弥勒褐煤结构特征及其分子模型构建

张殿凯; 李艳红; 常丽萍; 訾昌毓; 张远琴; 田国才; 赵文波

doi:10.19906/j.cnki.JFCT.2021026

弥勒褐煤结构特征及其分子模型构建

doi: 10.19906/j.cnki.JFCT.2021026

张殿凯^1,,
李艳红^{1, 2, ,},
常丽萍^2,,
訾昌毓¹,
张远琴¹,
田国才³,
赵文波¹

1.
昆明理工大学化学工程学院，云南昆明 650500
2.
太原理工大学煤科学与技术省部共建国家重点实验室培育基地，山西太原 030024
3.
昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室，云南昆明 650093

基金项目: 国家自然科学基金（21766013）和昆明理工大学分析测试基金（2020M20192208021）资助

详细信息

通讯作者:
E-mail: liyh_2004@163.com

中图分类号: TQ531
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出版历程
- 收稿日期: 2020-11-20
- 修回日期: 2020-12-27
- 网络出版日期: 2021-03-30
- 刊出日期: 2021-06-15

Structural characteristics of Mile lignite and its molecular model construction

1.
School of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China
2.
State Key Laboratory Breeding Base of Coal Science and Technology Co-founded by Shanxi Province and Ministry of Science and Technology, Taiyuan University of Technology, Taiyuan 030024, China
3.
State Key Lab of Complex Nonferrous Metal Resource Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China

Funds: The project was supported by the Natural Science Foundation of China (21766013) and Analysis and Testing Foundation of Kunming University of Science and Technology (2020M20192208021)

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Corresponding author: E-mail: liyh_2004@163.com

摘要

摘要: 以云南弥勒褐煤为研究对象，采用元素分析、傅里叶变换红外光谱、¹³C固体核磁共振波谱以及X射线光电子能谱等现代分析技术，获取了弥勒褐煤的结构参数信息。其中，芳香度为38.79%，芳香环取代基数量为3。芳香碳结构主要为苯和萘，脂肪碳结构以甲基、亚甲基为主；氧主要存在于醚氧、羧基和羰基中；氮主要以吡咯氮和吡啶氮的形式存在；硫主要为硫酚或硫醇。根据分析结果，构建出弥勒褐煤的分子结构模型，分子式为C₁₄₇H₁₄₈O₃₆N₂S。采用半经验法PM3基组和密度泛函理论M06-2X泛函对分子构型进行优化，优化后的模型立体构型显著，且芳香层片在空间上呈现不规则排列，各芳香环之间主要通过甲基、亚甲基、甲氧基以及脂肪环连接。模拟FT-IR光谱和模拟 ¹³C NMR波谱均与实验谱图吻合良好，证明了弥勒褐煤分子模型的准确性和合理性。
- 褐煤 /
- 分子模拟 /
- 分子结构 /
- 量子化学计算 /
- 结构优化
Abstract: The understanding of the structural characteristics of lignite is of very importance to the lignite utilization. The structure parameters of Mile lignite in Yunnan were ascertained via Fourier transform infrared spectroscopy, ¹³C solid-state nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy and ultimate analysis. The results indicate that the aromaticity and number of aromatic ring substituents of Mile lignite are 38.79% and 3, respectively. The aromatic carbon structure typically contains benzene and naphthalene, while the aliphatic carbon structure mainly includes methyl and methylene. Oxygen dominantly exists in ether oxygen, carboxyl and carbonyl; nitrogen occurs in the form of pyrrole nitrogen and pyridine nitrogen; and sulfur is mainly present in thiophenol and mercaptan. According to the analysis results, a molecular structure model of Mile lignite is constructed, with a molecular formula of C₁₄₇H₁₄₈O₃₆N₂S. The semi-empirical PM3 basis set and the density functional theory M06-2X were adopted to optimize the molecular configuration. The optimized model has a significant three-dimensional configuration, in which the aromatic layers are arranged irregularly in space and the aromatic rings are connected by methyl, methylene, methoxy and alicyclic rings. The simulated FT-IR spectrum and simulated ¹³C NMR spectrum are in great agreement with the experimental spectrum, which proves the accuracy and rationality of the molecular model of Mile lignite.
- lignite /
- molecular simulation /
- molecular structure /
- quantum chemical calculation /
- structure optimization

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FIG. 714. FIG. 714.

