神东煤惰质组结构特征及其与CH_4、CO_2和H_2O相互作用的分子模拟
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摘要
煤层气的能源效应使其吸附的研究成为热点之一,但是绝大多数研究都是采用传统的实验方法,很难从微观上认识煤对气体及水分的吸附机理。本文结合实验和计算机理论模拟两种方法,构建了神东煤惰质组(SI)大分子结构模型,系统研究了SI对CH4、CO2和H2O的吸附,以从分子水平上认识煤对气体及水分吸附的机理。
本文的研究方法及其主要结论如下:
1.基于核磁共振(13C NMR)分析所得煤结构参数构建了SI平面模型,通过化学位移计算软件进行修改,得到了实验谱图与计算谱图相一致的平面构型,并应用分子力学和分子动力学方法进行空间构型优化后,得出SI的密度是1.14 g/cm3,与实验数据也基本一致,证明了SI空间构型是合理的。
2.应用蒙特卡洛(GCMC)方法模拟了SI对CH4、CO2和H2O单组分的饱和吸附,得出如下结论:
1)在相同条件下,SI对单组分CH4、CO2和H2O的饱和吸附量大小是H2O>CO2>CH4。
2)通过观察SI对单组分CH4、CO2和H2O的饱和吸附构型发现,吸附质分子都是优先吸附于SI大分子边缘,而后才吸附于孔隙内。吸附质分子局部集中吸附,如甲烷两两集中吸附,其空间排列与乙烷的空间构型类似;二氧化碳分子出现两两交叉的排列形式。
3.应用分子动力学方法,在温度为298.15 K,压力为0.001 GPa的条件下,模拟了SI对单组分CH4、CO2和H2O的吸附,得到以下主要结论:
1)在同温同压下,SI对单组分CH4、CO2和H2O的吸附量大小是:CH4 2)观察各单组分的饱和吸附构型可以发现,CH4在吸附剂中的吸附排列是呈现两两交叉,类似于乙烷的分子构型。CO2分子在SI中的吸附排列呈平行或交叉,甚至垂直的特点。H2O分子更多的呈现平行排列。相比较而言,CH4和H2O分子在SI中的吸附排列比较单一,CH4呈交叉排列,H2O分子呈平行排列,而CO2分子的排列比较杂乱,既有平行的、交叉的,又有垂直排列的。这与应用蒙特卡洛(GCMC)方法得到的结论是相一致的。
4.用巨正则蒙特卡洛(GCMC)方法模拟了SI对CH4、CO2和H2O单组分的等温吸附,得出如下结论:
1)相同温度压力下,SI对单组分CH4、CO2和H2O的模拟等温吸附量大小是:H2O>CO2>CH4。
2)在相同压力条件下,温度与吸附量成负相关关系,高温不利于煤对单组分CO2、CH4和H2O的吸附。
3)压力对单组分CO2、CH4和H2O吸附的影响有一个临界值,这一临界值大约为8 MPa。当压力小于8 MPa时,随着压力的增大,各单组分的吸附量跟着增加,当压力大于8 MPa时,随着压力的增大,各单组分的吸附量不再增加,而有减小的趋势。而且,在相同温度压力条件下,压力的变化对H2O吸附量的影响比CO2和CH4大。
4)通过对等量吸附热的分析,得出SI对单组分CO2、CH4和H2O的吸附属于物理吸附。
5.应用蒙特卡洛(GCMC)方法模拟了SI对二元混和体系CH4/CO2、CH4/H2O和CO2/H2O等温吸附,得出如下结论:
1)通过吸附选择性系数的判断,得出吸附质中竞争吸附的优势大小是H2O>CO2>CH4。
2)在相同温度压力条件下,吸附量的大小顺序是CH4CO2>CH4。
3)压力的变化对竞争吸附中处于弱势的吸附质的吸附量影响不大,而对竞争中处于优势的吸附质的吸附量影响很大,呈正相关关系。
6.应用蒙特卡洛(GCMC)方法模拟了SI对三元体系CH4/CO2/H2O的等温吸附,得出如下结论:
1)在相同压力条件下,吸附量大小顺序是CH4 2)压力的变化对竞争吸附中处于弱势的吸附质的吸附量影响不大,即对CO2和CH4吸附量的影响不大,而对竞争中处于优势的吸附质的吸附量影响很大,呈正相关关系,这一结论与二元组分等温吸附所到的结论相一致。通过对三元组分CH4/CO2/H2O竞争吸附的研究,发现压力对竞争吸附中处于优势吸附质的吸附量影响有一个临界值,大约为6 MPa,当压力小于6 MPa时,随着压力的增大,吸附量增加的很快,当压力大于6 MPa时,随着压力的增大,吸附量的增加相对较慢。
The study of adsorption of coalbed methane by energy efficiency is a hot spots, but most experimental methods are traditional ideas, and they are difficult to recognize the adsorption mechanism of gases on coal from microscopic scale. In this paper, experimental methods were combined with models to build macromolecular structure model of Shendong inertinite (SI), and analyse the adsotption of the CH4,CO2,and H2O, then the adsorption mechanism in molecular level could be known. The following results were obtained:
1.The spatial crossing macromolecular structure model of SI was obtained after the optimization of the plain model by Molecular Mechanics and Molecular Dynamic, which based on the structure parameters from the analysis of the experiment of 13C NMR. And the consistence of simulated IR spectrum and density (1.14 g/cm3) with the experimental results showed that SI was reasonable.
2.The simulation of saturated adsorption of pure CH4, CO2, H2O on SI by Grand Canonical Monte Carlo (GCMC), the following results were obtained:
