煤田地质与勘探
Coal Geology & Exploration
————————————————————
基金项目:国家自然科学基金项目(41502160,41802187);西安科技大学优秀青年科技基金项目(2019YQ2-08)
Foundation item: National Natural Science Foundation of China(41502160,41802187);Outstanding Youth Science Fund of Xi’an University of
Science and Technology(2019YQ2-08)
第一作者简介:李焕同,1986 年生,男,山东单县人,博士,讲师/硕士生导师,从事煤田地质与煤田构造工作. E-mail:htlcumt@126.com
高煤级煤—隐晶质石墨的 Raman 光谱表征及结构演化
李焕同
1,2
,王 楠
1
,朱志蓉
1
,范晶晶
3
,张卫国
1,2
(1. 西安科技大学地质与环境学院,陕西 西安 710054;2. 陕西省煤炭绿色开发地质保障重点实验室,陕
西 西安 710054;3. 中国石油勘探开发研究院,北京 100083)
摘要:拉曼光谱能够反映碳材料结构的有序程度和结构缺陷,可用来表征高煤级煤—隐晶质石墨演
化过程中结构变化。通过对受岩浆热变质影响的不同变形变质程度样品的拉曼参数与面网间距(d
002
)
之间关系的研究表明:G 峰位置与 d
002
呈现阶梯变化,能较好地区分出石墨与高煤级煤,S
2
峰位、
D
1
与 G 半峰宽与 d
002
呈较好的线性关系;D
1
与 G 峰峰位差和半峰宽比随 d
002
减小而减小,S
2
与 S
4
峰的峰位差随 d
002
减小先增大后减小,而其强度比及面积比逐渐增大;d
002
与拉曼参数关系显示两
次明显的结构演化跃变,即无烟煤至变质无烟煤阶段(R
max
>6.5%,P
(D1-G)
<235 cm
-1
,P
(S2-S4)
>525 cm
-1
以及半峰宽比显著下降,La/Lc 减小 2~3 倍),为芳构化、芳环缩合作用增强向芳环叠片拼叠转变;
半石墨至石墨演化阶段(P
(D1-G)
、I
D1
/I
G
与 A
D1
/A
G
显著降低,La、Lc 迅速增加)。以 d
002
为标度能较好
地反映煤结构在不同演化阶段的 Raman 光谱特征。
关 键 词:高煤级煤;隐晶质石墨;结构演化;X 射线衍射;拉曼光谱;跃变
中图分类号:P618.11,P619.252 文献标识码:A
Raman spectrum characteristic and structural evolution of high rank coals -
cryptocrystalline graphite
LI Huantong
1, 2
, WANG Nan
1
, ZHU Zhirong
1
, FAN Jingjing
3
, ZHANG Weiguo
1, 2
(1. College of Geology and Environment, Xi’an University of Science and Technology, Xi’an 710054, China;
2. Shaanxi Provincial Key Laboratory of Geological Support for Coal Green Exploitation, Xi’an 710054, China;
3. Research Institute of Petroleum Exploration and Development, Petro China, Beijing 100083, China)
Abstract: Raman spectroscopy can reflect the order degree and structural defects of carbon materials, and can be used
to characterize the structural changes during the evolution of high rank coal-cryptocrystalline graphite, and analyze the
relationship between Raman parameters of coal with different deformation and metamorphic degrees and the spacing
of surface network (d
002
). The results showed that: (1) there was stepped variation between the G peak position and
d
002
, but the graphite and high rank coal could be distinguished well. The S
2
peak, the full width at half maximum of
D
1
and G had a good linear relationship with d
002;
(2) the peak difference between D
1
and G and the full width at half
maximum ratio decreased with the decrease of d
002
; the peak difference between S
2
and S
4
increased first and then
decreased with the decrease of d
002
, while the intensity ratio and area ratio increased gradually; (3) the relationship of
interlayer spacing (d
002
) and Raman parameters figure shows the structure of two obvious evolutionary step, namely
anthracite to ultra-anthracite (R
max
> 6.5 %, P
(
D1-G
)
<235 cm
-1
, P
(S2-S4)
>525 cm
-1
and half peak width ratio dropped
significantly, La/Lc reduce 2 ~ 3 times), semi-graphite to graphite evolutionary stages (P
(D1-G)
, I
D1
/I
G
, A
D1
/A
G
significantly reduced; La, Lc increase rapidly). The Raman spectral characteristics of coal structure at different
evolution stages can be well reflected by taking d
002
as the scale.
Keywords: High rank coals; cryptocrystalline graphite; structural evolution; XRD; Raman spectrum; mutation
近年来,拉曼光谱常用来表征无定形碳至不同石
墨化度的 sp
2
和 sp
3
键合的碳材料微观结构,合成碳材
料或天然样品的拉曼光谱散射特性随变质程度的变化
特征
[1-6]
、随不同构造变形机制的变化特征
[7-8]
等方面
得到广泛研究。通常,碳材料的拉曼光谱被分为一级
模与二级模两个部分,完好石墨结构的拉曼光谱一级
模只显示位于 1 580 cm
-1
附近与 E
2g
振动模相应的 G
峰(亦称石墨峰),属于芳香族面域内环与链中所有 sp
2
晶格格位的伸缩振动,
对称群
[9]
;相对于无序碳
而言,该峰向高频率范围(1 580~1 600 cm
-1
)移动。煤
是由基本结构单元的芳香核与烷基侧链、官能团、桥
键组成的有机大分子,是一种短程有序、长程无序的
非晶态物质
[10-11]
,芳香层内存在缺陷或杂原子等无序
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