伊敏褐煤腐植酸结构特征及其分子模型构建  

Structural characterization and molecular model construction ofhumic acid from Yimin lignite

作　　者：赵云刚 李美芬 崔曦[4,5] 赵月圆 王小令 邵燕 穆瑞峰 胡子晗 ZHAO Yungang;LI Meifen;CUI Xi;ZHAO Yueyuan;WANG Xiaoling;SHAO Yan;MU Ruifeng;HU Zihan(China Coal Research Institute Corporation Ltd.,Beijing 100013,China;National Energy Technology&Equipment Laboratory of Coal Utilization and Emission Control,Beijing 100013,China;Beijing Key Laboratory of Coal-based Carbon Materials,Beijing 100013,China;College of MiningEngineering,Taiyuan Universiy of Technology,Taiyuan 030024,China;Shanxi Key Laboratory of Coal and Coal Measure Gas Geology,Taiyuan Universiy of Technology,Taiyuan 030024,China;Material Cycles Division,National Institute for Environmental Studies,Tsukuba,Ibaraki 305-8506,Japan;College of Geoscience&Surveying Engineering,China University of Mining&Technology-Beijing,Beijing 100083,China)

机构地区：[1]煤炭科学技术研究院有限公司,北京100013 [2]国家能源煤炭高效利用与节能减排技术装备重点实验室,北京100013 [3]煤基节能环保炭材料北京市重点实验室,北京100013 [4]太原理工大学矿业工程学院,山西太原030024 [5]太原理工大学煤与煤系气地质山西省重点实验室,山西太原030024 [6]日本国立环境研究所材料循环事业部,日本筑波305-8506 [7]中国矿业大学(北京)地球科学与测绘工程学院,北京100083

出　　处：《煤质技术》2024年第3期1-12,共12页Coal Quality Technology

基　　金：国家自然科学基金——山西煤基低碳联合基金重点资助项目(U1910204);煤炭科学技术研究院有限公司科技发展基金资助项目(2023CX-Ⅱ-04)。

摘　　要：从褐煤中提取腐植酸对于实现褐煤的清洁高效利用具有重要的意义,而探究蒙东地区褐煤腐植酸结构并构建相应的分子模型对于该地区褐煤应用具有广泛的指导作用。采用碱溶酸析法提取蒙东伊敏褐煤的腐植酸,通过采用X射线衍射、^(13)C核磁共振以及X射线光电子能谱等方法对腐植酸的结构特征进行全面表征。结果表明:伊敏褐煤腐植酸中的芳香结构是基础,而脂肪结构主要以交联键以及侧链形式存在;褐煤腐植酸中的芳香团簇尺寸较小,芳香层间距相对较大,且呈现无序排列。根据结构表征相关参数,重构了具有代表性的中国蒙东伊敏褐煤腐植酸分子模型。所构建的伊敏褐煤腐植酸分子结构模型计算数据与实验数据大体吻合,能够充分反映伊敏褐煤腐植酸的化学结构特点。模型中芳香碳结构主要以苯、萘环的形式呈现,少量以菲环形式的存在;脂肪碳主要以较短的侧链和脂肪环形式存在,起到连接芳香基本结构单元的作用。氧元素主要以羧基和酯等O—C=O形式存在,同时还包括一定量的酮、醛、醌、酚、醇以及醚氧,其中羰基C O和醚氧具有交联作用。氮元素则主要以吡咯环的形式存在,并伴有少量的吡啶环和季氮。与西南地区云南褐煤腐植酸结构相比,伊敏褐煤中的芳香碳含量更高且吡咯含氮官能团所占比例也更大,并呈现出一定的地区差异性。Extraction of humic acid from lignite is of great significance in realizing the clean and efficient utilization of lignite.Exploring the structure of lignite humic acid and constructing the corresponding structural model in the eastern region of Inner Mongolia provides extensive guidance for the application of lignite in this region.In this paper,the humic acid of lignite from Yimin in eastern Inner Mongolia was extracted by alkali dissolution and acid precipitation method.The structural characteristics of humic acid were comprehensively analyzed using X-ray diffraction,^(13)C nuclear magnetic resonance,and X-ray photoelectron spectroscopy.The results showed that the aromatic structure forms the basis of humic acid from Yimin lignite,while the aliphatic structure primarily exists in the form of cross-linking bonds and side chains.The aromatic clusters in lignite humic acid were relatively small in size,with a significant spacing between aromatic layers and a disordered arrangement.Based on the parameters related to structural characterization,a representative structural model of lignite humic acid from Yimin,East Inner Mongolia,China,was reconstructed.The calculated data of the structural model of humic acid from Yimin lignite is in good agreement with the experimental data and can fully reflect the chemical structure of humic acid from Yimin lignite.In the model,the aromatic carbons are primarily in the form of benzene and naphthalene rings,with a small amount of phenanthrene rings.The aliphatic carbons mainly consist of shorter side chains and aliphatic rings,serving to connect the fundamental aromatic units.Oxygen mainly exists in the form of O—C=O,such as carboxyl groups and esters.It also includes a certain amount of ketones,aldehydes,quinones,phenols,alcohols,and ether oxygen.Carbonyl C=O and ether oxygen have a cross-linking effect.Nitrogen primarily exists in the form of a pyrrole ring,with a small amount found in pyridine rings and quaternary nitrogen.The samples in this study have a higher aromatic ca

关 键 词：腐植酸 结构特征 分子模型 伊敏褐煤 芳香结构 脂肪碳 吡咯环 交联键 

分 类 号：TQ530[化学工程—煤化学工程]