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页岩中气体的超临界等温吸附研究
引用本文:刘圣鑫,钟建华,马寅生,尹成明,刘成林,李宗星,李勇,刘选,毛毳,刘晓光.页岩中气体的超临界等温吸附研究[J].煤田地质与勘探,2015,43(3):45-50.
作者姓名:刘圣鑫  钟建华  马寅生  尹成明  刘成林  李宗星  李勇  刘选  毛毳  刘晓光
作者单位:1. 中国石油大学,山东青岛,266580
2. 中国石油大学,山东青岛 266580; 中科院广州地球化学研究所,广东广州 510640
3. 中国地质科学院地质力学研究所,北京 100081; 中国地质科学院页岩油气评价重点实验室,北京 100081
4. 中国地质科学院地质力学研究所,北京,100081
基金项目:国土资源大调查综合研究类项目
摘    要:页岩气等温吸附实验多为临界温度以上的吸附实验,其得到的吸附量为过剩吸附量。为了研究页岩气超临界等温吸附机理,运用重力法,在临界温度以上,分别进行了甲烷和二氧化碳在页岩中的高压等温吸附实验。在分析经典型吸附和超临界吸附区别的基础上,通过修改的超临界等温吸附模型(Langmuir方程和微孔充填(Dubinin Radushkevich,D-R))对实验数据进行了拟合。结果表明:简单的Langmuir方程可近似拟合甲烷吸附实验数据,但精度不高,且无法拟合二氧化碳的吸附数据;将吸附相密度作为可优化参数,修改的微孔充填模型和Langmuir模型能很好地拟合甲烷和二氧化碳的吸附数据,其中修改的微孔充填模型拟合效果最好,且回归得到的超临界甲烷吸附相密度同文献报道的一致,表明吸附气可能以微孔充填的形式存在。 

关 键 词:过剩吸附量    超临界吸附    Langmuir方程    Dubinin  Radushkevich方程
收稿时间:2014-07-12

Super-critical isothermal adsorption of gas in shale
LIU Shengxin,ZHONG Jianhua,MA Yinsheng,YIN Chengming,LIU Chenglin,LI Zongxing,LI Yong,LIU Xuan,MAO Cui,LIU Xiaoguang.Super-critical isothermal adsorption of gas in shale[J].Coal Geology & Exploration,2015,43(3):45-50.
Authors:LIU Shengxin  ZHONG Jianhua  MA Yinsheng  YIN Chengming  LIU Chenglin  LI Zongxing  LI Yong  LIU Xuan  MAO Cui  LIU Xiaoguang
Abstract:Shale gas isothermal adsorption experiments are mostly experiments above the critical temperature, the adsorption quantity obtained from the experiments is excess adsorption. In order to study super-critical isothermal adsorption mechanism of the shale gas, the weighting method was used in this study, the high pressure isothermal adsorption experiment have been made for methane and carbon dioxide in shale above the critical temperature. Based on the analysis of the typical adsorption and super-critical adsorption difference, through modified super-critical isothermal adsorption model (Langmuir equation and pore filling (Dubinin Radushkevich D-R)), experimental data were fitted. Study indicates that the simple Langmuir equation can approximately fit experimental data of methane adsorption, but the accuracy is not high, and can't fit carbon adsorption data. When the density of the adsorbed phase as parameter can be optimized, the modified microporous packing model and the Langmuir model can fit well adsorption data of methane and carbon dioxide, Fitting effect is the best with the modified microporous packing model, the adsorption phase density of super-critical methane is consistent with literature reports, suggesting that adsorbed gas may exists in the form of pore filling. 
Keywords:excess adsorption  super-critical adsorption  Langmuir equation  Dubinin Radushkevich (D-R) equation
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