High-temperature and high-pressure simulation of coal graphitization with SiO2 additive
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摘要: 为研究自然条件下二氧化硅矿物对煤石墨化作用的影响，将二氧化硅添加剂与分选后的煤中镜质组(来自中国西南部贵州省格目底矿区)充分混合后，开展实验条件为600~1 200 ℃、1.5~2.0 GPa的高温高压模拟实验，对煤系石墨形成环境进行反演。通过X射线衍射、拉曼光谱和高分辨率透射电镜对石墨化产物进行分析，研究二氧化硅对煤的石墨化过程的影响。研究发现，二氧化硅在高温高压环境下存在阻碍石墨化作用的效果，抑制煤石墨化程度的增长。这一结果可为自然条件下构造强烈地区煤石墨化程度较低的现象提供一种解释。Abstract: This study investigates the effect of SiO2 minerals on coal graphitization under natural conditions through high-temperature and high-pressure simulation experiment to invert the coal-based graphite formation environment.We thoroughly mixed the SiO2 additive with the sorted vitrinite in coal (from the Gemudi mining area in Guizhou province[SW China]) and then carried out high-temperature and high-pressure simulation experiment with ranging from 600 ℃ to 1 200 ℃, 1.5 GPa to 2.0 GPa.The graphitization products of the samples were analyzed by X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy (HRTEM) to investigate the influence of the SiO2 additive on the process of coal graphitization.Results show that in contrast to the graphitization-promoting ability exhibited in high-temperature environments, SiO2 demonstrates a hindering effect on graphitization in high-temperature and high-pressure environments, inhibiting the growth of coal graphitization.This finding provides an hypothesis for the lower graphitization of coal in areas with strong tectonics under natural conditions.
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Key words:
- coal-based graphite /
- high temperature and high pressure /
- SiO2 additive /
- graphitization
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图 1 高温高压实验设备——六面顶压机
Figure 1. High-temperature and high-pressure experimental equipment (six-sided press)
图 2 二次酸洗脱矿实验样品XRD结果对比
Figure 2. Comparative XRD patterns of secondary acid-washed and demineralized experimental samples
图 5 600~900 ℃条件下G、GS样品的HRTEM特征
Figure 5. High-resolution transmission electron microscopic images of G/GS at 600~900 ℃
图 6 1 200 ℃条件下G/GS样品的HRTEM特征
Figure 6. High-resolution transmission electron microscopic images of G/GS at 1 200 ℃
图 7 GS样品d002随温压变化柱状图
Figure 7. The d002 parameters of G and GS samples with temperature and pressure
图 9 G、GS样品微晶结构参数(La、Lc)
Figure 9. Microcrystalline structure parameters (La, Lc) of G and GS samples
图 10 G、GS样品拉曼参数随温压变化柱状图
Figure 10. Raman parameters with temperature and pressure of G and GS samples
表 1 格目底镜质组的工业分析及元素分析数据
Table 1. Industrial and elemental analyses data of vitrinite in Gemudi
% 采集地 Ro，max 显微组分体积分数 工业分析 元素分析 镜质组 惰质组 壳质组 Mad Ad Vdaf FCdaf Cdaf Hdaf Ndaf Odaf 贵州格目底 1.7 92.4 7.6 0 0.72 5.72 17.03 78.22 90.88 3.98 1.88 2.38 
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表 2 高温高压模拟实验方案
Table 2. Scheme of high-temperature and high-pressure simulation experiment
样品编号 实验条件 无添加剂 添加SiO2 温度/℃ 压力/GPa G-1 GS-1 600 1.5 G-2 GS-2 900 1.5 G-3 GS-3 2.0 G-4 GS-4 1 200 1.5 G-5 GS-5 2.0
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表 3 模拟实验样品XRD参数
Table 3. XRD parameters of the experimental samples
编号 温度/℃ 压力/GPa 2θ002/(°) Lc/nm La/nm d002/nm GS-1 600 1.5 25.603 2.08 3.32 0.347 7 G-1 25.663 2.36 2.74 0.346 9 GS-2 900 1.5 25.842 2.27 4.85 0.344 5 G-2 26.079 3.05 8.03 0.341 4 GS-3 2 25.955 2.32 6.40 0.343 7 G-3 25.966 2.61 9.65 0.342 9 GS-4 1 200 1.5 26.130 9.98 14.48 0.340 7 G-4 26.291 17.23 54.01 0.338 7 GS-5 2 26.278 10.15 15.86 0.338 9 G-5 26.327 18.78 50.70 0.338 2
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表 4 实验样品拉曼参数
Table 4. Raman parameters of the experimental samples
编号 温度/℃ 压力/GPa FWHM(G) R1 R2 R3 GS-1 600 1.5 63.06 1.39 0.411 0.868 G-1 59.21 0.69 0.408 0.866 GS-2 900 1.5 32.80 2.77 0.75 0.842 G-2 38.19 2.48 0.698 0.761 GS-3 2 40.80 1.96 0.710 0.800 G-3 40.00 2.14 0.686 0.768 GS-4 1 200 1.5 31.44 0.93 0.598 0.639 G-4 21.07 0.58 0.461 0.503 GS-5 2 26.89 0.66 0.514 0.547 G-5 20.75 0.46 0.429 0.454
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