无烟煤微晶结构的高分辨率透射电镜分析

雷蕾; 相建华; 曾凡桂; 邓小鹏

doi:10.1016/S1872-5813(21)60050-6

无烟煤微晶结构的高分辨率透射电镜分析

doi: 10.1016/S1872-5813(21)60050-6

1.
太原理工大学地球科学与工程系煤与煤系气地质山西省重点实验室，山西太原 030024
2.
山西能源学院，山西晋中 030600

基金项目: 国家自然科学基金（41572144，U1910204，41973077）和山西省应用基础研究基金（201601D021137）资助

详细信息

作者简介:
雷蕾：雷蕾：1498007688@qq.com

通讯作者:
E-mail: xiangjianhua@tyut.edu.cn

中图分类号: TQ533
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出版历程
- 收稿日期: 2020-12-24
- 修回日期: 2021-01-27
- 网络出版日期: 2021-03-30
- 刊出日期: 2021-06-30

High resolution TEM image analysis of anthracite coal microcrystalline structure

1.
Department of Geoscience and Engineering, Key Laboratory of Coal and Coal-measure Gas Geology in Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China
2.
Shanxi Institute of Energy, Jinzhong 030600, China

Funds: The project was supported by National Natural Science Foundation of China (41572144, U1910204, 41973077), Applied Basic Research Fund of ShanXi Province (201601D021137)

More Information

Corresponding author: E-mail: xiangjianhua@tyut.edu.cn

摘要

摘要: 对阳泉3号无烟煤4张HRTEM图像的条纹长度、取向和堆垛分布进行了定量表征。结果表明，条纹分布特征均符合无烟煤的煤级特点。对图片1中3个不同微晶结构区域的条纹进行统计，结果表明，1号区域中，晶格条纹较短平均长度为0.87 nm，整体条纹取向分布杂乱，但短条纹之间以及长条纹之间仍各自存在小范围的有序排列，堆垛最大层数仅4层；3号条纹区域中，晶格条纹较长平均为1.01 nm，取向在135°−180°有较高富集，比例达62.46%，同时堆垛最大层数可达到6层；2号区域条纹分布特征则介于1号和3号之间。大部分条纹表现出弯曲的形态，可能其中有杂元环以及脂肪环的存在。FT-IR和 ¹³C NMR的数据表明，脂肪结构多以脂肪环形式存在，其在短条纹拼接形成长条纹的过程中发挥着重要作用。
- HRTEM /
- 无烟煤 /
- 晶格条纹 /
- 微晶结构
Abstract: Four HRTEM images of Yangquan No. 3 anthracite were quantitatively characterized, including fringe length, orientation and stacking distribution. The result indicates that the fringe characteristics are consistent with the coal rank characteristics of anthracite. The fringe of three different microcrystalline regions in image 1 was statistically analyzed. In region 1, the average fringe length is 0.87 nm, the overall fringe orientation distribution is disorderly, but there is still a small range of orderly arrangement between the short fringes and between the long fringes, and the maximum number of stacking layers is 4; In region 3, the fringe length is 1.01 nm on average, the orientation is higher in the range of 135°−180° with a ratio of 62.46%, and the maximum number of stacking layers can reach 6. The fringe distribution characteristic of region 2 is between 1 and 3. Most of the fringes are curved, and there may be heterocyclic rings and aliphatic rings. The FT-IR and ¹³C NMR data show that the aliphatic structure mainly exists in the form of aliphatic rings, which plays an important role in the process of forming long fringes by short fringes.
- HRTEM /
- anthracite coal /
- lattice fringe /
- microcrystalline structure

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FIG. 716. FIG. 716.

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图 1 煤样的 ¹³C NMR谱图

Figure 1 ¹³C NMR spectrum of coal sample

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图 2 煤样的2800−3000 cm⁻¹红外光谱谱图

Figure 2 2800−3000 cm⁻¹ FT-IR spectrum of coal sample

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图 3 原始图像及晶格条纹图像

Figure 3 Original and lattice fringe images

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图 4 基于六边形生长的环形连锁方式

Figure 4 Circular catenation method based on hexagonal growth

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图 5 条纹长度分布

Figure 5 Distribution of fringe length

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图 6 条纹角度分布

Figure 6 Distribution of fringe direction

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图 7 条纹堆垛结构分布

Figure 7 Distribution of fringe stacking structure

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图 8 原图及晶格条纹图像

Figure 8 Original and lattice fringe images

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图 9 区域1、2、3的原始HRTEM图像及晶格条纹图像

