基于红外光谱的不同农作物秸秆磨木木质素差异表征
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摘要
木质素是植物细胞壁中主要组分之一,其苯丙烷结构单元的单体结构和连接方式的复杂性直接影响木质素脱除和利用效果,了解不同农作物秸秆中木质素的差异,对提高秸秆的综合利用效率是非常必要的。该文选取代表性棉秆、玉米秸和小麦秆,分别提取磨木木质素,利用傅里叶变换中红外技术对棉秆、玉米秸和小麦秆三类秸秆磨木木质素进行红外表征,分析比较三类秸秆磨木木质素的差异,结果表明:1)三类秸秆磨木木质素G/S相对比值差别不大,并无明显规律;2)三类秸秆磨木木质素中,对羟基结构单元:玉米秸>小麦秆>>棉秆;愈创木基结构单元:棉秆>玉米秸>小麦秆;紫丁香基结构单元:玉米秸>小麦秆>棉秆;3)玉米秸和小麦秆磨木木质素相似度较高,而棉秆磨木木质素则更加接近于木本植物。
As vast agricultural byproduct and an important source of lignocellulosic biomass in China,straws of maize,cotton and wheat are now being developed as renewable energy resources to address a serious energy shortage and environmental issues related to other energy sources.It is necessary to improve the comprehensive utilization efficiency of the three types of straw.Although maize(monocotyledon),cotton(dicotyledon)and wheat(monocotyledon)belong to therophyte herbage from the perspective of phytology,but their straw forms are totally different.For the sake of the difference among them,the utilization cannot be generalized without regard to the effect of chemical composition,in particular the characteristics of lignin.It is composed of phenyl propane monomers connected by the ether and carbon-carbon bonds,containing a variety of active groups.There are three types of phenylpropane,p-hydroxy phenyl,guaiacyl and syringyl,which correspond to hydroxy phenyl lignin(H-lignin),syringyl lignin(S-lignin)and guaiacyl lignin(G-lignin),respectively.Lignin within plants has different shares of the three constitutional units.The heterogeneity of linkage types among the phenyl propane monomers has different effects on the pretreatment for the utilization and removal of lignin.Previous researches have shown that the relative ratio of G-lignin/S-lignin(G/S value)is relevant to the ease or complexity of delignification.Therefore,the higher the ratio,the harder the delignification is.In this paper,three samples of each kind of straw were collected,coarse grinded,degreased,dewaxed,and fine grinded,in sequence.Then the milled wood lignin(MWL)was isolated from the straws of cotton,corn and wheat.After the all procedures above,MWL was studied with FT-IR,by potassium bromide pellet technique.Normalization was conducted with 9 spectra obtained,at the wavelength of 1 506 cm-1(to make A1 506=1)as spectral pretreatment.Then the spectra were compared in 3 aspects:the relative G/S ratio represented by A1 265/A1 329,the identification of lignin types based on plant taxonomy,and the differences and similarities comparing with the MWL from eucalyptus.The results indicate that there is more guaiacyl and less syringyl in the MWL isolated from the samples,the relative ratio of G/S among the three kinds of straws was not significant difference,and no evident regularity is found.Secondly,the identification results based on plant taxonomy show that the MWL from cotton straw is the type of GS1,while that from corn and wheat straw belong to the type of HGS;the content of basic units of lignin in mole percent in these straws have following laws:for H-lignin,corn straw>wheat straw>>cotton straw;for G-lignin,cotton straw>corn straw>wheat straw;for S-lignin,corn straw>wheat straw>cotton straw.Thirdly,the MWL isolated from straw of corn and wheat share the generality of gramineous plants,while the MWL from cotton straw is closer to ligneous plants,which have distinguish peak at 1 265 and 1 226 cm~(-1).
