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摘要: 以咪唑类高铼酸盐为催化剂，以离子液体1-烯丙基-3-甲基咪唑氯盐（[Amim]Cl）为溶剂降解微晶纤维素（MCC）。分别考察反应温度、反应时间、反应物浓度、催化剂用量和结构对纤维素降解反应的影响。结果表明，以5% 1-（3-磺酸）丙基-3-甲基咪唑高铼酸盐（[mim-（CH2）3SO3H]ReO4）为催化剂，在微波辅助加热条件下，0.1 g纤维素在2.0 g离子液体[Amim]Cl中于160 ℃降解30 min，还原糖收率（TRS）和葡萄糖收率最高可达89.6%和46.7%。研究还对咪唑类高铼酸催化纤维素降解反应的催化机理进行讨论，认为催化剂芳环阳离子、ReO4-中Re=O与纤维素分子中羟基的相互作用是促进纤维素降解的关键。Abstract: Imidazolium perrhenate was applied as the catalyst to promote the degradation of microcrystalline cellulose (MCC) with the solvent of ionic liquid 1-allyl-3-methyl imidazolium chloride ([Amim]Cl). The effects of reaction temperature, reaction time, reactant concentration, the amount and structure of catalyst on the degradation of cellulose were studied in details. When using 5% of [mim-(CH2)3SO3H]ReO4, 70μL of water, 0.1g cellulose and 2.0g [Amim]Cl under microwave irradiation for 30min at 160℃, 89.6% of total reducing sugar (TRS) and 46.7% of glucose yield can be obtained. The degradation mechanism of cellulose catalyzed by imidazolium perrhenate was also studied.The hydrogen bonding between hydroxyl groups of cellulose and ReO4 anion and aromatic ring cation of catalyst is assumed to be the key step for depolymerization of cellulose.
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Key words:
- imidazolium perrhenate /
- cellulose /
- total reducing sugar /
- glucose
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图 1 反应温度和催化剂对纤维素降解效果的影响
Figure 1 Effect of temperature and catalyst on cellulose hydrolysis
■: TRS with 70 μL of water; ◆: glucose yield with 70 μL of water; ▲:TRS with 5% of [C4mim]ReO4 and 70 μL of water; ○: glucose yield with 5% of [C4mim]ReO4 and 70 μL of water
图 3 反应物浓度对纤维素降解反应的影响
Figure 3 Effect of reactant concentration on cellulose hydrolysis
图 5 高铼酸盐催化纤维素降解机理示意图
Figure 5 Proposed mechanism for cellulose hydrolysis with perrhenate catalysts and water
图 6 [C4mim]ReO4与纤维二糖红外光谱谱图
Figure 6 FT-IR of [C4mim]ReO4 and cellobiose
a: cellobiose; b: [C4mim]ReO4; c: [C4mim]ReO4+cellobiose
表 1 不同催化剂催化的纤维素降解反应
Table 1 Degradation of cellulose catalyzed by different catalyst
Catalyst Yield wmol/% TRS glucose oligosaccharides glucose+oligosaccharides 5-HMF - 28.0 7.0 - 7.0 0.3 NH4ReO4 (1) 62.3 22.9 4.5 27.4 1.8 AgReO4 (2) 69.2 29.6 5.8 35.4 3.1 [C2mim]ReO4 (3) 90.1 44.6 12.1 56.7 3.5 [C4mim]ReO4 (4) 88.1 43.2 10.1 53.3 3.9 [C6mim]ReO4 (5) 90.5 43.5 8.3 51.8 3.8 [mim-(CH2)3SO3H]ReO4 (6) 89.6 46.7 11.2 57.9 4.1 [HOOC-CH2-mim]ReO4 (7) 90.3 45.4 9.5 54.9 3.7 [mim-(CH2)3SO3H]Cl (8) 61.3 27.7 - 27.7 7.5 [HOOC-CH2-mim]Cl (9) 52.1 21.6 - 21.6 6.3 
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