Figure 9 Original HRTEM images and lattice fringe images of region 1, 2, and 3

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图 10 不同区域短、中、长条纹长度假色晶格条纹图像

Figure 10 Short, medium, and long fringes false-colored by length of different regions

(a1), (b1), (c1) total fringes of region 1, 2, and 3; (a2), (b2), (c2) short fringes of region 1, 2, and 3; (a3), (b3), (c3) medium fringes of region 1, 2, and 3; (a4), (b4), (c4) long fringes of region 1, 2, and 3

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图 11 不同区域条纹取向假色晶格条纹图像

(a) region 1; (b) region 2; (c) region 3

Figure 11 Fringes false-colored by direction of different regions

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图 12 不同区域条纹堆垛假色晶格条纹图像

(a): region 1; (b): region 2; (c): region 3

Figure 12 Fringes false-colored by stacking number of different regions

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图 13 依据堆垛中的层片个数得到的堆垛分布

Figure 13 Distribution of stacks according to the number of layers in a stack

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表 1 样品的工业元素分析及镜质组反射率

Table 1 Proximate and ultimate analyses, vitrinite reflectance of coal sample

Sample	Proximate analysis w/%			Ultimately analysis w_daf/%					R_{o, max}/%
Sample	M_ad	A_ad	V_daf	C	H	O	N	S	R_{o, max}/%
YQ-3	0.95	10.88	9.90	91.72	3.79	2.71	1.34	0.44	2.59

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表 2 煤样的 ¹³C NMR结构参数

Table 2 Structural parameters derived from ¹³C NMR spectrum of coal sample

Sample	f_a	f_a^c	f_a’	f_a^H	f_a^N	f_a^B	f_a^S	f_a^P	f_al	f_al*	f_al^H	f_al^O
YQ-3	0.93	0.02	0.91	0.53	0.38	0.24	0.12	0.02	0.07	0.01	0.03	0.03
note: f_a-total sp² hybridized C; f_al-total sp³ hybridized C; f_a^c -carbonyl group or carboxyl group C; f_a’-aromatic C; f_a^H-protonated and aromatic C; f_a^N -non-protonated and aromatic C; f_a^P-aromatic C bonded to hydroxyl or ether oxygen (δ = 150−165); f_a^S -alkylated aromatic C; f_a^B - aromatic bridgehead C; f_al*-CH₃ or quaternary C; f_al^H -CH or CH₂; f_al^O-aliphatic C bonded to oxygen

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表 3 六边形芳香片层长度参数

Table 3 Length parameters of hexagonal-shaped aromatic layers

C number	Min L/nm	Max L/nm	Mean L/nm
Benzene	0.246	0.284	0.265
Naphthalene	0.284	0.492	0.388
C13	0.492	0.497	0.495
C24	0.710	0.738	0.724
C27	0.738	0.923	0.831
C37	0.923	0.984	0.954
C54	1.136	1.230	1.183
C80	1.476	1.610	1.543
C96	1.540	1.704	1.622

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表 4 每15°范围内的条纹分布

Table 4 Distribution of fringe within 15° bins

Angle/(°)	Distribution of fringes/%
Angle/(°)	region 1	region 2	region 3
0−45	24.23	18.09	25.59
45−90	16.04	6.48	2.66
90−135	24.91	18.43	9.30
135−180	34.81	56.99	62.46

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参考文献(28)

