-2-呋喃甲醛及树脂催化剂再生方法探究[J]. 化学学报, 2024, 82(12): 1216-1225.

Jiahao Ju, Jilei Xu, Kangjun Wang, Jiahui Huang. One-step Preparation of 5-(Methoxymethyl)-2-furaldehyde from Fructose and Regeneration of Resin Catalyst[J]. Acta Chimica Sinica, 2024, 82(12): 1216-1225.

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图/表 16

图1. 部分可从MMF得到的化合物

Figure 1. Compounds that can be obtained from MMF

图式1. 果糖制备MMF途径

Scheme 1. The pathway of preparing of MMF from Fructose

Entry	Catalyst	Fructose conversion/%	HMF yield/%	MMF yield/%
1	Blank	34.6	0.3	0
2	DA-330	100	4.9	62.3
3	DB-757	100	5.8	60.9
4	DNW-Ⅱ	100	11.7	58.5
5	[BMIM]Cl+H₂SO₄	100	1.6	53.7
6	[BMIM]Cl+TsOH	100	4.2	61.7
7	[BMIM]Cl+TfOH	100	1.7	55.8
8	盐酸	100	1.6	46.9
9	硫酸	100	1.3	33.3
10	对甲苯磺酸	100	0.1	9.8
11	三氟甲基磺酸	100	0.5	40.1

表1. 不同催化剂对果糖制备MMF的催化反应结果a

Table 1. Production of MMF from fructose with different catalystsa

Entry	Resin	NaOH volume consumed/mL	Acid content/ (mmol•g^-1)
1	DA-330	5.9	11.8
2	DB-757	5.8	11.6
3	DNW-Ⅱ	4.8	9.6

表2. 树脂的酸含量

Table 2. Acid content of resin

Entry	Cosolvent	Fructose conversion/%	HMF yield/%	MMF yield/%
1	甲醇	100	0	0.3
2	乙腈	100	2.8	50.5
3	DMF	100	30.7	8.7
4	NMP	100	0	59
5	DMSO	100	0.3	35.0
6	THF	100	0	7.2
7	[BMIM]Br	100	4.9	62.3
8	[BMIM]Cl	100	7.9	60.1

表3. 共溶剂对果糖制备MMF反应的影响

Table 3. The influence of cosolvent on the preparation of MMF from fructose

图2. 反应温度对反应的影响

Figure 2. The influence of temperature on the reaction Reaction condition: fructose 20 mg, DA-330 100 mg, MeOH 1.52 g, [BMIM]Br 0.38 g, t=390 min

图3. 反应时间对反应的影响

Figure 3. The influence of time on the reaction Reaction condition: fructose 20 mg, DA-330 100 mg, MeOH 1.52 g, [BMIM]Br 0.38 g, T=120 ℃

图4. 催化剂量对反应的影响

Figure 4. The influence of catalyst dosage on the reaction Reaction condition: fructose 20 mg, MeOH 1.52 g, [BMIM]Br 0.38 g, T=120 ℃, t=240 min

图5. 果糖浓度对反应的影响

Figure 5. The influence of fructose concentration on the reaction Reaction condition: DA-330 100 mg, MeOH 1.52 g, [BMIM]Br 0.38 g, T=120 ℃, t=240 min

图6. 催化剂循环使用

Figure 6. Recycling of catalysts Reaction condition: fructose 20 mg, DA-330 100 mg, MeOH 1.52 g, [BMIM]Br 0.38 g, T=120 ℃, t=240 min

图7. 未使用、使用后和处理后催化剂的红外对比图

Figure 7. Infrared comparison of fresh, used and generated catalysts

Entry	Sample	S%	N%	C%	H%	C/N	C/H
1	DA-330	13.3	0.04	43.1	5.6	1066.5	7.8
2	Used DA-330	9.6	6.5	51.2	6.5	7.8	7.8
3	Generated DA-330	12.8	0.7	45.8	5.1	61.7	9.0

表4. 使用前后催化剂元素分析

Table 4. Element analysis of catalysts

Entry	Sample	Surface area/(m²•g^-1)	Pore volume/(cm³•g^-1)	Pore size/nm	Acid content/(mmol•g^-1)
1	DA-330	7.2	0.007	68.5	11.8
2	Used DA-330	10.5	0.003	68.4	6.6
3	Generated DA-330	13.0	0.006	61.8	12.0

表5. 使用前后催化剂的BET和酸含量分析

Table 5. BET and acid content analysis of catalysts

图8. 再生催化剂循环套用

Figure 8. Recycling of regenerated catalyst Reaction condition: fructose 20 mg, DA-330 100 mg, MeOH 1.52 g, [BMIM]Br 0.38 g, T=120 ℃, t=240 min

Entry	Substrate	Conversion/%	HMF yield/%	MMF yield/%
1	Glucose	100	6.6	0.1
2	Inulin	100	12.3	49.4
3	Starch	100	0	0
4	Sucrose	100	7.3	34.1

表6. 由其它碳水化合物制备MMF

Table 6. Preparation of MMF from other carbohydrates

图式2. DA-330催化果糖制备MMF可能的反应机理

Scheme 2. Possible reaction mechanism for the conversion of fructose to MMF catalyzed by DA-330

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