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利用SAXS表征不同变质程度煤纳米孔隙特征

刘阳, 姚素平, 汤中一   

  • 出版日期:2019-02-20 发布日期:2019-03-07

Characterization of Nanopore of Different Metamorphic Coals by SAXS

LIU Yang,YAO Suping,TANG Zhongyi   

  • Online:2019-02-20 Published:2019-03-07

摘要: 文章通过小角X 射线散射(SAXS) 的方法研究了自然演化系列不同煤级煤的纳米孔隙结构和分布特征。结果表明,
随着煤级的增高,孔隙表面分形呈多阶段变化: Ro<0.89%,壳质组开始逐渐液化,发育大量孔隙,分形维数不断增大;
Ro 为0.9%~1.5%,因挥发分生油充填孔隙和原油沥青的芳构化等作用,而使微孔表面平整光滑,分形维数减小;Ro 为1.5%
~3.5%,镜质组裂解生气发育了大量纳米孔隙,分形维数再次增大;随后逐渐石墨化,表面分形再次降低。煤中纳米级孔
隙主要集中在50~100 nm 范围内。其中细介孔(2~10 nm) 体积百分比占0.21%~3.12%,中介孔(10~25 nm) 体积百分比占
5.06%~11.28%,粗介孔(25~50 nm) 体积百分比占21.06%~26.36%,大孔(50~100 nm) 所占体积百分比最大,高达
64.63%~68.36%。随着煤级升高,煤样的最可几孔径不断减小,最可几孔径由80 nm 减小到10 nm,减小的速度由缓到快;
中介孔和细介孔体积百分比不断增大,与成熟度分别呈对数和线性关系;粗介孔和大孔百分比不断减少,与成熟度呈对数
关系。最可几孔径变化也十分明显,在低煤化烟煤阶段时,随煤化程度增高最可几孔径略有下降(峰值处的孔径范围在
75~71 nm 内),中高煤化烟煤阶段时,随煤化程度的增高最可几孔径呈较明显的下降趋势(峰值处的孔径范围在78~53 nm
内),到无烟煤阶段时,其孔径则快速下降(峰值处的孔径范围在72~9 nm)。

关键词: 煤, 小角散射, 纳米孔隙, 孔径分布

Abstract: In this paper, the small-angle X-ray scattering (SAXS) is used to study the structure and distribution characteristics of
nanopores in the coals of a natural evolution series. Our results show that, with the increase of coal rank, the pore surface fractal changed
in multiple stages: Ro < 0.89%, the exinite began to liquefy gradually, developing a lot of pores, and the fractal dimension increased
continuously; 0.9%<Ro<1.5%, the pores were filled with volatile oil, and the crude oil asphalt underwent aromatization, both lead to the
micropore surface smooth and the fractal dimension decreased; 1.5%<Ro<3.5%, the vitrinite pyrolysis generated a large number of
nanopores, and the fractal dimension increased again; then it gradually graphitized, and the surface fractal decreased again. The
nano-sized pores in coal are mainly concentrated in the range of 50-100 nm. The volume percentages of the fine mesopores (2-10 nm),
the mesopores (10-25 nm), and coarse mesopores (25-50 nm) are 0.21%-3.12%, 5.06%-11.28%, and 21.06%-26.36%, respectively.
Large pores (50-100 nm) account for the largest percentage of volume, up to 64.63%-68.36%. With the increase of coal ranks, the most
measurable pore size of coal sample decreased continuously from 80 to 10 nm, and its decreasing speed increased gradually; the volume
percentage of mesopore and fine mesopore increased continuously, showing a logarithm and linear relationship with maturity
respectively, while the percentage of rough mesopores and macropores decreased, showing a logarithm relationship with maturity. The
most measurable pore diameter changed obviously. In the low-coal bituminous coal stage, as the degree of coalification increased, the
most measurable pore diameter decreased slightly (the pore diameter at the peak ranges from 75 to 71 nm). In the middle-high coal
bituminous coal stage, with the increase of the degree of coalification, the most measurable pore diameters showed a more obvious
downward trend (the pore diameter at the peak ranges from 78 to 53 nm). In the anthracite stage, the pore size decreased rapidly (the
pore size at the peak ranged from 72 to 9 nm)

Key words: coal, SAXS, nanopores, pore size distribution