低吸附量煤岩和页岩等温吸附实验的负吸附原因
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摘要
低吸附样品等温吸附实验经常出现反"V"形先升后降"负吸附"现象,成为困扰相关实验的测试难题。为此,基于前人的研究成果,引入大样量重量法等温吸附仪,分析了大样量重量法的测试原理和操作流程,对比了体积法、磁悬浮重量法和大样量重量法3种方法的优缺点,进而选取大样量重量法等温吸附仪对内蒙古二连盆地吉尔噶朗图凹陷吉煤2井低煤阶煤岩和川南地区某井下志留统龙马溪组页岩样品进行了等温吸附实验,以期在消除系统累计误差影响之后,探究出现"负吸附"现象的根本原因。实验结果表明:(1)大样量重量法测试中未出现"负吸附"现象,其对低煤阶煤岩和页岩样品的测试结果可靠,拟合度高(R~2>0.99);(2)电子传感器误差(天平、压力和温度等采集器件)、系统累计误差、吸附相密度取值差异等不会导致吸附曲线形态的反转性变化;(3)样品缸空体积误差是引起"负吸附"的根本原因。结论认为,在等温吸附解释算法中增加体积校正参数,可以提高测试的准确性。
Negative adsorption of an inverse V type which rises first and then drops is often observed in the adsorption test of low adsorption samples. In view of this, a gravimetric isotherm rig with a large sample quantity was introduced. Its testing principles and operation processes were analyzed based on the previous research results. Then, the volumetric method, magnetic-levitation gravimetric method and large-sample-quantity gravimetric method were compared in terms of their advantages and disadvantages. Accordingly, this gravimetric isotherm rig with a large sample quantity was adopted to perform isotherm adsorption experiments on the low-rank coal samples taken from Well Jimei 2 in the Jiergalangtu sag, Erlian Basin, Inner Mongolia, and shale samples from the Lower Silurian Longmaxi Fm in the southern Sichuan Basin, so as to explore the essential reason for the "negative adsorption" after the effect of a systematical cumulative error is eliminated. And the following research results were obtained. First, when the large-sample-quantity gravimetric method is adopted, the phenomenon of "negative adsorption" doesn't occur and the test results of low-rank coal and shale samples are reliable with a high fitting degree(R~2> 0.99). Second, an electronic sensor error(e.g. electronic balance and P&T sensors), a system accumulative error and an adsorbed phase density error are not the factors leading to the reversal of negative adsorption curves. Third, the void volume error of a sample cell is the essential reason for the negative adsorption. In conclusion, the test accuracy can be improved by introducing the volume correction factor into the isotherm adsorption interpretation algorithm.
Negative adsorption of an inverse V type which rises first and then drops is often observed in the adsorption test of low adsorption samples. In view of this, a gravimetric isotherm rig with a large sample quantity was introduced. Its testing principles and operation processes were analyzed based on the previous research results. Then, the volumetric method, magnetic-levitation gravimetric method and large-sample-quantity gravimetric method were compared in terms of their advantages and disadvantages. Accordingly, this gravimetric isotherm rig with a large sample quantity was adopted to perform isotherm adsorption experiments on the low-rank coal samples taken from Well Jimei 2 in the Jiergalangtu sag, Erlian Basin, Inner Mongolia, and shale samples from the Lower Silurian Longmaxi Fm in the southern Sichuan Basin, so as to explore the essential reason for the "negative adsorption" after the effect of a systematical cumulative error is eliminated. And the following research results were obtained. First, when the large-sample-quantity gravimetric method is adopted, the phenomenon of "negative adsorption" doesn't occur and the test results of low-rank coal and shale samples are reliable with a high fitting degree(R~2> 0.99). Second, an electronic sensor error(e.g. electronic balance and P&T sensors), a system accumulative error and an adsorbed phase density error are not the factors leading to the reversal of negative adsorption curves. Third, the void volume error of a sample cell is the essential reason for the negative adsorption. In conclusion, the test accuracy can be improved by introducing the volume correction factor into the isotherm adsorption interpretation algorithm.
引文
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[14]聂海宽,张金川,马晓彬,边瑞康.页岩等温吸附气含量负吸附现象初探[J].地学前缘,2013,20(6):282-288.Nie Haikuan,Zhang Jinchuan,Ma Xiaobin&Bian Ruikang.A preliminary study of negative adsorption phenomena of shale adsorption gas content by isothermal adsorption[J].Earth Science Frontiers,2013,20(6):282-288.
