拉曼光谱参数在不同成熟度煤显微组分分析中的应用

高志伟; 张聪; 李美俊; 方镕慧; 腾格尔; 肖洪; 朱志立

doi:10.11781/sysydz202204705

拉曼光谱参数在不同成熟度煤显微组分分析中的应用

doi: 10.11781/sysydz202204705

高志伟^{1, 2,},
张聪^{3, 4},
李美俊^{1, 2, ,},
方镕慧^{3, 4},
腾格尔^{3, 4},
肖洪^{1, 2},
朱志立⁵

1.
中国石油大学(北京) 油气资源与勘探国家重点实验室, 北京 102249
2.
中国石油大学(北京) 地球科学学院, 北京 102249
3.
中国地质调查局油气资源调查中心, 北京 100083
4.
中国地质调查局非常规油气地质重点实验室, 北京 100083
5.
中国石化石油勘探开发研究院无锡石油地质研究所, 江苏无锡 214126

基金项目:

全国地质调查评价专项项目“油气地质调查钻井岩心保存参数采集与应用” DD20201114

详细信息

作者简介:
高志伟(1996—), 男, 硕士, 从事油气地球化学研究。E-mail: 2019215032@student.cup.edu.cn

通讯作者:
李美俊(1972—), 男, 博士, 教授, 从事油气地球化学研究。E-mail: meijunli@cup.edu.cn

中图分类号: TE135
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- 文章访问数: 538
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- 被引次数: 0
出版历程
- 收稿日期: 2021-07-07
- 修回日期: 2022-06-14
- 刊出日期: 2022-07-28

Application of laser Raman spectroscopic parameters of coal maceral analysis with different maturity

GAO Zhiwei^{1, 2
,},
ZHANG Cong^{3, 4},
LI Meijun^{1, 2
, ,},
FANG Ronghui^{3, 4},
BORJIGIN Tenger^{3, 4},
XIAO Hong^{1, 2},
ZHU Zhili⁵

1.
State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum (Beijing), Beijing 102249, China
2.
College of Geosciences, China University of Petroleum (Beijing), Beijing 102249, China
3.
Oil and Gas Survey, China Geological Survey, Beijing 100083, China
4.
Key Laboratory of Unconventional Oil & Gas Geology Center, China Geological Survey, Beijing 100083, China
5.
Wuxi Research Institute of Petroleum Geology, SINOPEC, Wuxi, Jiangsu 214126, China

摘要

摘要: 激光拉曼光谱在显微组分分析中已显示出良好的应用前景。对不同成熟度(R_o为0.49%~1.88%)煤样中的不同显微组分(镜质体、半丝质体、粗粒体)进行拉曼光谱分析后发现，不同显微组分的拉曼光谱参数存在明显差异，这在煤显微组分分析中有以下应用：(1)利用拉曼光谱参数组合可区分煤样中的显微组分，该研究中可区分的参数组合达21种，它们均可作为区分此类显微组分的参考标准；(2)可区分煤样中显微组分的参数组合中最关键的参数是峰位移W_D1，使用时需考虑热演化程度影响，这可能对下古生界处于高—过成熟阶段且光学性质逐渐趋同的显微组分差异研究提供帮助。因此拉曼光谱参数可作为显微组分分析的一种有效方法。
- 显微组分 /
- 成熟度 /
- 拉曼光谱参数 /
- 煤样
Abstract: Laser Raman spectroscopy has shown a good application prospect for maceral analysis. Raman spectroscopic analysis of different macerals (e.g., vitrinite, semifusinite and macrinite) in coal samples with different maturity (%R_o=0.49%-1.88%) was carried out in this study, and results show that three macerals have significantly different Raman spectrum parameters, which have the following implications for the macerals analysis of coal: (1) Macerals in coal samples can be distinguished by the combination of Raman spectrum parameters. There are 21 kinds of parameter combinations discussed in this study, which can be used as reference standard for the classification of these organic macerals; (2) Peak displacement (W_D1) is the most critical parameter to distinguish the macerals of coal samples. The influence of thermal evolution should be considered, which may assistant for the study of maceral differences in the Lower Paleozoic which are in the high to over mature stage with optical properties gradually converging. Therefore, Raman spectrum parameters can be used as an effective method for maceral analysis.
- macerals /
- maturity /
- Raman spectrum parameters /
- coal sample

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图 1 样品2中粗粒体的拉曼光谱分峰拟合结果

Figure 1. Fitting results of Raman spectra of macrinite in sample 2

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图 2 样品2中不同有机显微组分的镜下照片

A.半丝质体；B.粗粒体；C.镜质体

Figure 2. Micrographs of various organic macerals in sample 2

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图 3 样品2中不同有机显微组分的拉曼光谱

Figure 3. Raman spectra of different organic macerals in sample 2

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图 4 区分显微组分的拉曼光谱参数组合

Figure 4. Combination of Raman spectral parameters for the classification of macerals

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图 5 文献中不同显微组分的参数特征

Figure 5. Parameter characteristics of different macerals in literature

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表 1 拉曼光谱谱图预处理方法参数优选及结果

Table 1. Optimization of pretreatment parameters and results of laser Raman spectroscopy

