工业碱木素的纯化分级及其氨氧化研究
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摘要
利用酸析法纯化工业碱木素得到纯化碱木素,然后采用乙醇溶解分级的方法将纯化碱木素分级为不同相对分子质量的3个级分,各级分的质均相对分子质量分别为2194、2294、4237;并利用氧化剂和氨化剂使纯化碱木素及各级分发生氨氧化反应。通过傅里叶变换红外光谱仪、凯氏定氮、元素分析等方法对氨氧化前后的纯化碱木素和各级分的结构变化、氮含量进行了表征,探究不同因素对纯化碱木素氨氧化反应的影响。结果表明,纯化碱木素氨氧化反应的最佳条件为:纯化碱木素用量10%,氨水用量30%,H_2O_2用量20%,反应温度45℃,反应时间1. 5 h。在最佳氨氧化反应条件下,质均相对分子质量低的级分1的氨氧化产物C∶N数值较低,总氮含量较高(可达13. 06%),适宜用作肥料。
The industrial alkaline lignin was purified by acid precipitation and classified into fractions of different molecular weights by fractional dissolution with ethanol,then it was carried out oxiammonolysis reaction with clean oxidants and ammonizators. FT-IR,the Kjeldahl and elemental analysis methods were used to characterize the structural changes of different fractions,structural changes after oxiammonolysis and nitrogen content of purified alkaline lignin,which were helped to research the effects of different factors on the oxiammonolysis. The results showed that the optimal reaction conditions were as followes,10% alkaline lignin concentration,30% ammonia charge,20% hydrogen peroxide dosage,45℃ reaction temperature,1. 5 h reaction time. The nitrogen content after the oxiammonolysis under the operating conditions increased significantly,and the ratio of carbon to nitrogen of the purified alkaline lignin decreased as the molecular weight decreased,which could be used as fertilizer.
The industrial alkaline lignin was purified by acid precipitation and classified into fractions of different molecular weights by fractional dissolution with ethanol,then it was carried out oxiammonolysis reaction with clean oxidants and ammonizators. FT-IR,the Kjeldahl and elemental analysis methods were used to characterize the structural changes of different fractions,structural changes after oxiammonolysis and nitrogen content of purified alkaline lignin,which were helped to research the effects of different factors on the oxiammonolysis. The results showed that the optimal reaction conditions were as followes,10% alkaline lignin concentration,30% ammonia charge,20% hydrogen peroxide dosage,45℃ reaction temperature,1. 5 h reaction time. The nitrogen content after the oxiammonolysis under the operating conditions increased significantly,and the ratio of carbon to nitrogen of the purified alkaline lignin decreased as the molecular weight decreased,which could be used as fertilizer.
引文
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[16]Tian Zhen,Qiu Xue-qing,Wang Xiao-dong.Progressin studying the properties and application alkali lignin[J].Fine Chemicals,2001,18(2):63.田震,邱学青,王晓东.碱木素性能及应用研究进展[J].精细化工,2001,18(2):63.
[17]Wang Xiao-hong,Ma Yu-hua,Liu Jing,et al.Aminatingmodifition of lignin[J].China Pulp&Paper Industry,2010,29(6):42-44.王晓红,马玉花,刘静,等.木质素的胺化改性[J].中华纸业,2010,29(6):42.
[18]Sun Yong-chang.Efficient Separation and Structural Characterization of Lignin,and Lignin Degradation in Ionic Liquid-based Systems[D].Beijing:Beijing Forestry University,2014.孙永昌.木质素高效分离、表征结构及基于离子液体的降解机理研究[D].北京:北京林业大学,2014.
[2]Cao Ling,Quan Jin-ying,Li Zhong-zheng.A study on the structure of ammoxidative lignin[J].Journal of Nanjing Forestry University,1998,22(2):66.曹玲,全金英,李忠正.氧化氨解木质素化学结构的研究[J].南京林业大学学报,1998,22(2):66.
[3]Wang Guan-hua,Chen Hong-zhang.Lignin classification method and its effect on product performance[J].The biotechnology industry,2015,(5):14.王冠华,陈洪章.木质素分级方式及其对产品性能的影响[J].生物产业技术,2015,(5):14.
[4]Wang Guan-hua.Fractionation of lignin from steam-exploded corn stalk and lignin-based materials preparation[D].Beijing:University of Chinese Academy of Sciences,2015.王冠华.汽爆秸秆木质素分级方式及其材料的制备[D].北京:中国科学院大学,2015.