1) In the same condition,the size order of saturated adsorption was: H2O> CO2> CH4.
2) Through the simulation of saturated adsorption of pure CH4, CO2, H2O on SI, it is found that adsorbate molecules were first adsorbed on the edge of SI molecules, and after that in the pores.Adsorbate molecules were both sides of the molecular chain in the SI, and some of the local concentration of adsorbate molecules, such as the adsorption of methane, and the spatial arrangement was similar to the ethane; carbon dioxide molecule was arranged in Cross-form.
3.Through the simulation of adsorption of pure CH4, CO2, H2O on SI applying the molecular dynamics when the tempreture is 298.15 K and the pressure is 0.001 GPa, the following results were obtained:
1) The size order of simulated adsorption isotherm for pure CH4, CO2 and H2O in the same tempreture and fugacity was: CH4 2) From the single-component adsorption configuration, we can find that, similar to ethane, CH4 in the arrangement is in Cross-form,.and the CO2 molecules in the adsorption arranged was in parallel or cross, or even vertical, more H2O molecule was parallel. In comparison, CH4 and H2O molecule adsorption in relatively simple arrangement, while the CO2 molecules are more messy, which and the GCMC was consistent.
4. The simulation of the adsorption isotherm of pure CH4, CO2, H2O by Grand Canonical Monte Carlo (GCMC) on SI, the following results were obtained:
1) The size order of simulated adsorption isotherm for pure CH4, CO2 and H2O in the same tempreture and fugacity was: H2O> CO2> CH4.
2) The tempreture and the adsorption was linear negative in the same fugacity, and it was difficult that the adsorption of CH4, CO2 and H2O on coal in the high-temperature region.
3) A threshold about 8 MPa was appeared while the single-component CO2, CH4 and H2O adsorption when the pressure was less than 8 MPa, as the pressure increases, the single-component adsorption was increased, but when the pressure was greater than 8 MPa, with pressure increasing, the adsorption was decrease moreover, at the same temperature and pressure conditions, the impact on H2O adsorption by pressure was greater than CO2 and CH4 .
4) Through the analysis of isosteric heat ,the adsorption of pure CH4, CO2 and H2O on SI was physical adsorption
5.Through the simulation of the adsorption isotherm of binary CH4/CO2, CH4/H2O and CO2/ H2O on SI, the following results were obtained:
1) The size order of advantage of sorbates in competitive adsorption was: H2O> CO2> CH4.
2) In the same tempreture and fugacity ,The size order of advantage of sorbates in competitive adsorption was: CH4 3) The change of pressure had great impact on the adsoption of the advantage sorbate in the competitive adsorption,they were linear positive, and the adsoption of the disadvantage sorbate had not this Phenomenon.