参数优选及结果		平滑处理		基线校正
参数优选及结果		平滑窗口	多项式拟合阶次	平滑次数	多项式拟合阶次
固定参数		平滑窗口=9	多项式拟合阶次=3	平滑窗口=9，拟合阶次=6	用优选参数进行平滑处理
变化参数		平滑窗口=5~99	拟合阶次=2~8	平滑次数=1~10	拟合阶次=1~12
比较拟合效果	光谱谱图	处理谱图与原始谱图视觉比较
比较拟合效果	光谱参数/ 双峰拟合	I_D/FWHM-D，I_G/FWHM-G，RBS，R₁，鞍座指数SI
参数优选结果		平滑窗口=9	拟合阶次=6	平滑次数=1	拟合阶次=3
注：I_D1、I_G分别为D1峰和G峰的峰强度；FWHM-D1、FWHM-G分别为D1峰和G峰的半峰宽高；位移差RBS=W_G-W_D1(W_D1、W_G分别为D1峰和G峰的峰位移)；峰强度比R₁=I_D1/I_G；SI为鞍座指数。

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表 2 样品2中不同显微组分的拉曼光谱参数

Table 2. Raman spectroscopic parameters of different macerals in sample 2

显微组分	D1峰		G峰		RBS/cm^-1
显微组分	W_D1/cm^-1	FWHM-D1	W_G/cm^-1	FWHM-G	RBS/cm^-1
镜质体	1 364.32	112.89	1 597.07	68.32	232.75
半丝质体	1 357.74	108.27	1 598.93	63.54	241.20
粗粒体	1 350.03	101.95	1 597.02	67.04	246.99

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表 3 不同成熟度样品中显微组分的拉曼光谱参数

Table 3. Raman spectroscopic parameters of macerals in different maturity samples

样品号	R_o/%	显微组分	W_D1/cm^-1	FWHM-D1	W_G/cm^-1	FWHM-G	RBS/cm^-1
1	0.55	粗粒体	1 349.95	121.35	1 598.37	69.28	248.42
		半丝质体	1 358.20	119.56	1 598.66	65.77	240.46
		镜质体	1 378.85	125.58	1 599.34	81.47	220.49
2	0.62	粗粒体	1 350.03	101.95	1 597.02	67.04	246.99
		半丝质体	1 357.74	108.27	1 598.93	63.54	241.20
		镜质体	1 364.32	112.89	1 597.07	68.32	232.75
3	0.71	半丝质体	1 358.08	117.01	1 595.66	63.89	237.58
4	0.82	粗粒体	1 351.68	127.99	1 598.52	63.75	246.84
4	0.82	镜质体	1 373.53	134.41	1 587.56	73.08	214.03
5	0.96	镜质体	1 368.28	104.56	1 597.78	68.66	229.50
6	1.08	粗粒体	1 352.35	110.36	1 598.30	63.85	245.95
		半丝质体	1 357.83	101.52	1 598.74	65.93	240.91
		镜质体	1 367.97	109.03	1 597.90	67.72	229.92
7	1.24	粗粒体	1 348.16	109.21	1 599.75	61.89	251.59
7	1.24	镜质体	1 365.59	100.59	1 597.66	63.81	232.07
8	1.35	粗粒体	1 343.26	121.59	1 599.48	63.50	256.22
8	1.35	镜质体	1 365.16	94.76	1 598.16	63.68	233.01
9	1.40	粗粒体	1 347.80	111.51	1 598.63	62.29	250.84
		半丝质体	1 354.76	65.68	1 594.82	64.93	240.06
		镜质体	1 359.56	94.57	1 595.57	62.26	236.01
10	1.57	粗粒体	1 342.28	119.04	1 599.25	59.26	256.97
10	1.57	半丝质体	1 352.23	89.18	1 599.60	57.44	247.36
11	1.66	粗粒体	1 341.46	117.85	1 600.30	58.52	258.84
11	1.66	半丝质体	1 357.41	86.01	1 600.08	60.35	242.67
12	1.88	粗粒体	1 351.09	90.00	1 598.33	57.40	247.24
12	1.88	半丝质体	1 355.38	92.07	1 600.55	57.61	245.17

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表 4 区分显微组分的拉曼光谱参数组合(R_o=0.55%~1.88%)

Table 4. Combination of Raman spectral parameters for the classification of macerals(R_o=0.55%-1.88%)

交汇类型	参数	与R_o相关性	是否区分	交汇类型	与W_D1相关性	交汇参数		是否区分
基本参数—R_o	W_D1	-	是	参数—参数	0	W_G，FWHM-D1，FWHM-G，R₁，A_D1/A_G	W_G，FWHM-D1，FWHM-G，R₁，A_D1/A_G	否
	W_G	+	否
	I_D1	--	否
	I_G	--	否
	A_D1	--	否		1	W_D1，W_D1/W_G，RBS	W_G，FWHM-D1，FWHM-G，R₁，A_D1/A_G	是
	A_G	--	否
	FWHM-D1	-	否
	FWHM-G	-	否
衍生参数—R_o	W_D1/W_G	-	是		2	W_D1，W_D1/W_G，RBS	W_D1，W_D1/W_G，RBS	是
	RBS	+	是
	R₁	+	否
	A_D1/A_G	+	否
注：①A_D1、A_G分别为D1峰和G峰的峰面积，峰强度比R₁=I_D1/I_G；②与W_D1相关性是指参数中含有W_D1或者W_D1的衍生参数(W_D1/W_G、RBS)的个数；③-指负相关，+指正相关，--指相关性较差；④交汇参数是指与热成熟度R_o具有相关性的拉曼光谱参数。

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