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[16]刘圣鑫,钟建华,马寅生,尹成明,刘成林,李宗星,等.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.Liu Shengxin,Zhong Jianhua,Ma Yinsheng,Yin Chengming,Liu Chenglin,Li Zongxing,et al.Super-critical isothermal adsorption of gas in shale[J].Coal Geology&Exploration,2015,43(3):45-50.
[17]国家能源局.煤的多组分气体等温吸附实验方法NB/T10019—2015[S].北京:中国电力出版社,2015.National Energy Administration.Experimental method of multicomponent gas isothermal adsorption on coal NB/T 10019-2015[S].Beijing:China Electric Power Press,2015.
[18]Sudibandriyo M,Pan Zhejun,Fitzgerald JE,Robinson RL&Gasem KAM.Adsorption of methane,nitrogen,carbon dioxide,and their binary mixtures on dry activated carbon at 318.2 K and pressures up to 13.6 MPa[J].Langmuir,2003,19(13):5323-5331.
[19]Mavor MJ,Hartman C&Pratt TJ.Uncertainty in sorption isotherm measurements[C]//2004 International Coalbed Methane Symposium,May 2004,Tuscaloosa:University of Alabama.
[20]Haydel JJ&Kobayashi R.Adsorption equilibria in the methane-propane-silica system at high pressures[J].Industrial and Engineering Chemistry Fundamentals,1967,6(4):546-554.
[2]朱庆忠,左银卿,杨延辉.如何破解我国煤层气开发的技术难题——以沁水盆地南部煤层气藏为例[J].天然气工业,2015,35(2):106-109.Zhu Qingzhong,Zuo Yinqing&Yang Yanhui.How to solve the technical problems in CBM development:A case study of a CMB gas reservoir in the southern Qinshui Basin[J].Natural Gas Industry,2015,35(2):106-109.
[3]邹才能,董大忠,王玉满,李新景,黄金亮,王淑芳,等.中国页岩气特征、挑战及前景(二)[J].石油勘探与开发,2016,43(2):166-178.Zou Caineng,Dong Dazhong,Wang Yuman,Li Xinjing,Huang Jinliang,Wang Shufang,et al.Shale gas in China:Characteristics,challenges and prospects(II)[J].Petroleum Exploration and Development,2016,43(2):166-178.
[4]陈康,张金川,唐玄.湘鄂西下志留统龙马溪组页岩含气性测井评价[J].特种油气藏,2016,23(1):16-20.Chen Kang,Zhang Jinchuan&Tang Xuan.Gas content logging evaluation of Lower Silurian Longmaxi Shale in Western Hunan-Hubei[J].Special Oil&Gas Reservoirs,2016,23(1):16-20.
[5]刘洪林,王红岩.中国南方海相页岩吸附特征及其影响因素[J].天然气工业,2012,32(9):5-9.Liu Honglin&Wang Hongyan.Absorptivity and influential factors of marine shales in South China[J].Natural Gas Industry,2012,32(9):5-9.
[6]俞凌杰,范明,陈红宇,刘伟新,张文涛,徐二社.富有机质页岩高温高压重量法等温吸附实验[J].石油学报,2015,36(5):557-563.Yu Lingjie,Fan Ming,Chen Hongyu,Liu Weixin,Zhang Wentao&Xu Ershe.Isothermal adsorption experiment of organic-rich shale under high temperature and pressure using gravimetric method[J].Acta Petrolei Sinica,2015,36(5):557-563.
[7]马行陟,柳少波,姜林,田华,郝加庆.页岩吸附气含量测定的影响因素定量分析[J].天然气地球科学,2016,27(3):488-493.Ma Xingzhi,Liu Shaobo,Jiang Lin,Tian Hua&Hao Jiaqing.Quantitative analysis on affecting factors of gas adsorption capacity measurement on the shale[J].Natural Gas Geoscience,2016,27(3):488-493.
[8]端祥刚,胡志明,高树生,沈瑞,刘华勋,常进,等.页岩高压等温吸附曲线及气井生产动态特征实验[J].石油勘探与开发,2018,45(1):119-127.Duan Xianggang,Hu Zhiming,Gao Shusheng,Shen Rui,Liu Huaxun,Chang Jin,et al.Shale high pressure isothermal adsorption curve and the production dynamic experiments of gas well[J].Petroleum Exploration and Development,2018,45(1):119-127.
