Catalytic conversion of sweet sorghum stalk juice to furan compounds over Hβ zeolite
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摘要: 以γ-丁内酯为溶剂，研究了Hβ分子筛催化富含蔗糖、葡萄糖和果糖的甜高粱秆汁转化制呋喃类化合物（5-羟甲基糠醛或糠醛）的性能。结果表明，甜高粱秆汁在Hβ分子筛上主要转化为5-羟甲基糠醛，而含糖量相同的模型甜高粱秆汁在相同的反应条件下，主要产物却是糠醛。27Al固体核磁结果表明，甜高粱秆汁中的微量碱性金属钾等能与Hβ分子筛发生离子交换，导致Hβ分子筛上六配位铝转变为四配位铝；因为六碳糖生成糠醛需要Hβ分子筛上具备合适的铝配位环境，而离子交换引起铝配位状态的变化，导致了甜高粱秆汁在Hβ分子筛上的主要产物是5-羟甲基糠醛。Abstract: The conversion of sweet sorghum stalk juice rich in sucrose, glucose and fructose to furan compounds (5-hydroxymethylfurfural or furfural) was investigated over Hβ zeolite in γ-butyrolactone solvent. The results indicated that the main product for the conversion of sweet sorghum stalk juice (SSSJ) was 5-hydroxymethylfurfural; however, high yield of furfural was obtained in the conversion of model sweet sorghum stalk juice (MSSSJ) containing the same amount of hexose under the same conditions. The 27Al MAS NMR results showed that ion-exchange took place between the Hβ zeolite and alkaline ions (mainly potassium) in the sweet sorghum stalk juice, resulting in the transformation of octahedrally coordinated aluminum into tetrahedrally coordinated framework aluminum. As an appropriate configuration environment of aluminum for Hβ was necessary for the formation of furfural from hexose, high yield of 5-hydroxymethylfurfural was achieved for the conversion of sweet sorghum stalk juice (SSSJ) due to the ion-exchange of Hβ with alkaline ions.
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Key words:
- sweet sorghum stalk juice /
- Hβ /
- furan compounds /
- furfural /
- 5-hydroxymethylfurfural
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图 1 不同处理条件下Hβ分子筛的铝固体核磁谱图
Figure 1 27Al MAS NMR spectra of samples a: fresh Hβ zeolite; b: Hβ zeolite after reaction in the model of sweet sorghum stalk juice; c: Hβ zeolite after reaction in the sweet sorghum stalk juice; d: KHβ
图 2 甜高粱秆汁转化为呋喃化合物的路径示意图
Figure 2 Proposed reaction pathways for the conversion of sweet sorghum stalk juice to furan compounds
表 1 甜高粱秆汁在不同分子筛上的转化a
Table 1 Conversion of sweet sorghum stalk juice over various zeolites a
Entry Catalyst Conversion x/% Yield w/% Ara LA HMF FFA 1 Hβ 98.5 4.1 0.9 37.3 3.4 2 HY 91.3 4.5 0 6.2 1.2 3 H-M 73.5 1.2 0 35.1 1.5 a: 0.5g catalyst; sweet sorghum stalk juice 4 g; 14.5 g γ-butyrolactone as solvent; 150 ℃, 120 min, 2 MPa N2; Ara: Arabinose, LA: levulic acid, HMF: 5-hydroxymethylfurfural, FFA: furfural, H-M: H-mordenite 
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表 2 甜高粱秆汁在Hβ分子筛上的转化
Table 2 Conversion of sweet sorghum stalk juice over Hβ zeolite
Entry t/℃ Time t/min SSSJ m/g Solvent m/g Conversion x/% Yield w/% Ara LA HMF FFA 1 150 60 4 9.0 92.2 5.5 0.2 42.0 0.1 2 150 120 4 6.0 95.8 4.7 0.4 35.0 2.4 3 150 120 4 9.0 98.3 4.5 0.8 37.5 2.7 4 150 120 4 14.5 98.5 4.1 0.9 37.3 3.4 5 170 120 4 14.5 99.8 2.3 1.8 34.0 3.4 6 170 360 2 14.5 99.8 2.1 8.0 28.0 8.3 7 170 360 1 14.5 99.7 0.5 44.1 0.1 12.1 8b 150 120 4 14.5 99.1 2.3 0.2 6.2 1.5 9b 170 120 4 14.5 99.5 1.9 0.7 3.8 1.1 a: Hβ 0.5 g, sweet sorghum stalk juice(SSSJ) 4 g, γ-butyrolactone as solvent, 2 MPa N2; b: Hβ 0.1 g
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表 3 甜高粱秆汁、模型甜高粱秆汁及六碳糖在Hβ分子筛上的转化a
Table 3 Conversion of sweet sorghum stalk juice, model of sweet sorghum stalk juice and hexose over Hβ zeolite a
Entry t/℃ Time t/min Substrate Conversion x/% Yield w/% Ara LA HMF FFA 1b 150 120 SSSJ 98.5 4.1 0.9 37.3 3.4 2c 150 120 MSSSJ 100 4.3 7.5 14.4 42.5 3d 150 120 glucose 100 3.6 8.6 4.6 36.7 4e 150 60 fructose 100 2.1 4.7 9.0 48.5 5f 160 120 sucrose 100 1.7 5.7 1.8 35.0 a: 2MPa N2; b: Hβ 0.5 g, sweet sorghum stalk juice(SSSJ) 4 g, γ-butyrolactone 14.5 g as solvent; c: Hβ 0.5 g, Model sweet sorghum stalk juice(MSSSJ) 4 g, γ-butyrolactone 14.5 g as solvent; d: 0.1 g Hβ, glucose 0.5 g, γ-butyrolactone 9.0 g and water 0.5 g as solvent; e: 0.1 g Hβ, fructose 0.5 g, γ-butyrolactone 9.0 g and water 0.5 g as solvent; f: 0.2 g Hβ, sucrose 0.5 g, γ-butyrolactone 9.0 g and water 0.5 g as solvent
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表 4 钾对Hβ分子筛性能的影响a
Table 4 Effects of potassium on the catalytic performance of Hβ zeolite in the conversion of model sweet sorghum stalk juice to furan compoundsa
Catalyst Conversion x/% Yield w/% Acid sites density /(mmol·g-1)b HMF FFA Brønsted Lewis Hβ 100 14.4 42.5 0.28 0.17 KHβ 100 35.4 20.7 0.033 0.057 a: 2 MPa N2, 150 ℃, 120 min; Hβ 0.5 g; Model sweet sorghum stalk juice(MSSSJ); γ-butyrolactone 14.5 g as solvent; b: Adsorbed pyridine after desorption at 200 ℃[3]
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