6.Through the simulation of the adsorption isotherm of Ternary CH4/CO2/H2O on SI, the following results were obtained:
1) The size order of simulated adsorption was CH4 2) The change on the pressure had a weak effect on the disadvantage sorbate, such as CO2 and CH4 ,while the competition dominant adsorbate have a great influence on the adsorption, this conclusion and binary component adsorption isotherms are consistent. Through the simulation of the adsorption isotherm of ternary CH4/CO2/H2O,it was found that the pressure on the competition dominant adsorbate had threshold of about 6 MPa,When the pressure was less than 6 MPa. As the pressure increases,the adsorption capacity increases rapidly,while the pressure was more than 6 MPa,the result was the opposite .
本文的研究方法及其主要结论如下:
1.基于核磁共振(13C NMR)分析所得煤结构参数构建了SI平面模型,通过化学位移计算软件进行修改,得到了实验谱图与计算谱图相一致的平面构型,并应用分子力学和分子动力学方法进行空间构型优化后,得出SI的密度是1.14 g/cm3,与实验数据也基本一致,证明了SI空间构型是合理的。
2.应用蒙特卡洛(GCMC)方法模拟了SI对CH4、CO2和H2O单组分的饱和吸附,得出如下结论:
1)在相同条件下,SI对单组分CH4、CO2和H2O的饱和吸附量大小是H2O>CO2>CH4。
2)通过观察SI对单组分CH4、CO2和H2O的饱和吸附构型发现,吸附质分子都是优先吸附于SI大分子边缘,而后才吸附于孔隙内。吸附质分子局部集中吸附,如甲烷两两集中吸附,其空间排列与乙烷的空间构型类似;二氧化碳分子出现两两交叉的排列形式。
3.应用分子动力学方法,在温度为298.15 K,压力为0.001 GPa的条件下,模拟了SI对单组分CH4、CO2和H2O的吸附,得到以下主要结论:
1)在同温同压下,SI对单组分CH4、CO2和H2O的吸附量大小是:CH4
4.用巨正则蒙特卡洛(GCMC)方法模拟了SI对CH4、CO2和H2O单组分的等温吸附,得出如下结论:
1)相同温度压力下,SI对单组分CH4、CO2和H2O的模拟等温吸附量大小是:H2O>CO2>CH4。
2)在相同压力条件下,温度与吸附量成负相关关系,高温不利于煤对单组分CO2、CH4和H2O的吸附。
3)压力对单组分CO2、CH4和H2O吸附的影响有一个临界值,这一临界值大约为8 MPa。当压力小于8 MPa时,随着压力的增大,各单组分的吸附量跟着增加,当压力大于8 MPa时,随着压力的增大,各单组分的吸附量不再增加,而有减小的趋势。而且,在相同温度压力条件下,压力的变化对H2O吸附量的影响比CO2和CH4大。
4)通过对等量吸附热的分析,得出SI对单组分CO2、CH4和H2O的吸附属于物理吸附。
5.应用蒙特卡洛(GCMC)方法模拟了SI对二元混和体系CH4/CO2、CH4/H2O和CO2/H2O等温吸附,得出如下结论:
1)通过吸附选择性系数的判断,得出吸附质中竞争吸附的优势大小是H2O>CO2>CH4。
2)在相同温度压力条件下,吸附量的大小顺序是CH4
3)压力的变化对竞争吸附中处于弱势的吸附质的吸附量影响不大,而对竞争中处于优势的吸附质的吸附量影响很大,呈正相关关系。
6.应用蒙特卡洛(GCMC)方法模拟了SI对三元体系CH4/CO2/H2O的等温吸附,得出如下结论:
1)在相同压力条件下,吸附量大小顺序是CH4
The study of adsorption of coalbed methane by energy efficiency is a hot spots, but most experimental methods are traditional ideas, and they are difficult to recognize the adsorption mechanism of gases on coal from microscopic scale. In this paper, experimental methods were combined with models to build macromolecular structure model of Shendong inertinite (SI), and analyse the adsotption of the CH4,CO2,and H2O, then the adsorption mechanism in molecular level could be known. The following results were obtained:
1.The spatial crossing macromolecular structure model of SI was obtained after the optimization of the plain model by Molecular Mechanics and Molecular Dynamic, which based on the structure parameters from the analysis of the experiment of 13C NMR. And the consistence of simulated IR spectrum and density (1.14 g/cm3) with the experimental results showed that SI was reasonable.
