Microwave-assisted extraction of lignin from bamboo by ionic liquid EmimOAc

doi:10.16085/j.issn.1000-6613.2019-0106

Abstract

Abstract:

The strong anti-deconstructive property of the bamboo （Phyllostachys pubescens Mazel） cell wall greatly limits its utilization as raw material in the fields of bioenergy, biomass-based materials, etc. Therefore, it is necessary to carry out pretreatment including main component separation to improve its utilization efficiency. In this work, microwave-assisted extraction of lignin from bamboo by using 1-ethyl-3-methylimidazolium acetate （EmimOAc） as solvent was carried out. The physicochemical properties of the obtained lignin fractions were characterized, and compared with the lignin extracted by EmimOAc using oil bath as heating source （110℃, 16h） and the alkali-soluble lignin extracted by 5% NaOH solution （50℃, 5h）. The results showed that the yield of lignin when EmimOAc was used as extractant under the microwave irradiation could reach 14.7% within 80min, which was more than twice of the yield （6.2%） when the lignin was extracted by EmimOAc using oil bath as heating source. Ionic liquid extracted lignin (ILL) and alkaline extracted lignin (AL) had a similar backbone structure, but under the effect of ionic liquid, more ester bonds between the ILL structural units were broken. Compared with AL, ILL showed higher thermal stability.

Key words: bamboo, lignin, microwave-assisted extraction, ionic liquid, chemical structure

摘要：

毛竹细胞壁强的抗解构特性大大限制了毛竹作为原料在生物质能源、生物质基材料等领域的应用，因此有必要对其进行包括主要组分分离在内的预处理以提高它的使用效率。本研究采用微波辅助1-乙基-3-甲基咪唑乙酸盐（EmimOAc）法从毛竹中分离出木质素，分析所获得的木质素的物理化学特性，并与用5% NaOH（50℃，5h）提取的毛竹木质素、油浴加热（110℃，16h）EmimOAc提取的毛竹木质素进行对比。结果表明：微波辅助EmimOAc处理80min后木质素得率14.7%，比油浴加热EmimOAc提取木质素的得率（6.2%）提高了2倍以上；离子液体提取的木质素（ILL）和碱提木质素（AL）具有相似骨架结构，但在离子液体的作用下，ILL结构中有更多的酯键链接发生断裂；与AL相比，ILL具有更高的热稳定性。

关键词: 毛竹, 木质素, 微波辅助提取, 离子液体, 化学结构

CLC Number:

O629.12

Lifang HU,Hongwei HE,Yu ZHANG,Qi XIA,Lin YUAN,Hong PENG,Rongsheng RUAN,Mengyang ZHOU. Microwave-assisted extraction of lignin from bamboo by ionic liquid EmimOAc[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4352-4360.

胡莉芳,何鸿伟,张宇,夏琪,袁林,彭红,阮榕生,周梦阳. 微波辅助离子液体EmimOAc提取毛竹木质素[J]. 化工进展, 2019, 38(9): 4352-4360.

Figures/Tables 7

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木质素	得率/%
ILL₁	2.3
ILL₂	1.8
ILL₃	13.6
ILL₄	14.7
ILL₅	6.2