As vast agricultural byproduct and an important source of lignocellulosic biomass in China,straws of maize,cotton and wheat are now being developed as renewable energy resources to address a serious energy shortage and environmental issues related to other energy sources.It is necessary to improve the comprehensive utilization efficiency of the three types of straw.Although maize(monocotyledon),cotton(dicotyledon)and wheat(monocotyledon)belong to therophyte herbage from the perspective of phytology,but their straw forms are totally different.For the sake of the difference among them,the utilization cannot be generalized without regard to the effect of chemical composition,in particular the characteristics of lignin.It is composed of phenyl propane monomers connected by the ether and carbon-carbon bonds,containing a variety of active groups.There are three types of phenylpropane,p-hydroxy phenyl,guaiacyl and syringyl,which correspond to hydroxy phenyl lignin(H-lignin),syringyl lignin(S-lignin)and guaiacyl lignin(G-lignin),respectively.Lignin within plants has different shares of the three constitutional units.The heterogeneity of linkage types among the phenyl propane monomers has different effects on the pretreatment for the utilization and removal of lignin.Previous researches have shown that the relative ratio of G-lignin/S-lignin(G/S value)is relevant to the ease or complexity of delignification.Therefore,the higher the ratio,the harder the delignification is.In this paper,three samples of each kind of straw were collected,coarse grinded,degreased,dewaxed,and fine grinded,in sequence.Then the milled wood lignin(MWL)was isolated from the straws of cotton,corn and wheat.After the all procedures above,MWL was studied with FT-IR,by potassium bromide pellet technique.Normalization was conducted with 9 spectra obtained,at the wavelength of 1 506 cm-1(to make A1 506=1)as spectral pretreatment.Then the spectra were compared in 3 aspects:the relative G/S ratio represented by A1 265/A1 329,the identification of lignin types based on plant taxonomy,and the differences and similarities comparing with the MWL from eucalyptus.The results indicate that there is more guaiacyl and less syringyl in the MWL isolated from the samples,the relative ratio of G/S among the three kinds of straws was not significant difference,and no evident regularity is found.Secondly,the identification results based on plant taxonomy show that the MWL from cotton straw is the type of GS1,while that from corn and wheat straw belong to the type of HGS;the content of basic units of lignin in mole percent in these straws have following laws:for H-lignin,corn straw>wheat straw>>cotton straw;for G-lignin,cotton straw>corn straw>wheat straw;for S-lignin,corn straw>wheat straw>cotton straw.Thirdly,the MWL isolated from straw of corn and wheat share the generality of gramineous plants,while the MWL from cotton straw is closer to ligneous plants,which have distinguish peak at 1 265 and 1 226 cm~(-1).
引文
[1]Li Changzhi,Zhao Xiaochen,Wang Aiqin,et al.Catalytic transformation of lignin for the production of chemicals and fuels[J].Chem Rev,2015,115(21):11559-11624.Doi:10.1021/acs.chemrev.5b00155
[2]Gosselink R J A,Snijder M H B,Kranenbarg A,et al.Characterization and application of Nova fiber lignin[J].Industrial Crops and Products,2004,20(2):191-203.Doi:10.1016/j.indcrop.2004.04.021
[3]陶用珍,管映亭.木质素的化学结构及其应用[J].纤维素科学与技术,2003,11(1):42-55.Tao Yongzhen,Guan Yingting.Study of chemical composition of lignin and its application[J].Journal of Cellulose Science and Technology,2003,11(1):42-45.(in Chinese with English abstract)
[4]蒋挺大.木质素[M].第2版.北京:化学工业出版社,2009.
[5]Rencoret J,Marques G,Gutiérrez A,et al.Isolation and structural characterization of the milled-wood lignin from Paulownia fortunei wood[J].Journal of Agricultural and Food Chemistry,2009,30(1):137-143.Doi:10.1016/j.indcrop.2009.03.004
[6]刘忠,齐宏升.麦草酸催化乙醇法制浆过程中木质素结构的变化[J].天津科技大学学报,2008,23(2):10-13.Liu Zhong,Qi Hongsheng.Configuration transformation of lignin in wheat straw acid-catalytic ethanol pulping process[J].Journal of Tianjin University of Science&Technology,2008,23(2):10-13.(in Chinese with English abstract)
