宁东红石湾煤大分子模型构建及量子化学计算

doi:10.11949/j.issn.0438-1157.20180013

化工学报 ›› 2018, Vol. 69 ›› Issue (5): 2208-2216.DOI: 10.11949/j.issn.0438-1157.20180013

宁东红石湾煤大分子模型构建及量子化学计算

李壮楣^1,2, 王艳美^1,2, 李平^1,2, 李和平^1,2, 白红存^1,2, 郭庆杰^1,2

1. 省部共建煤炭高效利用与绿色化工国家重点实验室(宁夏大学), 宁夏银川 750021;
2. 宁夏大学化学化工学院, 宁夏银川 750021

收稿日期:2018-01-05 修回日期:2018-01-10 出版日期:2018-05-05 发布日期:2018-05-05
通讯作者: 白红存
基金资助:
宁夏自然科学基金面上项目（NZ17008）；宁夏科技厅对外交流合作项目（2015年）；宁夏高等学校一流学科建设项目（化学工程与技术学科，NXYLXK2017A04）；宁夏大学研究生创新项目（GIP2017029）。

Macromolecular model construction and quantum chemical calculation of Ningdong Hongshiwan coal

LI Zhuangmei^1,2, WANG Yanmei^1,2, LI Ping^1,2, LI Heping^1,2, BAI Hongcun^1,2, GUO Qingjie^1,2

1. State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China;
2. College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China

Received:2018-01-05 Revised:2018-01-10 Online:2018-05-05 Published:2018-05-05
Supported by:
supported by the Natural Science Foundation of Ningxia (NZ17008), the External Cooperation Program of Science and Technology Department of Ningxia (2015), the National Academic Subjects Construction Project of Ningxia (Chemical Engineering and Technology, NXYLXK2017A04) and the Innovation Program for Graduate Students of Ningxia University (GIP2017029).

摘要/Abstract

摘要：

使用工业分析、元素分析、固体核磁（¹³C NMR）、X射线光电子能谱（XPS）、傅里叶变换红外光谱（FT-IR）对宁东红石湾（HSW）煤样进行表征，获得煤样中元素赋存的种类、价态、化学键环境等物质微观结构的关键参数。结果表明HSW煤结构以芳香族为主，占75.96%，桥接芳碳与周碳比为0.315，可知其结构中以萘为主，苯和蒽为辅。氧原子主要以醚氧基（C—O）、羰基（C=O）和羧基（—COO）的形式存在，其中C—O占53.57%。氮原子以吡啶和吡咯的形式存在。苯环的连接方式以三、四取代为主，分别占47.77%、32.97%，脂肪族中环烷烃或脂肪烃—CH₃占优势。确定HSW煤的分子式为C₂₂₁H₁₄₈O₂₈N₂，分子量为3142.32。在此基础上结合计算机辅助实现了二维和三维大分子模型构筑。应用量子化学计算对HSW煤大分子模型进行了优化及核磁共振、红外光谱模拟，验证了所建模型的合理性。最终实现了HSW煤的微观分子结构的实验与量子化学描述。

关键词: 煤, 模型, 计算化学, 结构优化, 分子模拟, 光谱模拟

Abstract:

Hongshiwan (HSW) coal from Ningdong China was characterized to determine key microstructural parameters of materials, such as elements, valence and chemical bonding, with proximate and ultimate analyses, solid state ¹³C nuclear magnetic resonance (¹³C NMR), X ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). The results revealed that main structure of HSW coal was 75.96%(mass) aromatic skeleton and 0.315 ratio of aromatic bridge carbon to aromatic peripheral carbon, indicating more naphthalene than benzene and anthracene in coal. Oxygen predominantly presented in the form of ether (C-O), carbonyl (C=O) and carboxyl (-COO), which C-O was accounted for 53.57%. Nitrogen presented in the form of pyridine and pyrrole. Tri-and tetra-substituents were mainly located on benzene ring at 47.77% and 32.97%, respectively. Methyl (-CH₃) group was predominant in cyclic and aliphatic hydrocarbons. Thus, coal molecular formula was defined as C₂₂₁H₁₄₈O₂₈N₂ with molecular weight of 3142.32. Based on these results, macromolecular 2D and 3D model of HSW coal was built with computer-aided modelling. The model was optimized and further verified by FT-IR and ¹³C NMR spectra simulation by quantum chemical calculations. Therefore, molecular microstructures of HSW coal have been depicted from both experimental and quantum chemical approaches.

Key words: coal, model, computational chemistry, structural optimization, molecular simulation, spectral simulation

中图分类号:

TQ530

李壮楣, 王艳美, 李平, 李和平, 白红存, 郭庆杰. 宁东红石湾煤大分子模型构建及量子化学计算[J]. 化工学报, 2018, 69(5): 2208-2216.

LI Zhuangmei, WANG Yanmei, LI Ping, LI Heping, BAI Hongcun, GUO Qingjie. Macromolecular model construction and quantum chemical calculation of Ningdong Hongshiwan coal[J]. CIESC Journal, 2018, 69(5): 2208-2216.

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宁东红石湾煤大分子模型构建及量子化学计算

Macromolecular model construction and quantum chemical calculation of Ningdong Hongshiwan coal

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