[5]Jiang Qi-pei,Zhang Xiao-yong,Li Zuo-hu.Study on ammoxidation of straw-pulp alkaline lignin by hydrogen peroxide to slow-release fertilizer[J].Chinese Journal of Environmental Engineering,2009,3(2):281.江启沛,张小勇,李佐虎.草浆碱木素过氧化氢氧化氨解制备氨化木质素缓释肥料的研究[J].环境工程学报,2009,3(2):281.
[6]Qiu Xue-qing,Li Hao,Deng Yong-hong,et al.The acetylation of alkali lignin and Its use for spherical micelles preparation[J].Acta Polymerica Sinica,2014,(11):1457.邱学青,李浩,邓永红,等.碱木质素的乙酰化及其球形胶束的制备[J].高分子学报,2014,(11):1457.
[7]Ren Xue-yong,Cai Hong-zhen,Chang Jian-min,et al.TG-FTIRStudy on the Pyrolysis Properties of Lignin from Different Kinds of Woody Biomass[J].Paper and Biomaterials,2018,3(2):2.
[8]Xue Jing-wen,Li Zhong-zheng,Tai Die-sheng.Study on oxidationammonolysis reaction of alkali lignin[J].Journal of Cellulose Science and Technology,2000,8(3):21.薛菁雯,李忠正,邰瓞生.工业木质素氧化氨解反应研究[J].纤维素科学与技术,2000,8(3):21.
[9]LI Yuanyuan,WANG Chuangui,ZHANG Shuangyan.Extraction and Characterization of Lignin from Kraft Pulping Black Liquor of Eucalyptus[J].China Pulp&Paper,2017,36(10):19.李媛媛,王传贵,张双燕.桉木硫酸盐法制浆黑液木素提取与表征[J].中国造纸,2017,36(10):19.
[10]ZHOU Lichun,PING Qingwei,ZHAO Lijun,et al.Study on Purification of the Ethanol Lignin[J].China Pulp&Paper,2017,36(2):30.周立春,平清伟,赵丽君,等.乙醇木素的提纯研究[J].中国造纸,2017,36(2):30.
[11]Wang Xiao-hong,Chen Wen-jin,Zeng Xiang-qin.Aminatemodifition of lignin[J].Journal of Guizhou University of Technology,2000,29(3):65.王晓红,陈文瑾,曾祥钦.木质素的胺化改性[J].贵州工业大学学报,2000,29(3):65.
[12]Zhou Qiang,Chen Zhonghao.Chemical Properties of the Fractionated Compounds from Wheat Straw Alkail Lignin[J].Transactions of China Pulp and Paper,1998,13(6):1.周强,陈中豪.麦草碱木素级分的官能团研究[J].中国造纸学报,1998,13(6):1.
[13]Lapierre C.Sructural investigation of kraft lignins transformed vai oxo-ammoniation to potential nitrogenous fertilizers[J].Holzforschung,1994,(48):63.
[14]Jin Yong-can,Quan Jin-ying,Wang Yue-qiu,et al.Oxiammonolysis of wheat straw alkaline lignin by hydroperoxide II.The effect of oxiammonolysis on main functional groups[J].Journal of Cellulose Science and Technology,2001,9(4):21.金永灿,全金英,王悦球,等.麦草碱木质素的过氧化氢氨解II.氧化氨解对木质素主要官能团的影响[J].纤维素科学与技术,2001,9(4):21.
[15]Ramirez F,Varela G,Delgado E,et al.Reactions characterization and uptake of ammoxidized kraft lignin labeled with 15N[J].Bioresource Technology,2007,98(7):1494.
[16]Tian Zhen,Qiu Xue-qing,Wang Xiao-dong.Progressin studying the properties and application alkali lignin[J].Fine Chemicals,2001,18(2):63.田震,邱学青,王晓东.碱木素性能及应用研究进展[J].精细化工,2001,18(2):63.
[17]Wang Xiao-hong,Ma Yu-hua,Liu Jing,et al.Aminatingmodifition of lignin[J].China Pulp&Paper Industry,2010,29(6):42-44.王晓红,马玉花,刘静,等.木质素的胺化改性[J].中华纸业,2010,29(6):42.
[18]Sun Yong-chang.Efficient Separation and Structural Characterization of Lignin,and Lignin Degradation in Ionic Liquid-based Systems[D].Beijing:Beijing Forestry University,2014.孙永昌.木质素高效分离、表征结构及基于离子液体的降解机理研究[D].北京:北京林业大学,2014.