镜煤逐级抽提超临界吸附响应及其机理
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摘要
采用有机溶剂抽提与超声振荡相结合的技术方法,选用CS2、苯、丙酮、和四氢呋喃做为抽提溶剂,对黔西—滇东5套不同煤级镜煤样品进行逐级抽提实验,并分析了原煤、抽提物和抽余物的物理性质、物质组成和物质结构,由此进一步开展了平衡水条件下镜煤及其抽余物的等温吸附/解吸实验,目的是研究镜煤逐级抽提超临界吸附响应及其作用机理。
通过研究,较为系统地探讨了不同煤级镜煤在有机溶剂逐级抽提作用下抽提率、抽提物族组成和抽余物“微晶”结构的演化特征,分析了它们随抽提级数和煤级的变化规律。初步揭示了逐级抽提过程中镜煤孔隙结构随煤级的演化规律,提出了液氮孔隙结构的自然分类方法,探讨了抽提前后孔隙及其连通性的演化特征,分析了原煤及其抽余物表面ζ电位的变化规律和影响因素。
同时,描述了超临界条件下煤及其抽余物吸附甲烷特征,发现传统的等温吸附模型能够拟合煤储层条件下甲烷吸附等温曲线。计算了它们在30℃条件下吸附甲烷的表面自由能、吸附势和特征吸附能,根据吸附势理论吸附特征曲线唯一性特征对不同温度条件下原煤及其抽余物吸附甲烷量及其表面自由能进行了预测。应用热力学原理阐释了原煤及其抽余物吸附甲烷能力的差异,分析了原煤及其抽余物吸附能力与地层环境条件和煤储层物性之间的关系。
There have been step-extraction-experiments on the 5 sets of coals collected from western Guizhou and Eastern Yunnan. The main experiment methods are traditional organic solvent extraction method and ultrasonic oscillations technology, in which CS2, benzene, acetone and tetrahydrofuran are used as extraction solvents. The physical characteristics, composition and structure of raw coal, extract and extracted residue are analyzed. The isothermal adsorption and desorption experiment of vitrain and extracted residue are completed under the equilibrium water condition in order to show the supercritical adsorption response of vitrain step-extraction and its mechanism.
The extraction yield, group component of extract and evolution characteristics of extracted residues micro-crystallite structure of different solvents for different rank coals are discussed, and the evolution with different extraction yield and coal rank are analyzed. The relationship between extraction yeild and pore structure of vitrain are preliminarily discosed. The natural classification of pore structure tested by fluid nitrogen are put forward. The pore and connectivity are dicussed from extraction start to finish. The change and effect factor ofζelectric potential of raw coals and their extracted residues are analyzed.
On the basis of these, the methane adsorption of raw coals and their extracted residues under supercritical condition are described. It is discovered that traditional isothermal adsorption equation can be used to fit methane isothermal adsorption curve under reservoir conditions. The free energy, adsorption potential and adsorption energy of theirs are calculated under 30℃. The volume of methane adsorped and free energy of raw coals and their extracted residues are predicted according to the characteristics that the adsorption character curve is single. The difference of adsorption ability of raw coals and their extracted residues are explained with thermodynamics theory. The relationship between raw coals and their extracted residues and strata setting and coal permeability are analyzed. There are 218 maps, 21 tables, and 130 references in this paper.
通过研究,较为系统地探讨了不同煤级镜煤在有机溶剂逐级抽提作用下抽提率、抽提物族组成和抽余物“微晶”结构的演化特征,分析了它们随抽提级数和煤级的变化规律。初步揭示了逐级抽提过程中镜煤孔隙结构随煤级的演化规律,提出了液氮孔隙结构的自然分类方法,探讨了抽提前后孔隙及其连通性的演化特征,分析了原煤及其抽余物表面ζ电位的变化规律和影响因素。
同时,描述了超临界条件下煤及其抽余物吸附甲烷特征,发现传统的等温吸附模型能够拟合煤储层条件下甲烷吸附等温曲线。计算了它们在30℃条件下吸附甲烷的表面自由能、吸附势和特征吸附能,根据吸附势理论吸附特征曲线唯一性特征对不同温度条件下原煤及其抽余物吸附甲烷量及其表面自由能进行了预测。应用热力学原理阐释了原煤及其抽余物吸附甲烷能力的差异,分析了原煤及其抽余物吸附能力与地层环境条件和煤储层物性之间的关系。
There have been step-extraction-experiments on the 5 sets of coals collected from western Guizhou and Eastern Yunnan. The main experiment methods are traditional organic solvent extraction method and ultrasonic oscillations technology, in which CS2, benzene, acetone and tetrahydrofuran are used as extraction solvents. The physical characteristics, composition and structure of raw coal, extract and extracted residue are analyzed. The isothermal adsorption and desorption experiment of vitrain and extracted residue are completed under the equilibrium water condition in order to show the supercritical adsorption response of vitrain step-extraction and its mechanism.
The extraction yield, group component of extract and evolution characteristics of extracted residues micro-crystallite structure of different solvents for different rank coals are discussed, and the evolution with different extraction yield and coal rank are analyzed. The relationship between extraction yeild and pore structure of vitrain are preliminarily discosed. The natural classification of pore structure tested by fluid nitrogen are put forward. The pore and connectivity are dicussed from extraction start to finish. The change and effect factor ofζelectric potential of raw coals and their extracted residues are analyzed.
On the basis of these, the methane adsorption of raw coals and their extracted residues under supercritical condition are described. It is discovered that traditional isothermal adsorption equation can be used to fit methane isothermal adsorption curve under reservoir conditions. The free energy, adsorption potential and adsorption energy of theirs are calculated under 30℃. The volume of methane adsorped and free energy of raw coals and their extracted residues are predicted according to the characteristics that the adsorption character curve is single. The difference of adsorption ability of raw coals and their extracted residues are explained with thermodynamics theory. The relationship between raw coals and their extracted residues and strata setting and coal permeability are analyzed. There are 218 maps, 21 tables, and 130 references in this paper.
引文
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