收稿日期: 2016-09-18
修回日期: 2016-12-31
网络出版日期: 2017-02-10
基金资助
国家科技重大专项“彭水地区常压页岩气勘探开发示范工程”（编号：2016ZX05061）；四川省教育厅重点项目（编号：16ZA0077）；
国家自然科学基金(编号：51674209)联合资助.
Effect of particle size on methane sorption capacity of shales
Received date: 2016-09-18
Revised date: 2016-12-31
Online published: 2017-02-10
为了研究粒径对页岩吸附甲烷的作用机理，分别制成粒径范围为1 700～3 350μm、850～1 000μm、180～250μm和106～131μm的4种样品，开展了高温高压等温吸附实验，根据Langmuir吸附理论并拟合实验结果获得了不同粒径下的吸附参数，分析基于粒径作用下的孔隙连通性、比表面积和粗糙度对吸附能力的影响，并探讨页岩吸附的粒径敏感性。结果表明：随页岩粒径减小，甲烷吸附量增加，Langmuir体积呈现出先急剧增大后减小再增大的趋势；粒径从1 700～3 350μm减小至180～250μm，中孔体积增加了72.46倍，直径小于5nm孔隙的孔容贡献率从57.94%增至80.36%，比表面积贡献率从74.34%增至92.85%。结论认为：①粒径随颗粒碾碎减小，改善了孔隙连通性，减少了吸附阻碍，优化了甲烷分子的传质吸附路径，提高了吸附速率；②粒径越小，被包裹的闭孔暴露出来，2～5nm的中孔数量增加，孔隙体积和比表面积得到了较大的提高，为甲烷分子提供了更大的吸附空间；③粒径减小增强了孔隙表面的粗糙程度，贡献了比表面积的同时也使得颗粒中的有机质和黏土矿物一定程度地暴露出来，增加了更多的高能吸附位。
康毅力，陈益滨，李相臣，游利军，陈明君 . 页岩粒径对甲烷吸附性能影响[J]. 天然气地球科学, 2017 , 28(2) : 272 -279 . DOI: 10.11764/j.issn.1672-1926.2017.01.006
In order to research the effect of particle size on adsorption properties of shale,shale samples rich in gases are collected from the Silurian Longmaxi in the Sichuan Basin and four types of coal specimens are made.The grain diameters of these specimens are within the ranges of 1 700-3 350μm,850-1000μm,180-250μm and 106-131μm,respectively.The isothermal adsorption experiments were conducted under the condition of high pressure and high temperature,which are aimed at carrying out further study on the effect of the pore connectivity,specific surface area and roughness on the methane adsorption and the effect of the sensitivity of particle size.Results showed that methane adsorption capacity were negatively related to the particle size,the value of Langmuir volume decreased after showing sharp increase and then increased with the particle size going down.Specific surface area increased from 6.09m2/g to 8.81m2/g,while the particle size from 1 700-3 350μm down to 180-250μm.Furthermore,both value of pore volume and the rate of contribution on specific surface area whose diameter is less than 5nm increased from 57.94% to 80.36% and from 74.34% to 92.85%,respectively.It could be safely drawn out the conclusion that,(1)The pore connectivity got to be better with the decrease of particle size,which is actually conducive to improve the adsorption ability motivated by removing obstacles and optimizing path for the mass-transfer efficiency and methane adsorption of shale.(2)The smaller the particle size,the higher the quantity of the close pore which is exposed by crushing and the mesopore whose diameter is between 2nm and 5nm,pore volume and specific surface area has been greatly improved,the methane molecules have greater adsorption space to produce more of the adsorption quantity.(3)Considering the fact that the extent of pore roughness performed negative relationship to particle size,more considerable pore,organic and clay minerals are exposed while the particle size decreases,which makes the specific surface area increase in large region,as a consequence,supplying more high energy absorption sites on the pore surface are actually helpful to improve the adsorption ability.
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