褐煤中有机氮的赋存形态分布和分子结构特征

柳方景; 别蕾蕾; 郭佳培; 宗志敏; 魏贤勇

褐煤中有机氮的赋存形态分布和分子结构特征

中国矿业大学煤炭加工与高效利用教育部重点实验室, 江苏徐州 221116

基金项目:

国家自然科学基金青年科学基金 21808237

江苏省自然科学基金青年基金 BK20180642

中国博士后科学基金 2019T120478

详细信息

中图分类号: TQ530
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出版历程
- 收稿日期: 2020-06-17
- 修回日期: 2020-07-04
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-07-10

Occurrence forms and molecular structural characteristics of the organic nitrogen in lignite

Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining&Technology, Xuzhou 221116, China

Funds:

the National Natural Science Foundation of China 21808237

Basic Research Program of Jiangsu Province BK20180642

China Postdoctoral Science Foundation 2019T120478

More Information

Corresponding author: LIU Fang-jing, E-mail:fangjingliu@cumt.edu.cn

摘要

摘要: 利用X射线光电子能谱（XPS）分析了先锋褐煤（XL）、小龙潭褐煤（XLT）和胜利褐煤（SL）及其萃取残渣表面有机氮的形态分布。结果表明，三种萃取残渣表面五种有机氮的含量分布各异，但均以吡咯型氮为主。考察了在300℃下NaOH催化的褐煤萃取残渣的超临界甲醇解反应，XL、XLT和SL萃取残渣超临界甲醇解所得石油醚可溶物的收率分别为46.0%、43.8%和47.6%（质量分数）。用傅里叶变换离子回旋共振质谱（FTICR/MS）分析石油醚可溶物中的含氮化合物（NCCs）。结果表明，NCCs主要包括N₁、N₁O₁-N₁O₅、N₂、N₂O₁-N₂O₄、N₃O₂和N₅O₂-N₅O₄类化合物。根据不饱和度和碳原子数的分布推测了NCCs的分子结构特征，表明绝大部分NCCs含羟基和羧基等含氧官能团，氮原子主要以吡咯、吡啶和氨基的形式存在于芳环结构中，以1-3个芳环的结构为主。褐煤中的-C-O-桥键的断裂是生成NCCs的一个重要路径。
- 褐煤 /
- 有机氮 /
- 超临界甲醇解 /
- 傅里叶变换离子回旋共振质谱仪
Abstract: The occurrence forms of organic nitrogen in Xianfeng lignite (XL), Xiaolongtan lignite (XLT) and Shengli lignite (SL) as well as their extraction residues were characterized by X-ray photoelectron spectroscopy (XPS). The results show that the content distributions of organic nitrogen in the three extraction residues are different, but all are mainly dominated by pyrrole nitrogen. The NaOH-catalyzed supercritical methanolysis of lignite extraction residues at 300℃ was then investigated, which indicates that the yields of petroleum ether soluble portions from supercritical methanolysis of extraction residues derived from XL, XLT and SL are 46.0%, 43.8%, and 47.6% (mass ratio), respectively. The characterization of nitrogen-containing compounds (NCCs) in petroleum ether soluble portions by Fourier transform ion cyclotron resonance mass spectrometry (FTICR/MS) indicates that NCCs are mainly composed of N₁, N₁O₁-N₁O₅, N₂, N₂O₁-N₂O₄, N₃O₂ and N₅O₂-N₅O₄ class species. The molecular structural characteristics of NCCs were speculated according to the distributions of double bond equivalent values and carbon numbers, which shows that most of NCCs contain oxygen-functional groups like hydroxyl and carboxyl groups, and the nitrogen atoms are mainly present in aromatic structures (mainly 1-3 aromatic rings) in the forms of pyrrolic, pyridinic and amino groups. The cleavage of C-O bridged bonds in lignite is an important pathway for producing NCCs.
- lignite /
- organic nitrogen /
- supercritical methanolysis /
- FTICR/MS

