微波辅助杨木快速苯酚液化及产物表征

doi:10.11707/j.1001-7488.20141116

摘要/Abstract

摘要：

针对传统木材苯酚液化技术中存在的反应时间长、产物黏度高和反应活性降低等问题,采用微波加热方式,将杨木木粉在酸化苯酚溶剂中进行快速解聚反应.结果表明,微波加热条件下杨木苯酚液化的适宜条件为: 木粉含水率30%~40%,液化时间15 min,苯酚与木粉的比例(P/W)2.5,木粉粒径0.18~0.25 mm,在此条件下木材液化率达到87%.微波加热的木材苯酚液化速率比传统油浴加热提高至少6倍.木材被降解为醇类、酸类、醚类、醛类和酚类等低分子质量物质,液化产物黏度显著降低,仅为3 015 mPa·s,且与甲醛的反应活性较高,100 g液化产物反应消耗的甲醛达2.1 mol.微波加热与传统加热下的木材苯酚液化反应历程不尽相同,主要表现在纤维素和半纤维素降解为单糖后,单糖可进一步断裂为2,3-丁二醇、1,2-丙二醇、乙二醇和乙二醛等物质,这些物质相互之间可以发生脱水、羟醛缩合等反应进一步生成2-乙氧基-丙烷, 1,1-二乙氧基-乙烷、二异丙基缩甲醛和12-冠醚-4.

关键词: 微波加热, 杨木, 苯酚液化, 产物表征

Abstract:

A method for fast poplar wood liquefaction in phenol by using microwave energy was successfully developed. The optimum conditions for microwave-assisted poplar wood liquefaction in phenol are as follows: moisture content 30%-40%, reaction time 15 min, phenol to wood (P/W) ratio 2.5, wood powder diameter 0.18-0.25 mm, and liquefaction yield 87%. It was proved that microwave improved the liquefaction rate at least 6 times faster than conventional heating. Wood was degraded to low molecular weight substances including alcohols, acids, ether, aldehyde and phenolic compounds. Viscosity of liquefied wood products was remarkably decreased from 8 250 mPa·s to 3 015 mPa·s. And 100 g of liquefied wood reacted with about 2.1 mol of formaldehyde. There were only seven main conpounds, including phenol, 2,3-butanediol, 1,2-propanediol, 2-ethoxy-propane, 1,1-diethoxy-ethane, diisopropyl formal and 12-crown-4 in diethyl ether-soluble portions from liquefied wood products. It was concluded that the reaction mechanism was somewhat different between microwave-assisted and traditional wood phenolation. Cellulose and hemicellulose were firstly degraded into monosaccharides. And monosaccharides could be further cracked into 2, 3- butanediol, 1, 2-propanediol, ethylene glycol and ethanedial, and so on. These substances reacted with each other and converted to 2-ethoxy-propane, 1, 1-diethoxy-ethane, diisopropyl formal and 12-crown-4.

Key words: microwave heating, poplar, phenolation, product characterization

中图分类号:

TQ351

李改云, 朱显超, 邹献武, 向琴, 何玉婵. 微波辅助杨木快速苯酚液化及产物表征[J]. 林业科学, 2014, 50(11): 115-121.

Li Gaiyun, Zhu Xianchao, Zou Xianwu, Xiang Qin, He Yuchan. Rapid Wood Liquefaction with Phenol by Microwave Heating and Product Characterization[J]. Scientia Silvae Sinicae, 2014, 50(11): 115-121.

参考文献

陈俊宏.2010.杉木苯酚液化产物及树脂的结构与性能表征.北京: 北京林业大学硕士学位论文.
(Chen J H. 2010. Characterization of structure and properties of liquefied products from Chinese fir with phenol and its resin. Beijing: MS thesis of Beijing Forestry University. [in Chinese] )
陈秋玲,李如燕,孙可伟,等.2009.利用麦秆制聚氨酯多元醇研究.高分子通报, (11):37-43.
(Chen Q L, Li R Y, Sun K W, et al. 2009. Research on liquefaction of wheat straw for polyurethane polyol. Polymer Bulletin, (11):37-43. [in Chinese] )
吴晔. 1989. 木材介电常数的研究. 安徽农学院学报, (1):59-74.
(Wu Y. 1989. Study on the dielectric constants of wood. Journal of Anhui Agricultural University, (1):59-74. [in Chinese] )
Faix O. 1991. Classification of lignin from different botanical origins by FT-IR spectroscopy. Holzforschung,45 (Suppl.):21-27.
Gardner DJ, Mcginnis G D. 1988. Comparison of the reaction rates of the alkali-catalyzed addition of formaldehyde to phenol and selected lignins. Journal of Wood Chemistry and Technology, 8 (2): 261-288.
Ge L, Wu X M, Chen J W, et al. 2011. A new method for industrial production of 2,3-butanediol. Journal of Biomaterials and Nanobiotechnology,2 (3): 335-336.
Hassan E B, Kim M, Wan H. 2009. Phenol-formaldehyde-type resins made from phenol-liquefied wood for the bonding of particleboard. Journal of Applied Polymer Science, 112 (3):1436-1443.
Hassan E B, Mun S P. 2002. Liquefaction of pine bark using phenol and lower alcohols with methanesulfonic acid catalyst. Journal of Industrial and Engineering Chemistry, 8 (4): 359-364.
Huber G W, Iborra S, Corma A. 2006. Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. Chem Rev,106 (9): 4044-4098.
Kr?an A, ?agar E. 2009. Microwave driven wood liquefaction with glycols. Bioresource Technology, 100 (12):3143-3146.
Kunaver M, Medved S, ? uk N, et al. 2010. Application of liquefied wood as a new particle board adhesive system. Bioresource Technology, 101 (4): 1361-1368.
Lee S H, Wang S Q. 2005. Effect of water on wood liquefaction and the properties of phenolated wood. Holzforschung, 59 (6):628-634.
Lin L Z, Nakagame S, Yao Y, et al. 2001. Liquefaction mechanism of β-o-4 lignin model compound in the presence of phenol under acid catalysts part 2 reaction behavior and pathways. Holzforschung, 55 (6): 625-630.
Lin L Z,Yao Y G,Yoshioka M, et al. 2004. Liquefaction mechanism of cellulose in the presence of phenol under acid catalysts. Carbohydrate Polymers, 57 (2):123-129.
Pan H. 2011. Synthesis of polymers from organic solvent liquefied biomass: a review. Renewable and Sustainable Energy Reviews, 15 (7): 3454-3463.
Pan H, Zheng Z F, Hse C Y. 2012. Microwave-assisted liquefaction of wood with polyhydric alcohols and its application in preparation of polyurethane (PU) foams. European Journal of Wood and Wood Products, 70 (4):461-470.
Schwanninger M, Rodrigues J C, Pereira H, et al. 2004. Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose. Vib Spectrosc, 36 (1): 23-40.
Xiao W H, Niu W J, Yi F, et al. 2013. Influence of crop residue types on microwave-assisted liquefaction performance and products. Energy Fuels, 27 (6): 3204-3208.
Zhang Y C, Ikeda A, Hori N, et al. 2006. Characterization of liquefied product from cellulose with phenol in the presence of sulfuric acid. Bioresour Technol, 97 (2): 313-321.
Zhuang Y B, Guo J X, Chen L M, et al. 2012. Microwave-assisted direct liquefaction of Ulva prolifera for bio-oil production by acid catalysis. Bioresource Technology, 116:133-139.

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