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图 1 分子模型构建流程图

Figure 1 Procedure of model construction

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图 2 ML的 ¹³C NMR分峰拟合谱图

Figure 2 ¹³C NMR peak fitting spectra of ML

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图 3 ML的红外光谱谱图

Figure 3 FT-IR spectrum of ML

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图 4 ML的XPS分峰拟合图

Figure 4 XPS peak fitting diagrams of ML

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图 5 ML的分子结构模型(C₁₄₇H₁₄₈O₃₆N₂S)

Figure 5 Molecular structure model of ML (C₁₄₇H₁₄₈O₃₆N₂S)

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图 6 计算谱图与实验谱图对比：（a）FT-IR谱图；（b） ¹³C NMR谱图

Figure 6 Comparison of the calculated spectra with the experimental spectra: (a) FT-IR spectra; (b) ¹³C NMR spectra

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表 1 ML的工业分析与元素分析

Table 1 Proximate analysis and Ultimate analysis of ML

Proximate analysis w/%				Ultimate analysis w_daf/%
M_ad	A_d	V_daf	FC_daf	C	H	N	S_t	O
7.22	9.55	59.18	40.82	69.66	5.83	1.10	0.83	22.58
notes: M_ad is the moisture mass fraction of sample on the air dry basis; A_d is the ash mass fraction of sample on the dry basis; V_daf is the volatile matter mass fraction of sample on the dry ash-free basis; FC_daf is the fixed carbon mass fraction of sample on the dry ash-free basis; S_t is the total sulfur

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表 2 ML ¹³C NMR分峰获得的含碳官能团的化学位移和含量

Table 2 The chemical shifts and the contents of carbon-containing functional groups obtained from ¹³C NMR peaks of ML

	Carbon type	Chemical shift δ	Symbol	Molar content/%
Aliphatic	aliphatic CH₃	15	f_al¹	3.40
	aromatic CH₃	20	f_al^a	11.20
	methylene	25, 31	f_al²	22.60
	quaternary sp³C	40, 47	f_al³	5.36
	oxygen aliphatic carbon	55, 63, 74, 83	f_al^o	11.62
Aromatic	aromatic protonated	105, 115, 127	f_a^H	23.95
	aromatic bridgehead	137	f_a^b	3.84
	alkylated aromatic	146	f_a^s	5.80
	oxygen aromatic carbon	154	f_a^o2	5.20
Carbonyl	carboxyl carbon	173	f_a^C1	4.00
Carbonyl	carbonyl carbon	205	f_a^C2	3.03

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表 3 ML的XPS分析

Table 3 XPS analysis results of ML

	Functional group	Binding energy E/eV	Content/%
C 1s	C−C/C−H	284.8(± 0.2)	77.22
	C−O	286.3(± 0.2)	15.61
	C=O/O−C−O	287.5(± 0.2)	4.51
	COOH	289.0(± 0.2)	2.66
O 1s	inorganic oxygen	530.3(± 0.2)	2.45
	C=O/O−C−O	531.4(± 0.2)	35.24
	C−O	532.5(± 0.2)	43.20
	COOH	533.9(± 0.2)	19.10
N 1s	pyridine nitrogen	399.5(± 0.2)	39.45
	pyrrolic nitrogen	400.5(± 0.2)	30.22
	quaternary nitrogen	401.3(± 0.2)	18.89
	oxidized nitrogen	402.8(± 0.2)	11.44
S 2p	mercaptan thiophenol	163.8(± 0.2)	48.82
	thiophene type sulfide	165.7(± 0.2)	8.62
	sulfoxide sulfur	168.0(± 0.2)	22.97
	sulfone type sulfur	169.5(± 0.2)	8.62
	inorganic sulfur	171.1(± 0.2)	10.97

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表 4 ML分子结构中芳香结构的种类和数量

Table 4 Types and quantities of aromatic structures in ML molecules

Type	Aromatic unit structure	Number
Benzene		3
Naphthalene		3
Pyridine		1
Pyrrole		1

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