山西高硫气肥煤结构表征与分子模型构建

doi:10.3964/j.issn.1000-0593(2020)11-3373-06

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摘要：气肥煤是炼焦煤的主要煤种之一，研究高硫气肥煤的结构并构建分子结构单元模型，对气肥煤脱硫提质，优化炼焦配煤，节约优质炼焦煤资源具有重要意义。选择山西高阳矿区高硫气肥煤，利用FTIR，¹³C CP/MAS-NMR，XPS等测试分析方法表征煤中碳、氧、氮、硫赋存特征，结合煤质分析结果，计算芳香结构、脂肪结构和杂原子结构参数，并构建高阳高硫气肥煤分子结构单元模型。研究结果表明：与芳环上π电子形成的羟基 π 氢键是高阳高硫气肥煤最主要的羟基结构，占比为73.20%，羟基自缔合氢键、醚氧键与羟基形成的氢键含量较高，占羟基总量的24.38%，游离羟基含量仅占2.42%，煤中缔合结构以多聚体形式为主。含氧官能团主要以共轭羰基和酚羟基的形式存在，芳基醚和羧基含量较少。亚甲基是最主要的脂肪烃结构，占比为41.85%，甲基、次甲基占比分别为29.86和28.29%。芳香烃结构主要有苯环五取代、苯环三取代和苯环四取代三种形式，占比分别为41.42%，30.65%和19.82%。芳氢率和芳碳率分别为0.34～0.35和0.73～0.77，芳核平均结构尺寸X_b为0.43。煤中噻吩、（亚）砜、硫醇（醚）和无机硫含量分别为35.90%，27.61%，18.40%和18.09%。氮主要以吡啶和吡咯结构存在，质子化吡啶和氮氧化物较少。通过对煤结构的表征，设计分子结构单元中有芳香烃碳原子118个，羧基和羰基共5个，脂肪烃碳原子35个，氧、硫、氮原子各8、2、2个；根据煤中杂原子结构解析结果，确定分子结构模型单元中包含噻吩、亚砜、吡啶、吡咯、酚羟基、醚氧键等官能团。以此研究为基础构建分子式为C₁₆₅H₁₂₈O₈N₂S₂的高阳高硫气肥煤分子结构单元模型。

关键词：高硫气肥煤；FTIR；¹³C CP/MAS-NMR；XPS；分子模型

Abstract：Gas-fat coal is one of the main coal types of coking coal. To study the structure of high sulfur gas fat coal and construct a molecular structural unit model is of great significance for desulfurization and upgrading, optimizing coking coal blending and saving high quality coking coal resources. The high sulfur gas-fat coal in Gaoyang mining area in Shanxi was selected. Its carbon, oxygen, nitrogen and sulfur structural characteristics were characterized by FTIR, ¹³C CP/MAS-NMR and XPS. The molecular structure unit model of Gaoyang high sulfur gas-fat coal was constructed by combining the results of coal quality analysis, calculate aromatic structure, fat structure and hetero atom structure parameters. The results show that the hydroxy π hydrogen bond formed by π electrons on the aromatic ring is the most important hydroxy structure of Gaoyang high sulfur gas fat coal, accounting for 73.20%. Hydroxyl self-association hydrogen bond, ether oxygen bond and hydroxyl group form a high hydrogen bond content, accounting for 24.38% of the total hydroxyl groups. The free hydroxyl content is only 2.42%, and the association structure in coal is mainly in the form of the multimer. Conjugated carbonyl and phenolic hydroxyl are mainly forms of the oxygen containing functional groups. The aryl ether and carboxyl groups are low. Methylene is the most important aliphatic hydrocarbon structure. Accounting for 41.85%. The proportion of methyl and methine groups was 29.86 and 28.29% respectively. The aromatic hydrocarbon structure mainly has three forms of benzene ring penta-substituted, benzene ring tri-substituted and benzene ring tetra-substituted, accounting for 41.42%, 30.65% and 19.82%, respectively. The aromatic hydrogen ratio and the aromatic carbon ratio is 0.34～0.35 and 0.73～0.77 respectively. The average structure size of the aromatic nucleus X_b was 0.43. The contents of thiophene, (sub)sulfone, thioether (thiol) and inorganic sulfur in coal is 35.90%, 27.61%, 18.40% and 18.09% respectively. Nitrogen is mainly present in the structure of pyridine and pyrrole, with less protonated pyridine and nitrogen oxides. The molecular structure unit has 118 aromatic carbon atoms, 5 carboxyl groups and carbonyl groups, 35 aliphatic hydrocarbon atoms, and 8, 2, 2 oxygen, sulfur and nitrogen atoms. According to the analysis of the structure of heteroatoms in coal. It is determined that the molecular structure model unit contains functional groups such as thiophene, sulfoxide, pyridine, pyrrole, phenolic hydroxyl group, ether oxygen bond and the like. The molecular structure unit model of high-yang high-sulfur gas fat coal with molecular formula C₁₆₅H₁₂₈O₈N₂S₂ was constructed.

Key words：High sulfur gas-fat coal; FTIR; ¹³C CP/MAS-NMR; XPS; Molecular model

收稿日期: 2019-10-27 修订日期: 2020-02-12

中图分类号:

TQ536.9

基金资助: 安徽省自然科学基金项目(2008085ME144)，中国博士后科学基金项目（2018M632519，2014M561809），高校优秀青年骨干人才国外访问研修项目（gxgwfx2019013），国家自然科学基金项目（E041102）资助

作者简介: 葛涛，1980年生，安徽理工大学材料科学与工程学院副教授 e-mail：getao2007@163.com

引用本文:

葛涛，李洋，WANG Meng，李芬，张明旭. 山西高硫气肥煤结构表征与分子模型构建[J]. 光谱学与光谱分析, 2020, 40(11): 3373-3378.
GE Tao, LI Yang, WANG Meng, LI Fen, ZHANG Ming-xu. Structural Characterization and Molecular Model Construction of Gas-Fat Coal With High Sulfur in Shanxi. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2020, 40(11): 3373-3378.

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