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图 1 NaOH催化的褐煤萃取残渣的超临界甲醇解、后续处理和分析的流程示意图

Figure 1 Procedure for NaOH-catalyzed supercritical methanolysis of extraction residues from lignites, subsequent treatments and analyses

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图 2 褐煤及ER_XL、ER_XLT和ER_SL的XPS N 1s谱图和曲线拟合

Figure 2 XPS N 1s spectra and their fitting curves of lignites, ER_XL, ER_XLT and ER_SL

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图 3 ESI FTICRMS分析褐煤萃取残渣超临界甲醇解所得石油醚可溶物中NCCs的相对含量

Figure 3 Relative abundance of NCCs in the PESPs from lignite ERs by ESI FTICRMS analysis

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图 4 褐煤萃取残渣超临界甲醇解所得石油醚可溶物中N₁O₁-N₁O₃类化合物的DBE对应碳数分布

Figure 4 Plots of DBE versus CN plots offor the N₁O₁-N₁O₃ class species in the PESPs from lignite ERs

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图 5 甲醇解生成烷基咔唑酚、烷基氨基萘甲酸和烷基咔唑甲酸类化合物的可能反应历程示意图

Figure 5 Reaction pathway for the formation of alkylcarbazolols, alkylaminonaphthoic acids, and alkylcarbazolecarboxylic acids from lignite extraction residues via methanolysis

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表 1 褐煤的工业分析和元素分析

Table 1 Proximate and ultimate analyses of lignite

Lignite	Proximate analysis w/%			Ultimate analysis w/%					H/C (molar ratio)
Lignite	M_ad	A_d	V_daf	C_daf	H_daf	N_daf	O_diff	S_{t, d}	H/C (molar ratio)
XL	25.67	18.45	36.52	63.07	6.01	1.79	28.73	0.40	1.14
XLT	20.40	7.55	38.50	68.85	5.89	1.67	22.65	0.95	1.02
SL	20.40	19.00	37.85	69.26	5.50	0.86	23.23	1.15	0.95
daf = dry and ash-free basis; M_ad = moisture (air-dried basis); A_d = ash (moisture-free basis); V_daf = volatile matter (dry and ash-free basis); O_diff = oxygen content, calculated by difference

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表 2 褐煤萃取残渣的工业分析和元素分析

Table 2 Proximate and ultimate analyses of extraction residues from lignites

ER	Proximate analysis w/%			Ultimate analysis w/%					H/C (molar ratio)
ER	M_ad	A_d	V_daf	C_daf	H_daf	N_daf	O_diff	S_{t, d}	H/C (molar ratio)
ER_XL	27.46	19.73	32.09	62.77	6.01	1.61	> 29.15	0.46	1.1409
ER_XLT	21.08	7.80	36.45	68.13	5.45	1.76	> 23.60	1.05	0.9532
ER_SL	21.06	19.62	35.83	69.53	5.55	1.00	> 22.85	1.07	0.9511

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表 3 XPS分析褐煤及ER_XL、ER_XLT和ER_SL表面N的形态分布

Table 3 Distributions of N forms on the surface of lignites, ER_XL, ER_XLT, and ER_SL from XPS analysis

Binding energy E/eV	Forms	Relative content w/%
Binding energy E/eV	Forms	XL	XLT	SL	ER_XL	ER_XLT	ER_SL
398.5±0.2	pyridinic	5.2	7.4	6.5	6.3	13.9	19.1
399.5±0.1	amino	23.1	20.4	10.9	25.6	18.0	13.4
400.5±0.1	pyrrolic	39.8	41.1	37.4	41.1	48.7	33.7
401.4±0.1	quaternary	25.3	14.8	16.9	15.7	4.4	15.5
402.8	pyridine oxide	6.6	16.3	28.3	11.4	15.0	18.3

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