Catalytic depolymerization of organosolv lignin to phenolic monomers and low molecular weight oligomers

被引:91
作者
Liu, Xudong [1 ]
Jiang, Zhicheng [2 ]
Feng, Shanshan [1 ]
Zhang, Hui [1 ]
Li, Jianmei [1 ]
Hu, Changwei [1 ]
机构
[1] Sichuan Univ, Coll Chem, Key Lab Green Chem & Technol, Minist Educ, Chengdu 610064, Sichuan, Peoples R China
[2] Sichuan Univ, Natl Engn Lab Clean Technol Leather Mfg, Chengdu 610064, Sichuan, Peoples R China
基金
中国国家自然科学基金;
关键词
Lignin; Solvolytic fractionation; Catalytic depolymerization; Phenolic monomers; Oligomers; BIOMASS FRACTIONATION; PLANT BIOMASS; REDUCTIVE DEPOLYMERIZATION; CORNCOB RESIDUE; KRAFT LIGNIN; HIGH-YIELD; BIO-OIL; CONVERSION; ACID; HYDROGENOLYSIS;
D O I
10.1016/j.fuel.2019.01.117
中图分类号
TE [石油、天然气工业]; TK [能源与动力工程];
学科分类号
0807 ; 0820 ;
摘要
The lignin-first strategy provides significant potential for producing value-added phenolics and high-quality biofuels. In this contribution, stepwise extraction and depolymerization of lignin in corncob residue towards the production of phenolic monomers, lignin-derived dimers and trimers was investigated. H2O/n-butanol (4:6, v/v) co-solvent could extract 87.1% of lignin in corncob residue, retaining a high-purity (86.0%) cellulose pulp. Ni/HZSM-5 catalysts with different Ni loadings were prepared and applied for further degradation of organosolv lignin. Over 5% Ni/HZSM-5, the highest yield of phenolic monomer was 19.5% with the selectivity of 66.7% towards 4-ethyl phenols (4-ethyl phenol and 4-ethyl guaiacol) at 300 degrees C, and liquid products with higher heating value (HHV) of 29.2 MJ kg(-1) were obtained. The 5% Ni/HZSM-5 catalyst promoted the cleavage of intramolecular beta-O-4 and C-beta-C-gamma. linkages, resulting in substantially decreased weight-average molecular weight (M-w)/number-average molecular weight (M-n) of the organosolv lignin from 2541/1064 Da to 562/391 Da, which implied the degradation of high-Mw oligomers to dimers and trimers. The catalyst also contributed to the hydrogenation of C-alpha = C-beta bonds in unsaturated intermediates (coniferyl alcohol and coumaryl alcohol). The possible cleavage mechanism for the degradation of lignin-derived oligomers was also proposed.
引用
收藏
页码:247 / 257
页数:11
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