^(13)C NMR、FT-IR、Raman和建模技术对烟煤和无烟煤分子结构的应用研究  

Characterization of Molecular Structure of Bituminous Coal and Anthracite by ^(13)C NMR,FT-IR,Raman and Modeling Techniques

作　　者：李元吉 代诚欣 孟上九 张保勇 张强 LI Yuanji;DAI Chengxin;MENG Shangjiu;ZHANG Baoyong;ZHANG Qiang(School of Safety Engineering,Heilongjiang University of Science and Technology,Harbin 150022,China)

机构地区：[1]黑龙江科技大学安全工程学院,哈尔滨150022

出　　处：《太原理工大学学报》2024年第6期1063-1072,共10页Journal of Taiyuan University of Technology

基　　金：国家自然科学基金资助项目(52374199);黑龙江省自然科学基金优秀青年项目(YQ2022E041);黑龙江科技大学博士科研启动基金;黑龙江省省属高等学校基本科研(2023-KYYWF-0507);黑龙江省博士后面上项目(LBH-Z23030)。

摘　　要：【目的】探究高精度煤的结构演化及其机理的定量表征。【方法】通过显微组分鉴定、镜质体反射率、工业品质、元素分析和光谱分析,确定了烟煤(FS1)和无烟煤(ZY1)碳骨架结构、官能团的赋存状态等信息,并通过计算机辅助分子设计建立2个分子结构模型。【结果】结果表明,随着煤化作用的进行,烟煤到无烟煤过程中,亚甲基的损失速率比甲基的损失速率快,芳香性增强,芳香环的脂肪族链变短且支化度较高,含氧官能团逐渐减少,煤结晶程度增强,煤的化学结构趋于成熟稳定,且煤中的脂肪碳减少,芳香碳增加,甲基碳和亚甲基碳含量减少。经过多次尝试确定了芳香炭、脂肪族侧链和氧官能团之间的键合模式,获得最终的分子结构模型:C_(175)H_(162)O_(13)N_(2)(FS1)、C_(190)H_(159)O_(5)N_(3)(ZY1).该模型较好地反映煤的真实结构,模拟的^(13)C NMR光谱与实验光谱具有良好的一致性。上述研究为不同变质程度煤的分子结构演化提供了理论参考,为建立高可信度的分子结构表征提供了方法。【Purposes】While extensive research has been conducted on the evolution of coal´s molecular structure during coalification,the heterogeneity and complexity of coal continue to impede the accurate and precise quantitative characterization of its structural evolution mechanism.【Methods】Through maceral identification,vitrinite reflectance,industrial quality,elemental analysis,and spectral analysis,the carbon skeleton structure and occurrence state of functional groups of bituminous coal(FS1)and anthracite coal(ZY1)were determined.Two molecular structure models were established by computer-aided molecular design.【Finding】The results show that with the progress of coalification,the loss rate of methylene is faster than that of methyl in the process of bituminous coal to anthracite,the aromaticity is enhanced,the aliphatic chain of aromatic ring becomes shorter and the degree of branching is higher,the oxygen-containing functional groups is gradually reduced,the crystallinity of coal is enhanced,and the chemical structure of coal tends to be mature and stable.At the sometime,the content of aliphatic carbon in coal decreases,the content of aromatic carbon increases,and the content of methyl carbon and methylene carbon decreases.After several attempts,the bonding mode between aromatic carbon,aliphatic side chain,and oxygen functional group was determined,and the final molecular structure models were obtained:C_(175)H_(162)O_(13)N_(2)(FS1),C_(190)H_(159)O_(5)N_(3)(ZY1).These models well reflect the real structure of coal,and the simulated ^(13)C NMR spectra are in good agreement with the experimental spectra.The above research provides a theoretical reference for the molecular structure evolution of coal with different metamorphic degrees,and provides a method for establishing high-reliability molecular structure characterization.

关 键 词：煤 ^(13)C NMR FT-IR RAMAN 分子结构模型 

分 类 号：TQ531.1[化学工程—煤化学工程] TQ533.6