[7]邝仕均.桉树木材性质对其硫酸盐法制浆性能的影响[J].中国造纸,2011,30(12):51-54.Kuang Shijun.Effect of eucalyptus wood properties on its kraft pulping performance[J].China Pulp&Paper,2011,30(12):51-54.(in Chinese with English abstract)
[8]郑秋闿,范晶晶,许凯,等.木质素结构在聚丙烯中抗氧化作用的影响[J].实验室研究与探索,2013,32(6):8-11.Zheng Qiukai,Fan Jingjing,Xu Kai,et al.Effect of lignin structure on antioxidation in polypropylene[J].Research and Exploration In Laboratory,2013,32(6):8-11.(in Chinese with English abstract)
[9]梁文学,邱学青,杨东杰,等.麦草碱木质素的氧化和磺甲基化改性[J].华南理工大学学报:自然科学版,2007,35(5):117-121.Liang Wenxue,Qiu Xueqing,Yang Dongjie,et al.Modificaion of wheat straw alkali lignin by oxidation and sulfomethylation[J].Journal of South China University of Technology:Natural Science Edition,2007,35(5):117-121.(in Chinese with English abstract)
[10]陈方,肖习蓉,陈嘉翔.桉木化机浆制浆过程中木素结构的变化[J].纤维素科学与技术,1996,4(3):30-35.Chen Fang,Xiao Xirong,Chen Jiaxiang.Characterization of protolignin in Eucalyptus CMP[J].Journal of Cellulose Science and Technology,1996,4(3):30-35.(in Chinese with English abstract)
[11]周学飞.麦草木素在臭氧处理中的作用行为[J].纤维素科学与技术,2004,12(4):35-37,56.Zhou Xuefei.Behavior of wheat straw lignin during ozone treatment[J].Journal of Cellulose Science and Technology,2004,12(4):35-37,56.(in Chinese with English abstract)
[12]王勇,邹献武,秦特夫.生物质醇解重质油燃烧动力学研究[J].林产化学与工业,2012,32(1):35-38.Wang Yong,Zou Xianwu,Qin Tefu.Combustion kinetics analysis of fuel oil derived from biomass liquefaction with 1-octanol[J].Chemistry and Industry of Forest Products,2012,32(1):35-38.(in Chinese with English abstract)
[13]宋湛谦,Han J S,Rowell R M.花旗松纤维和槿麻纤维的硝酸化学改性[J].林产化学与工业,1999,19(1):1-5.Song Zhanqian,Han J S,Rowell R M.Chemical modification of douglas fir and kenaf fibers by nitric acid[J].Chemistry and Industry of Forest Products,1999,19(1):1-5.(in Chinese with English abstract)
[14]娄瑞,武书彬,吕高金,等.草本类木素的化学结构与热化学性质[J].华南理工大学学报:自然科学版,2010,38(8):1-6.Lou Rui,Wu Shubin,LǜGaojin,et al.Chemical structure and thermochemical properties of lignin from herbaceous plant[J].Journal of South China University of Technology:Natural Science Edition,2010,38(8):1-6.(in Chinese with English abstract)
[15]金永灿,刘军,杨益琴,等.草浆废液制备生物质固沙材料及其在植被恢复上的应用(系列报道之二)生物质固沙材料的结构特性[J].中华纸业,2006,27(10):75-78.Jin Yongcan,Liu Jun,Yang Yiqin,et al.Preparation of biomass sand stabilization material from straw pulp effluent and its application on vegetation restoration(II):Structural characteristics of biomass sand stabilization material[J].China Pulp&Paper Industry,2006,27(10):75-78.(in Chinese with English abstract)
[16]徐汉卿等主编.植物学[M].北京:北京农业大学出版社,1994.
[17]李忠正.可再生生物质资源--木质素的研究[J].南京林业大学学报:自然科学版,2012,36(1):1-7.Li Zhongzheng.Research on renewable biomass resource:Lignin[J].Journal of Nanjing Forestry University:Natural Science Edition,2012,36(1):1-7.(in Chinese with English abstract)
[18]John Ralph,G?staBrunow,Philip J Harris,et al.Lignification:Are lignins biosynthesized via simple combinatorial chemistry or via proteinaceous control and template replication?[J].Recent Advances in Polyphenol Research,2008,1:36-66.Doi:10.1002/9781444302400.ch2
[19]Priscila Maziero,Mario de Oliveira Neto,Douglas Machado,et al.Structural features of lignin obtained at different alkaline oxidation conditions from sugarcane bagasse[J].Industrial Crops and Products,2012,35(1):61-69.Doi:10.1016/j.indcrop.2011.06.008
[20]Brownell H H.Isolation of milled lignin and lignin carbohydrate complex[J].TAPPI,1965,48:513-518.
[21]Anderson Guerra,Ilari Filpponen,Lucian A Lucia,et al.Comparative evaluation of three lignin isolation protocols for various wood species[J].Journal of Agricultural and Food Chemistry,2006,54(26):9696-9705.Doi:10.1021/jf062433c
[22]Faix O.Classification of lignins from different botanical origins by FT-IR spectroscopy[J].Holzforschung,1991,45(Supp.1):21-28.Doi:10.1515/hfsg.1991.45.s1.21
[23]Rumana Rana,Rosemarie Langenfeld-Heyser,Reiner Finkeldey,et al.FTIR spectroscopy,chemical and histochemical characterisation of wood and lignin of five tropical timber wood species of the family of Dipterocarpaceae[J].Wood Science and Technology,2009,44(2):225-242.Doi:10.1007/s00226-009-0281-2
[24]陈方,陈嘉翔.桉木木素的付立叶变换红外光谱研究[J].纤维素科学与技术,1994,2(2):14-20.Chen Fang,Chen Jiaxiang.FTIR study of lignin from Eucalyptus[J].Journal of Cellulose Science and Technology,1994,2(2):14-20.(in Chinese with English abstract)
[25]邸明伟.生物质材料现代分析技术[M].北京:化学工业出版社,2010.
