[1]沈德魁,胡珺,肖睿,等.造纸黑液中木质素的分离与结构表征[J].东南大学学报(自然科学版),2013,43(1):120-124.[doi:10.3969/j.issn.1001-0505.2013.01.023]
 Shen Dekui,Hu Jun,Xiao Rui,et al.Isolation and characterization of lignin in black liquor[J].Journal of Southeast University (Natural Science Edition),2013,43(1):120-124.[doi:10.3969/j.issn.1001-0505.2013.01.023]
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造纸黑液中木质素的分离与结构表征()
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《东南大学学报(自然科学版)》[ISSN:1001-0505/CN:32-1178/N]

卷:
43
期数:
2013年第1期
页码:
120-124
栏目:
化学化工
出版日期:
2013-01-20

文章信息/Info

Title:
Isolation and characterization of lignin in black liquor
作者:
沈德魁12胡珺1肖睿1张会岩1
1 东南大学能源热转换及其过程测控教育部重点试验室, 南京 210096; 2 中国科学院可再生能源与天然气水合物重点试验室, 广州 510640
Author(s):
Shen Dekui12 Hu Jun1 Xiao Rui1 Zhang Huiyan1
1 Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University, Nanjing 210096, China
2 Key Laboratory of Renewable Energy and Gas Hydrate, Chinese Academy of Sciences, Guangzhou 510640, China
关键词:
黑液 木质素 分离 结构
Keywords:
black liquor lignin isolation structure
分类号:
O636.2;TK6
DOI:
10.3969/j.issn.1001-0505.2013.01.023
摘要:
为了综合利用造纸黑液,分别采用H2SO4溶液和H3PO4溶液从黑液中沉淀粗木质素,并分别用苯-乙醇溶液和丙酮溶液对其抽提纯化.考察了采用不同酸沉淀及溶剂抽提对木质素得率的影响,并对黑液木质素进行了元素分析、傅里叶红外光谱分析、13C NMR以及1H NMR等结构表征.实验结果表明:采用不同酸沉淀及溶剂抽提得到的木质素结构相差不大,采用H2SO4沉淀及苯-乙醇抽提方法制备的苯-乙醇木质素得率最高;黑液木质素含有较多的愈创木酚-紫丁香酚单元结构,呈现明显的硬木木质素特征;在苯-乙醇木质素与丙酮木质素中,苯丙烷结构单元经验式分别为C9H12.61O1.1(OCH3)1.43和C9H13.33O2.10(OCH3)1.38,每个C9单元中的β—O—4键仅为0.28和0.27个,β—β键仅为0.15和0.11个;黑液木质素中羟基和羧基数量较磨木木质素丰富.黑液木质素具备多种活性官能团,表现出与磨木木质素不同的结构特征,应用前景广阔.
Abstract:
To utilize the black liquor effectively, crude lignin was precipitated with H2SO4 and H3PO4, and then extracted with benzene-ethanol and acetone for purification, respectively. Effects of different acids and solvents on lignin yield were studied, and the structural characteristics of black liquor lignin were examined by elemental analysis, Fourier transform infrared spectroscopy(FTIR), carbon-13 nuclear magnetic resonance(13C NMR)and proton nuclear magnetic resonance(1H NMR)spectroscopy. The results show that lignins prepared by different methods present no difference on structure, and benzene-ethanol-extracted lignin which is precipitated by H2SO4 and purified with benzene-ethanol gives the highest yield. The lignin presents a guaiacol-syringol structure characteristics assigned to hardwood. The chemical formula of phenyl propane units are estimated to be C9H12.61O1.1(OCH3)1.43 for benzene-ethanol-extracted lignin and C9H13.33O2.10(OCH3)1.38 for acetone-extracted lignin. The benzene-ethanol-extracted lignin and acetone-extracted lignin elucidate β—O—4 bonds as 0.28 and 0.27 and β—β bonds as 0.15 and 0.11 per C9 units, respectively. Moreover, the content of hydroxyl groups and carboxyl groups of black-liquor lignin was greater. Black-liquor lignin with various functionality groups presents an active chemical structure over milled wood lignin, exhibiting its potential utilization as an important feedstock.

