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煤的纳米孔隙特征及煤中封闭孔的定量分析

Nanopore Characteristics of Coal and Quantitative Analysis of Closed Holes in Coal.

作者信息

Li Xiangchun, Zhang Fan, Li Zhongbei, Chen Xiaolong, Zhang Qi, Nie Baisheng, Yang Tao

机构信息

School of Emergency Management and Safety Engineering, China University of Mining & Technology, Beijing 100083, China.

State Key Laboratory. of Coal Resources and Safe Mining, Beijing 100083, China.

出版信息

ACS Omega. 2020 Sep 17;5(38):24639-24653. doi: 10.1021/acsomega.0c03217. eCollection 2020 Sep 29.

Abstract

Methane gas is mainly present in coal in two forms: free and adsorbed. There are a large number of closed pores inside the coal, which makes it difficult to measure the gas content of the coal. Therefore, studying the nanoscale closed pores of coal is of great importance for gas control. To study the pore structure characteristics of coal with different deformation degrees and to analyze the volume fraction of closed pores in coal, various coal samples were analyzed by the low-temperature liquid nitrogen adsorption method (LT-NGA), the carbon dioxide adsorption method, and small-angle X-ray scattering (SAXS). The variation of parameters such as the pore size, pore volume, specific surface area, and degree of metamorphism was compared by using different methods to obtain the proportion of the closed pore volume of different coal samples. The results show that with the increase of the degree of coal metamorphism, the total pore volume and specific surface area of coal samples show a decreasing trend first and then an increasing trend, while the average pore diameter of coal samples gradually increases first and then decreases sharply. When the degree of deterioration of coal is low (volatile content > 20%), the closed pores of coal account for more than 48% of the open pores. When the degree of deterioration of coal samples is relatively high (volatile content <20%), the proportion of large pores in coal bodies decreased from 59.47 to 29.07%, and the proportion of pores in mesopores decreased from 12.15 to 11.09% and finally increased to 11.65%, and the proportion of micropore diameter increased from 28.38 to 59.28%. The volume fraction of the coal sample measured by the SAXS experiment shows that when the coal quality is high, the volume of the mesopores is large, which is consistent with the results of the low-temperature liquid nitrogen and CO adsorption experiments. Judging from the number of holes, the number of closed holes is 1 to 3 orders of magnitude greater than the number of open holes, and the number of closed holes of coal samples accounts for more than 94% of the total number of holes. It shows that the number of closed holes in the coal is far greater than the number of open holes, so the gas in the coal is mainly concentrated in the closed holes, and the formation of closed pores is partly because of the collapse of the internal structure and partly because of the volatilization of unstable substances. The research combined with LT-NGA, the carbon dioxide adsorption method, and SAXS test methods can better analyze the number of closed pores of coal and characterize the nanopore fracture structure of coal. The novelties of this article are that this is a quantitative analysis performed using a scientific method of SAXS. The findings of this study can lead to a better understanding of the coal and gas outburst mechanism and the existence of gas to adopt better prevention measures.

摘要

甲烷气体在煤中主要以两种形式存在

游离态和吸附态。煤内部存在大量封闭孔隙,这使得准确测量煤的瓦斯含量变得困难。因此,研究煤的纳米级封闭孔隙对于瓦斯防治具有重要意义。为了研究不同变形程度煤的孔隙结构特征,并分析煤中封闭孔隙的体积分数,采用低温液氮吸附法(LT - NGA)、二氧化碳吸附法和小角X射线散射(SAXS)对各种煤样进行了分析。通过不同方法比较孔径、孔体积、比表面积和变质程度等参数的变化,以获取不同煤样封闭孔体积的比例。结果表明,随着煤变质程度的增加,煤样的总孔体积和比表面积先呈下降趋势,然后呈上升趋势,而煤样的平均孔径先逐渐增大,然后急剧减小。当煤的变质程度较低(挥发分含量>20%)时,煤的封闭孔占开孔的比例超过48%。当煤样的变质程度相对较高(挥发分含量<20%)时,煤体中大孔的比例从59.47%降至29.07%,中孔的比例从12.15%降至11.09%,最终增至11.65%,微孔直径的比例从28.38%增至59.28%。SAXS实验测得的煤样体积分数表明,煤质较好时,中孔体积较大,这与低温液氮和CO吸附实验结果一致。从孔的数量来看,封闭孔的数量比开孔多1至3个数量级,煤样的封闭孔数量占总孔数量的比例超过94%。这表明煤中封闭孔的数量远大于开孔数量,因此煤中的瓦斯主要集中在封闭孔中,封闭孔的形成部分是由于内部结构的坍塌,部分是由于不稳定物质的挥发。结合LT - NGA、二氧化碳吸附法和SAXS测试方法的研究能够更好地分析煤中封闭孔的数量,并表征煤的纳米孔隙裂隙结构。本文的新颖之处在于这是一种采用SAXS科学方法进行的定量分析。本研究结果有助于更好地理解煤与瓦斯突出机理以及瓦斯赋存情况,从而采取更好的防治措施。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f0ba/7528341/b7e20f6d1f95/ao0c03217_0002.jpg

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