[1]	BASET Z H, PANCIROV R J, ASHE T R. Organic compounds in coal: Structure and origins[J]. Phys Chem Earth,1980,12:619−630. doi: 10.1016/0079-1946(79)90143-5
[2]	MATHEWS J P, CHAFFEE A L. The molecular representations of coal-A review[J]. Fuel,2012,96:1−14. doi: 10.1016/j.fuel.2011.11.025
[3]	张代钧, 鲜学福. 煤大分子结构研究的进展[J]. 重庆大学学报,1993,16(2):58−63. ZHANG Dai-jun, XIAN Xue-fu. Advances in the study of macromolecular structure of coal[J]. J Chongqing Univ,1993,16(2):58−63.
[4]	LI X M, CAO D Y, ZHANG S R, XING X Y. Study of the XRD parameter evolution of coal of different metamorphism types[J]. Coal Geol Explor,2003,31(3):5−7.
[5]	JIANG J Y, YANG W H, CHENG Y P, LIU Z D, ZHANG Q, ZHAO K. Molecular structure characterization of middle-high rank coal via XRD, Raman and FTIR spectroscopy: Implications for coalification[J]. Fuel,2019,239:559−572. doi: 10.1016/j.fuel.2018.11.057
[6]	NEOMAGUS H W, EVERSON R C, ROBERTS M J. Chemical-structural properties of South African bituminous coals: Insights from wide angle XRD-carbon fraction analysis, ATR-FTIR, solid state ¹³C NMR, and HRTEM techniques[J]. Fuel,2015,158:779−792. doi: 10.1016/j.fuel.2015.06.027
[7]	LI Y, CAO X Y, ZHU D Q, CHAPPELL M A, MILLER L F, MAO J D. Characterization of coals and their laboratory-prepared black carbon using advanced solid-state ¹³C nuclear magnetic resonance spectroscopy[J]. Fuel Process Technol,2012,96:56−64. doi: 10.1016/j.fuproc.2011.12.014
[8]	葛涛, 张明旭, 马祥梅. 新阳炼焦煤结构的FTIR和XPS谱学表征[J]. 光谱学与光谱分析,2017,37(8):2406−2411. GE Tao, ZHANG Ming-xu, MA Xiang-mei. XPS and FTIR spectroscopy characterization about the structure of coking coal in Xinyang[J]. Spectrosc Spect Anal,2017,37(8):2406−2411.
[9]	WU D, ZHANG H, HU G Q, ZHANG W Y. Fine characterization of the macromolecular structure of huainan coal using XRD, FT-IR, ¹³C-CP/MAS NMR, SEM, and AFM techniques[J]. Molecules,2020,25(11).
[10]	任秀彬, 辛文辉, 张亚婷, 周安宁. 基于HRTEM的低阶烟煤微晶结构研究[J]. 煤炭学报,2015,40(1):242−246. REN Xiu-bin, XIN Wen-hui, ZHANG Ya-ting, ZHOU An-ning. Structural alignment of low rank coal using HRTEM technique[J]. J China Coal Soc,2015,40(1):242−246.
[11]	王小令, 李霞, 曾凡桂, 边洁晶. 基于HRTEM的煤中不同聚集态结构表征[J]. 煤炭学报,2020,45(2):749−759. WANG Xiao-ling, LI Xia, ZENG Fan-gui, BIAN Jie-jing. Characterization of different aggregate structures in coal based on HRTEM[J]. J China Coal Soc,2020,45(2):749−759.
[12]	SHARMA A, KYOTANI T, TOMITA A. Direct observation of raw coals in lattice fringe mode using high-resolution transmission electron microscopy[J]. Energy Fuels,2001,14(6):1219−1225.
[13]	MATHEWS J P, SHARMA A. The structural alignment of coal and the analogous case of argonne upper freeport coal[J]. Fuel,2012,95:19−24. doi: 10.1016/j.fuel.2011.12.046
[14]	SHARMA A, KYOTANI T, TOMITA A. A new quantitative approach for microstructural analysis of coal char using HRTEM images[J]. Fuel,1999,78(10):1203−1212. doi: 10.1016/S0016-2361(99)00046-0
[15]	WANG S Q, CHEN H, ZHANG X M. Transformation of aromatic structure of vitrinite with different coal ranks by HRTEM in situ heating[J]. Fuel,2020,260:116309. doi: 10.1016/j.fuel.2019.116309
[16]	FENG B, BHATIA S K, BARRY J C. Variation of the crystalline structure of coal char during gasification[J]. Energy Fuels,2003,17(3):744−754. doi: 10.1021/ef0202541