[26]Sun R,Sun X F,Wang S Q,et al.Ester and ether linkages between hydroxycinnamic acids and lignins from wheat,rice,rye,and barley straws,maize stems,and fast-growing poplar wood[J].Industrial Crops and Products,2002,15(3):179-188.Doi:10.1016/S0926-6690(01)00112-1
[27]Li L,Zhou Y,Cheng X,et al.Combinatorial modification of multiple lignin traits in trees through multigene cotransformation[J].Proceedings of the National Academy of Science of the United States of America,2003,100(8):4939-4944.Doi:10.1073/pnas.0831166100
[28]Antonovic A,Jambrekovic V,Franjic J,et al.Influence of sampling location on content and chemical composition of the beech native lignin(Fagus sylvatica L)[J].Periodicum Biologorum,2010,112(3),327-332.
[2]Gosselink R J A,Snijder M H B,Kranenbarg A,et al.Characterization and application of Nova fiber lignin[J].Industrial Crops and Products,2004,20(2):191-203.Doi:10.1016/j.indcrop.2004.04.021
[3]陶用珍,管映亭.木质素的化学结构及其应用[J].纤维素科学与技术,2003,11(1):42-55.Tao Yongzhen,Guan Yingting.Study of chemical composition of lignin and its application[J].Journal of Cellulose Science and Technology,2003,11(1):42-45.(in Chinese with English abstract)
[4]蒋挺大.木质素[M].第2版.北京:化学工业出版社,2009.
[5]Rencoret J,Marques G,Gutiérrez A,et al.Isolation and structural characterization of the milled-wood lignin from Paulownia fortunei wood[J].Journal of Agricultural and Food Chemistry,2009,30(1):137-143.Doi:10.1016/j.indcrop.2009.03.004
[6]刘忠,齐宏升.麦草酸催化乙醇法制浆过程中木质素结构的变化[J].天津科技大学学报,2008,23(2):10-13.Liu Zhong,Qi Hongsheng.Configuration transformation of lignin in wheat straw acid-catalytic ethanol pulping process[J].Journal of Tianjin University of Science&Technology,2008,23(2):10-13.(in Chinese with English abstract)
[7]邝仕均.桉树木材性质对其硫酸盐法制浆性能的影响[J].中国造纸,2011,30(12):51-54.Kuang Shijun.Effect of eucalyptus wood properties on its kraft pulping performance[J].China Pulp&Paper,2011,30(12):51-54.(in Chinese with English abstract)
[8]郑秋闿,范晶晶,许凯,等.木质素结构在聚丙烯中抗氧化作用的影响[J].实验室研究与探索,2013,32(6):8-11.Zheng Qiukai,Fan Jingjing,Xu Kai,et al.Effect of lignin structure on antioxidation in polypropylene[J].Research and Exploration In Laboratory,2013,32(6):8-11.(in Chinese with English abstract)
[9]梁文学,邱学青,杨东杰,等.麦草碱木质素的氧化和磺甲基化改性[J].华南理工大学学报:自然科学版,2007,35(5):117-121.Liang Wenxue,Qiu Xueqing,Yang Dongjie,et al.Modificaion of wheat straw alkali lignin by oxidation and sulfomethylation[J].Journal of South China University of Technology:Natural Science Edition,2007,35(5):117-121.(in Chinese with English abstract)
[10]陈方,肖习蓉,陈嘉翔.桉木化机浆制浆过程中木素结构的变化[J].纤维素科学与技术,1996,4(3):30-35.Chen Fang,Xiao Xirong,Chen Jiaxiang.Characterization of protolignin in Eucalyptus CMP[J].Journal of Cellulose Science and Technology,1996,4(3):30-35.(in Chinese with English abstract)
[11]周学飞.麦草木素在臭氧处理中的作用行为[J].纤维素科学与技术,2004,12(4):35-37,56.Zhou Xuefei.Behavior of wheat straw lignin during ozone treatment[J].Journal of Cellulose Science and Technology,2004,12(4):35-37,56.(in Chinese with English abstract)
[12]王勇,邹献武,秦特夫.生物质醇解重质油燃烧动力学研究[J].林产化学与工业,2012,32(1):35-38.Wang Yong,Zou Xianwu,Qin Tefu.Combustion kinetics analysis of fuel oil derived from biomass liquefaction with 1-octanol[J].Chemistry and Industry of Forest Products,2012,32(1):35-38.(in Chinese with English abstract)
[13]宋湛谦,Han J S,Rowell R M.花旗松纤维和槿麻纤维的硝酸化学改性[J].林产化学与工业,1999,19(1):1-5.Song Zhanqian,Han J S,Rowell R M.Chemical modification of douglas fir and kenaf fibers by nitric acid[J].Chemistry and Industry of Forest Products,1999,19(1):1-5.(in Chinese with English abstract)
