Levoglucosenone production by catalytic pyrolysis of cellulose using ionic liquid as catalyst
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摘要: 纤维素是世界上含量最丰富的可再生有机碳资源之一,左旋葡萄糖酮(LGO)是来源于纤维素热解的一种高附加值平台化合物。本研究考察了离子液体烷基侧链长度对纤维素催化热解制备LGO的影响规律。实验结果表明,最短侧链的1-丁基-2,3-二甲基三氟甲烷磺酸咪唑离子液体对LGO表现了最好的催化效果,其原因是侧链长度减少导致离子液体阴阳离子间相互作用减弱,使离子液体扩散增强。在300 ℃热解时 LGO产率达到15.6%-C,离子液体的回收率为95.9%,其重复利用三次后LGO的产率只有轻微下降。通过密度泛函理论得到了LGO的最佳生成路径,其最低反应活化能为176.2 kJ/mol。此外,本方法也可同时获得多孔性的焦炭,其最高比表面积和孔容分别为389.4 m2/g和0.689 cm3/g。Abstract: Cellulose is one of the most abundant renewable organic carbon resources in the world. Levoglucosenone (LGO) is a high value-added platform chemical derived from cellulose pyrolysis. In this study, the influence of ionic liquid catalyst on the production of LGO by catalytic pyrolysis of cellulose was revealed. The results showed that 1-butyl-2,3-dimethylimidazolium triflate performed best for the LGO formation. The reason was that the decrease in the length of the side chain weakened the interaction between the cation and anion of the ionic liquid, which increased the diffusion of the ionic liquid. LGO reached a yield of 15.6%-C at pyrolysis temperature of 300 ℃, and the recovery rate of ionic liquid attained to 95.9%. Besides, LGO yield only slightly decreased after 3 times re-utilization of the ionic liquid. The formation path of LGO was calculated by density functional theory. The result showed the lowest activation energy was 176.2 kJ/mol. Moreover, this method was effective to obtain porous char at the same time, and the highest specific surface area and pore volume were 389.4 m2/g and 0.689 cm3/g, respectively.
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Key words:
- cellulose /
- ionic liquid /
- pyrolysis /
- levoglucosenone /
- porous char
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表 1 GC/MS检测到的化合物的定量分析(mg/g-纤维素)
Table 1 Quantitative analysis of compounds detected by GC/MS (mg/g-cellulose)
Peak Compound None Butyl Octyl Dodecyl Cetyl 300 ℃ 350 ℃ 300 ℃ 350 ℃ 300 ℃ 350 ℃ 300 ℃ 350 ℃ 300 ℃ 350 ℃ 1 furfural 0.9 1.0 13.8 2.9 6.7 3.3 4.4 5.6 5.9 3.1 2 4-hydroxydihydro
furan-2(3H)-one0.2 0.4 0.3 1.5 0.4 0.4 0.4 0.8 0.7 0.3 3 2-hydroxycyclopent
-2-enone0.4 0.6 0.6 − 0.8 1.1 0.5 2.9 0.5 0.8 4 5-methylfurfural 0.2 0.4 1.9 10.9 1.9 1.2 1.0 1.3 1.4 0.8 5 3-methylcyclopent-2-enone 0.3 0.4 1.3 − 1.0 2.8 1.8 2.9 0.6 1.7 6 methyl 2-furoate 0.4 0.4 2.8 − 1.0 1.2 1.6 1.7 1.4 0.5 7 furaneol 0.6 0.7 0.1 − 0.1 0.1 0.1 0.1 − − 8 LGO 6.0 1.4 121.7 107.8 96.5 80.8 96.7 78.2 91.9 85.1 9 LAC 1.9 2.4 5.3 6.6 40.3 21.0 31.7 12.2 4.6 2.6 10 DGP 7.6 5.7 19.8 56.5 17.3 9.2 13.8 11.7 13.4 9.1 11 HMF 1.1 1.2 1.2 − 0.1 − 1.9 − 0.5 − 12 DH − − 0.5 − 0.2 − 0.1 − 0.1 − 13 ADGH 0.9 1.1 1.3 − 1.2 0.9 1.1 0.6 0.9 0.4 14 LGA 211 284 11.1 8.9 9.9 19.5 51.5 18.5 34.5 10.4 15 AGF 14.6 20.1 − − − − − − − − (LAC) 1-hydroxy, (1R)-3,6-dioxabicyclo[3.2.1]octan-2-one, (DGP) 1,4:3,6-Dianhydro-α-D-glucopyranose, (HMF) 5-hydroxymethylfurfural, (DH) 6,8-dioxabicyclo[3.2.1]octane-2,4,4-triol, (ADGH) 1,5-anhydro-4-deoxy-D-glycero-hex-1-en-3-ulose, (AGF) 1,6-Anhydro-β-D-glucofuranose 表 2 焦炭的比表面积、孔容和平均直径
Table 2 Analysis of the specific surface area, pore volume and average diameter of char
Ionic
liquidsSBET/
(m2·g−1)vtotal/
(cm3·g−1)vmicro/
(cm3·g−1)dave Butyl 389.4 0.689 0.067 7.08 Octyl 281.2 0.408 0.045 5.80 Dodecyl 105.3 0.52 − 19.91 Cetyl 58.1 0.340 − 23.40 vmicro was calculated based on t-plot method -
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