木质素	得率/%
ILL₁	2.3
ILL₂	1.8
ILL₃	13.6
ILL₄	14.7
ILL₅	6.2

标注	δ _C/δ _H	结构归属
B_β	54.1/3.05	树脂醇结构中的C_β—H_β（B）
—OCH₃	56.3/3.73	甲氧基
A_γ	60.1/3.39/3.71	β-烷基-芳基醚键结构中的C_γ—H_γ（A）
I_γ	61.9/4.09	对羟基肉桂醇端基的C_γ—H_γ（I）
C_γ	62.8/3.68	苯基香豆满结构中的C_γ—H_γ（C）
B_γ	71.66/3.81/4.18	树脂醇结构中的C_γ—H_γ（B）
A_α	72.4/4.86	β-烷基-芳基醚键结构中的C_γ—H_γ（A）
D_α	81.7/5.09	螺旋二烯酮结构C_α—H_α（D）
B_β	85.4/4.66	树脂醇结构中的C_β—H_β（B）
A_β(S)	84.5/4.27	与S单元相连β-O-4′结构中的C_β—H_β（赤式，A）
A_β(S)	86.5/4.10	与S单元相连β-O-4′结构中的C_β—H_β（苏式，A）
C_α	88.1/5.57	苯基香豆满结构中的C_α—H_α（C）
S_2,6	104.5/6.69	紫丁香基单元结构中的C_2,6 —H_2,6（S）
S′_2,6	106.9/7.31	氧化（C_α O）S结构中的C_2,6—H_2,6（S′）
G₂	111.6/6.99	愈创木基结构中的C₂—H₂（G）
FA₂	111.5/7.28	阿魏酸中的C₂—H₂（FA）
pCA_β	115.7/6.27	对香豆酸中的C_β—H_β（pCA）
G₅	115.0/6.68	愈创木基结构中的C₅—H₅（G）
FA_β	115.7/6.29	阿魏酸中的C_β—H_β（FA）
pCA_3,5	116.1/6.78	对香豆酸中的C_3,5—H_3,5（pCA）
G₆	119.5/6.78	愈创木基结构中的C₆—H₆（G）
FA₆	123.1/7.08	阿魏酸中的C₆—H₆（FA）
H_2，6	128.4/7.19	对羟基苯基单元中的C_2,6—H_2,6（H）
pCA_2,6	130.5/7.51	对香豆酸中的C_2,6—H_2,6（pCA）

标注	δ _C/δ _H	结构归属
B_β	54.1/3.05	树脂醇结构中的C_β—H_β（B）
—OCH₃	56.3/3.73	甲氧基
A_γ	60.1/3.39/3.71	β-烷基-芳基醚键结构中的C_γ—H_γ（A）
I_γ	61.9/4.09	对羟基肉桂醇端基的C_γ—H_γ（I）
C_γ	62.8/3.68	苯基香豆满结构中的C_γ—H_γ（C）
B_γ	71.66/3.81/4.18	树脂醇结构中的C_γ—H_γ（B）
A_α	72.4/4.86	β-烷基-芳基醚键结构中的C_γ—H_γ（A）
D_α	81.7/5.09	螺旋二烯酮结构C_α—H_α（D）
B_β	85.4/4.66	树脂醇结构中的C_β—H_β（B）
A_β(S)	84.5/4.27	与S单元相连β-O-4′结构中的C_β—H_β（赤式，A）
A_β(S)	86.5/4.10	与S单元相连β-O-4′结构中的C_β—H_β（苏式，A）
C_α	88.1/5.57	苯基香豆满结构中的C_α—H_α（C）
S_2,6	104.5/6.69	紫丁香基单元结构中的C_2,6 —H_2,6（S）
S′_2,6	106.9/7.31	氧化（C_α O）S结构中的C_2,6—H_2,6（S′）
G₂	111.6/6.99	愈创木基结构中的C₂—H₂（G）
FA₂	111.5/7.28	阿魏酸中的C₂—H₂（FA）
pCA_β	115.7/6.27	对香豆酸中的C_β—H_β（pCA）
G₅	115.0/6.68	愈创木基结构中的C₅—H₅（G）
FA_β	115.7/6.29	阿魏酸中的C_β—H_β（FA）
pCA_3,5	116.1/6.78	对香豆酸中的C_3,5—H_3,5（pCA）
G₆	119.5/6.78	愈创木基结构中的C₆—H₆（G）
FA₆	123.1/7.08	阿魏酸中的C₆—H₆（FA）
H_2，6	128.4/7.19	对羟基苯基单元中的C_2,6—H_2,6（H）
pCA_2,6	130.5/7.51	对香豆酸中的C_2,6—H_2,6（pCA）

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