[9]熊伟,郭为,刘洪林,高树生,胡志明,杨发荣.页岩的储层特征以及等温吸附特征[J].天然气工业,2012,32(1):113-116.Xiong Wei,Guo Wei,Liu Honglin,Gao Shusheng,Hu Zhiming&Yang Farong.Shale reservoir characteristics and isothermal adsorption properties[J].Natural Gas Industry,2012,32(1):113-116.
[10]周尚文,王红岩,薛华庆,郭伟,卢斌.页岩过剩吸附量与绝对吸附量的差异及页岩气储量计算新方法[J].天然气工业,2016,36(11):12-20.Zhou Shangwen,Wang Hongyan,Xue Huaqing,Guo Wei&Lu Bin.Difference between excess and absolute adsorption capacity of shale and a new shale gas reserve calculation method[J].Natural Gas Industry,2016,36(11):12-20.
[11]张庆玲,曹利戈.煤的等温吸附测试中数据处理问题研究[J].煤炭学报,2003,28(2):131-135.Zhang Qingling&Cao Lige.Study of data processing in coal sorption isotherm testing[J].Journal of China Coal Society,2003,28(2):131-135.
[12]张庆玲,崔永君,曹利戈.煤的等温吸附实验中各因素影响分析[J].煤田地质与勘探,2004,32(2):16-19.Zhang Qingling,Cui Yongjun&Cao Lige.Analysis on different factors affecting coal isothermal adsorption test[J].Coal Geology&Exploration,2004,32(2):16-19.
[13]林腊梅,张金川,韩双彪,朱亮亮.泥页岩储层等温吸附测试异常探讨[J].油气地质与采收率,2012,19(6):30-32.Lin Lamei,Zhang Jinchuan,Han Shuangbiao&Zhu Liangliang.Study on abnormal curves of isothermal adsorption of shale[J].Petroleum Geology and Recovery Efficiency,2012,19(6):30-32.
[14]聂海宽,张金川,马晓彬,边瑞康.页岩等温吸附气含量负吸附现象初探[J].地学前缘,2013,20(6):282-288.Nie Haikuan,Zhang Jinchuan,Ma Xiaobin&Bian Ruikang.A preliminary study of negative adsorption phenomena of shale adsorption gas content by isothermal adsorption[J].Earth Science Frontiers,2013,20(6):282-288.
[15]何斌,宁正福,杨峰,赵天逸.页岩等温吸附实验及实验误差分析[J].煤炭学报,2015,40(增刊1):177-184.He Bin,Ning Zhengfu,Yang Feng&Zhao Tianyi.Shale isothermal adsorption experiment and experimental error analysis[J].Journal of China Coal Society,2015,40(S1):177-184.
[16]刘圣鑫,钟建华,马寅生,尹成明,刘成林,李宗星,等.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.Liu Shengxin,Zhong Jianhua,Ma Yinsheng,Yin Chengming,Liu Chenglin,Li Zongxing,et al.Super-critical isothermal adsorption of gas in shale[J].Coal Geology&Exploration,2015,43(3):45-50.
[17]国家能源局.煤的多组分气体等温吸附实验方法NB/T10019—2015[S].北京:中国电力出版社,2015.National Energy Administration.Experimental method of multicomponent gas isothermal adsorption on coal NB/T 10019-2015[S].Beijing:China Electric Power Press,2015.
[18]Sudibandriyo M,Pan Zhejun,Fitzgerald JE,Robinson RL&Gasem KAM.Adsorption of methane,nitrogen,carbon dioxide,and their binary mixtures on dry activated carbon at 318.2 K and pressures up to 13.6 MPa[J].Langmuir,2003,19(13):5323-5331.
[19]Mavor MJ,Hartman C&Pratt TJ.Uncertainty in sorption isotherm measurements[C]//2004 International Coalbed Methane Symposium,May 2004,Tuscaloosa:University of Alabama.
[20]Haydel JJ&Kobayashi R.Adsorption equilibria in the methane-propane-silica system at high pressures[J].Industrial and Engineering Chemistry Fundamentals,1967,6(4):546-554.