参考文献/References:

[1] 蒋挺大. 木质素 [M]. 北京: 化学工业出版社, 2008.
[2] Fengel D, Wegener G W. Chemistry, ultrastructure, reactions [M]. Berlin: Walter de Gruyter Inc., 1984.
[3] Yang Haiping. Characteristics of hemicellulose, cellulose and lignin pyrolysis [J]. Fuel, 2007, 86(12/13): 1781-1788.
[4] Lin S Y, Dence C W. Methods in lignin chemistry [M]. Berlin: Springer-Verlag, 1992.
[5] Lundquist K, Simonson R. Lignin preparations with very low carbohydrate content [J]. Svensk Papperstidn, 1975, 78(11):390.
[6] Baghy M O, Cunningham R L, Maloney R L. Ultraviolet spectral determination of lignin [J]. Tappi Tech Ass Pulp Pap Indus, 1973, 56(4): 162-163.
[7] Mussatto S I, Fernandes M, Roberto I C. Lignin recovery from brewers spent grain black liquor [J]. Carbohydrate Polymers, 2007, 70(2): 218-223.
[8] Sun R, Tomkinson J, Bolton J. Effects of precipitation pH on the physico-chemical properties of the lignins isolated from the black liquor of oil palm empty fruit bunch fibre pulping [J]. Polymer Degradation and Stability, 1999, 63(2): 195-200.
[9] Shen D K. The pyrolytic degradation of wood-derived lignin from pulping process [J]. Bioresource Technology, 2010, 101(15): 6136-6146.
[10] Shen D. The pyrolytic behavior of cellulose in lignocellulosic biomass: a review [J]. RSC Advances, 2011, 1(9): 1641-1660.
[11] Holtman K M. Quantitative 13C NMR characterization of milled wood lignins isolated by different milling techniques [J]. Journal of Wood Chemistry and Technology, 2006, 26(1): 21-34.
[12] 秦特夫. 杉木和-三北-一号杨磨木木质素化学官能团特征的研究[J]. 林业科学, 1999, 35(3): 69-75.
  Qin Tefu. The chemical structures and characteristics of the MWLs of Chinese fir(cunninghamia lanceolata)and polar “sanbei” No. 1(populus nigra×p.simonii)wood [J]. Scientia Silvae Sinicae, 1999, 35(3): 69-75.(in Chinese)
[13] Fukushima R S, Kerley M S. Use of lignin extracted from different plant sources as standards in the spectrophotometric acetyl bromide lignin method [J]. Journal of Agricultural and Food Chemistry, 2011, 59(8): 3505-3509.
[14] Nagy M. Characterization of CO2 precipitated kraft lignin to promote its utilization [J]. Green Chemistry, 2010, 12(1): 31-34.
[15] Adle E. Lignin chemistry—past, present and future [J]. Wood Science and Technology, 1977, 11(3): 169-218.
[16] Froass P M, Ragauskas A J, Jiang J. Chemical structure of residual lignin from kraft pulp [J]. Journal of Wood Chemistry and Technology, 1996, 16(4): 347-365.
[17] Froass P M, Ragauskas A J, Jiang J. Nuclear magnetic resonance studies. 4. analysis of residual lignin after kraft pulping [J]. Ind Eng Chem Res, 1998, 37(8): 3388-3394.
[18] Kosa M. Pyrolysis oils from CO2 precipitated kraft lignin [J]. Green Chemistry, 2011, 13(11): 3196-3202.

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备注/Memo

备注/Memo:
作者简介: 沈德魁(1981—),男,博士,副教授;肖睿(联系人),男,博士,教授,博士生导师, ruixiao@seu.edu.cn.
基金项目: 江苏省高校自然科学基金资助项目(12KJB480005)、中国科学院可再生能源与天然气水合物重点试验室开放基金资助项目.
引文格式: 沈德魁,胡珺,肖睿,等.造纸黑液中木质素的分离与结构表征[J].东南大学学报:自然科学版,2013,43(1):120-124. [doi:10.3969/j.issn.1001-0505.2013.01.023]
更新日期/Last Update: 2013-01-20