[14]娄瑞,武书彬,吕高金,等.草本类木素的化学结构与热化学性质[J].华南理工大学学报:自然科学版,2010,38(8):1-6.Lou Rui,Wu Shubin,LǜGaojin,et al.Chemical structure and thermochemical properties of lignin from herbaceous plant[J].Journal of South China University of Technology:Natural Science Edition,2010,38(8):1-6.(in Chinese with English abstract)
[15]金永灿,刘军,杨益琴,等.草浆废液制备生物质固沙材料及其在植被恢复上的应用(系列报道之二)生物质固沙材料的结构特性[J].中华纸业,2006,27(10):75-78.Jin Yongcan,Liu Jun,Yang Yiqin,et al.Preparation of biomass sand stabilization material from straw pulp effluent and its application on vegetation restoration(II):Structural characteristics of biomass sand stabilization material[J].China Pulp&Paper Industry,2006,27(10):75-78.(in Chinese with English abstract)
[16]徐汉卿等主编.植物学[M].北京:北京农业大学出版社,1994.
[17]李忠正.可再生生物质资源--木质素的研究[J].南京林业大学学报:自然科学版,2012,36(1):1-7.Li Zhongzheng.Research on renewable biomass resource:Lignin[J].Journal of Nanjing Forestry University:Natural Science Edition,2012,36(1):1-7.(in Chinese with English abstract)
[18]John Ralph,G?staBrunow,Philip J Harris,et al.Lignification:Are lignins biosynthesized via simple combinatorial chemistry or via proteinaceous control and template replication?[J].Recent Advances in Polyphenol Research,2008,1:36-66.Doi:10.1002/9781444302400.ch2
[19]Priscila Maziero,Mario de Oliveira Neto,Douglas Machado,et al.Structural features of lignin obtained at different alkaline oxidation conditions from sugarcane bagasse[J].Industrial Crops and Products,2012,35(1):61-69.Doi:10.1016/j.indcrop.2011.06.008
[20]Brownell H H.Isolation of milled lignin and lignin carbohydrate complex[J].TAPPI,1965,48:513-518.
[21]Anderson Guerra,Ilari Filpponen,Lucian A Lucia,et al.Comparative evaluation of three lignin isolation protocols for various wood species[J].Journal of Agricultural and Food Chemistry,2006,54(26):9696-9705.Doi:10.1021/jf062433c
[22]Faix O.Classification of lignins from different botanical origins by FT-IR spectroscopy[J].Holzforschung,1991,45(Supp.1):21-28.Doi:10.1515/hfsg.1991.45.s1.21
[23]Rumana Rana,Rosemarie Langenfeld-Heyser,Reiner Finkeldey,et al.FTIR spectroscopy,chemical and histochemical characterisation of wood and lignin of five tropical timber wood species of the family of Dipterocarpaceae[J].Wood Science and Technology,2009,44(2):225-242.Doi:10.1007/s00226-009-0281-2
[24]陈方,陈嘉翔.桉木木素的付立叶变换红外光谱研究[J].纤维素科学与技术,1994,2(2):14-20.Chen Fang,Chen Jiaxiang.FTIR study of lignin from Eucalyptus[J].Journal of Cellulose Science and Technology,1994,2(2):14-20.(in Chinese with English abstract)
[25]邸明伟.生物质材料现代分析技术[M].北京:化学工业出版社,2010.
[26]Sun R,Sun X F,Wang S Q,et al.Ester and ether linkages between hydroxycinnamic acids and lignins from wheat,rice,rye,and barley straws,maize stems,and fast-growing poplar wood[J].Industrial Crops and Products,2002,15(3):179-188.Doi:10.1016/S0926-6690(01)00112-1
[27]Li L,Zhou Y,Cheng X,et al.Combinatorial modification of multiple lignin traits in trees through multigene cotransformation[J].Proceedings of the National Academy of Science of the United States of America,2003,100(8):4939-4944.Doi:10.1073/pnas.0831166100
[28]Antonovic A,Jambrekovic V,Franjic J,et al.Influence of sampling location on content and chemical composition of the beech native lignin(Fagus sylvatica L)[J].Periodicum Biologorum,2010,112(3),327-332.