[17]	CASTRO-MARCANO F, WINANS R E, CHUPAS P. Fine structure evaluation of the pair distribution function with molecular models of the argonne premium coals[J]. Energy Fuels,2012,26:4336−4345. doi: 10.1021/ef300364e
[18]	FERNANDEZ-ALOS V, WATSON J K, WAL R V. Soot and char molecular representations generated directly from HRTEM lattice fringe images using fringe3D[J]. Combust Flame,2011,158(9):1807−1813. doi: 10.1016/j.combustflame.2011.01.003
[19]	NIEKERK D V, MATHEWS J P. Molecular representations of permian-aged vitrinite-rich and inertinite-rich south african coals[J]. Fuel,2010,89(1):73−82. doi: 10.1016/j.fuel.2009.07.020
[20]	YEHLIU K, WAL R L, ANDRÉ L BOEHMAN. Development of an HRTEM image analysis method to quantify carbon nanostructure[J]. Combust Flame,2011,158(9):1837−1851. doi: 10.1016/j.combustflame.2011.01.009
[21]	李霞, 曾凡桂, 司加康, 王威, 程丽媛. 不同变质程度煤的高分辨率透射电镜分析[J]. 燃料化学学报,2016,44(3):279−286. doi: 10.3969/j.issn.0253-2409.2016.03.004 LI Xia, ZENG Fan-gui, SI Jia-kang, WANG Wei, DONG Kui, CHENG Li-yuan. High resolution TEM image analysis of coals with different metamorphic degrees[J]. J Fuel Chem Technol,2016,44(3):279−286. doi: 10.3969/j.issn.0253-2409.2016.03.004
[22]	张小东, 孔令菲, 秦勇, 张鹏. 龙口褐煤萃取后微晶结构的XRD与HRTEM研究[J]. 煤炭学报,2013,38(6):1025−1030. ZHANG Xiao-dong, KONG Ling-fei, QING Yong, ZHANG Peng. Research on the microcrystalline structure of the fractionally-extracted longkou lignite by XRD and HRTEM[J]. J China Coal Soc,2013,38(6):1025−1030.
[23]	ZHANG X M, WANG S Q, CHEN H, GUO Q, LI L, LUO G L. Aromatic structural characterization of different-rank vitrinites: Using HRTEM, XRD and AFM[J]. Polycycl Aromat Comp,2019,(1):1−12.
[24]	王绍清, 陈昊, 张小梅, 沙玉明. 不同煤级含树皮体煤HRTEM特征研究[J]. 煤炭技术,2017,36(12):266−268. WANG Shao-qing, CHEN Hao, ZHANG Xiao-mei, SHA Yu-ming. HRTEM characteristics of different ranks with coals rich in barkinite[J]. Coal Technol,2017,36(12):266−268.
[25]	相建华, 曾凡桂, 李彬, 张莉, 李美芬, 梁虎珍. 成庄无烟煤大分子结构表征与模型及分子模拟[J]. 燃料化学学报,2013,41(4):391−399. doi: 10.3969/j.issn.0253-2409.2013.04.002 XIANG Jian-hua, ZENG Fan-gui, LI Bin, ZHANG Li, LI Mei-fen, LIANG Hu-zhen. Construction of macromolecular structural model of anthracite from Chengzhuang coal mine and its molecular simulation[J]. J Fuel Chem Technol,2013,41(4):391−399. doi: 10.3969/j.issn.0253-2409.2013.04.002
[26]	郝盼云, 孟艳军, 曾凡桂, 闫涛滔, 徐光波. 红外光谱定量研究不同煤阶煤的化学结构[J]. 光谱学与光谱分析,2020,40(3):787−792. HAO Pan-yun, MENG Yan-jun, ZENG Fan-gui, YAN Tao-tao, XU Guang-bo. Quantitative study of chemical structures of different rank coals based on infrared spectroscopy[J]. Spectrosc Spect Anal,2020,40(3):787−792.
[27]	李霞, 曾凡桂, 王威, 董夔, 程丽媛. 低中煤级煤结构演化的FTIR表征[J]. 煤炭学报,2015,40(12):2900−2908. LI Xia, ZENG Fan-gui, WANG Wei, DONG Kui, CHENG Li-yuan. FTIR characterization of structural evolution in low-middle rank coals[J]. J China Coal Soc,2015,40(12):2900−2908.
[28]	ZHONG Q F, MAO Q Y, ZHANG L Y, XIANG J H, XIAO J, MATHEWS J P. Structural features of qingdao petroleum coke from HRTEM lattice fringes: Distributions of length, orientation, stacking, curvature, and a large-scale image-guided 3D atomistic representation[J]. Carbon,2018,129:790−802. doi: 10.1016/j.carbon.2017.12.106