One-step Preparation of 5-(Methoxymethyl)-2-furaldehyde from Fructose and Regeneration of Resin Catalyst

doi:10.6023/A24080246

Abstract

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

Cite this article

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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Fig. & Tab. 16

Figure 1. Compounds that can be obtained from MMF

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

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

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

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

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

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 ℃

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

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

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

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

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

Table 5. BET and acid content analysis of catalysts

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

Table 6. Preparation of MMF from other carbohydrates

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

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