2.The simulation of saturated adsorption of pure CH4, CO2, H2O on SI by Grand Canonical Monte Carlo (GCMC), the following results were obtained:
1) In the same condition,the size order of saturated adsorption was: H2O> CO2> CH4.
2) Through the simulation of saturated adsorption of pure CH4, CO2, H2O on SI, it is found that adsorbate molecules were first adsorbed on the edge of SI molecules, and after that in the pores.Adsorbate molecules were both sides of the molecular chain in the SI, and some of the local concentration of adsorbate molecules, such as the adsorption of methane, and the spatial arrangement was similar to the ethane; carbon dioxide molecule was arranged in Cross-form.
3.Through the simulation of adsorption of pure CH4, CO2, H2O on SI applying the molecular dynamics when the tempreture is 298.15 K and the pressure is 0.001 GPa, the following results were obtained:
1) The size order of simulated adsorption isotherm for pure CH4, CO2 and H2O in the same tempreture and fugacity was: CH4
4. The simulation of the adsorption isotherm of pure CH4, CO2, H2O by Grand Canonical Monte Carlo (GCMC) on SI, the following results were obtained:
1) The size order of simulated adsorption isotherm for pure CH4, CO2 and H2O in the same tempreture and fugacity was: H2O> CO2> CH4.
2) The tempreture and the adsorption was linear negative in the same fugacity, and it was difficult that the adsorption of CH4, CO2 and H2O on coal in the high-temperature region.
3) A threshold about 8 MPa was appeared while the single-component CO2, CH4 and H2O adsorption when the pressure was less than 8 MPa, as the pressure increases, the single-component adsorption was increased, but when the pressure was greater than 8 MPa, with pressure increasing, the adsorption was decrease moreover, at the same temperature and pressure conditions, the impact on H2O adsorption by pressure was greater than CO2 and CH4 .
4) Through the analysis of isosteric heat ,the adsorption of pure CH4, CO2 and H2O on SI was physical adsorption
5.Through the simulation of the adsorption isotherm of binary CH4/CO2, CH4/H2O and CO2/ H2O on SI, the following results were obtained:
1) The size order of advantage of sorbates in competitive adsorption was: H2O> CO2> CH4.
2) In the same tempreture and fugacity ,The size order of advantage of sorbates in competitive adsorption was: CH4
6.Through the simulation of the adsorption isotherm of Ternary CH4/CO2/H2O on SI, the following results were obtained:
1) The size order of simulated adsorption was CH4
引文
[1] Van Krevelen D.W,‘Coal’,Amsterdam,Elservier,1981.
[2]曾凡桂,张通,王三跃,谢克昌.煤超分子结构的概念及其研究途径与方法.煤炭学报,2005,30(1):85-89
[3] Carlson G A.Granoff B.Am Chem Soc Div Fuel Chem Preprints,1989,34(3):38.
[4]沈家骢等.超分子层状结构—组装与功能.北京:科学出版社,2004
[5]张希,沈家骢.超分子科学:认识物质世界的新层面.科学通报,2003,14:1477.
[6]谢克昌,煤的结构与反应性[M].北京:科学出版社,2002,115.
[7]陈昌国.煤的物理化学结构和和吸附(解吸)甲烷机理的研究[D].博士学位论文.重庆:重庆大学,1995.
[8] Hirsch P B.X-ray scattering from coals [J].Proceedings of the Royal Society (London),A226(1954):143-169
[9] T Green,J Kovac,D Brenner,etc.Coal Structure. ed. by R.A. Meyers [M].Academic Press, New York:1982,199.
[10] Given P H,Marzec A,Barton W A,.etc.The concept of a mobile or molecular phase within the macromolecular network of coal: A debate[J].Fuel,1986,65:155-163.
[11] Nishioka M.The associated molecular nature of bituminous coal[J].Fuel,1992,71:941-948.
[12] Van Krevelen D W,Chermin H A.Chemical Structure and Properties of Coal[J].Fuel,1954,33:79-87.
[13] Given P H.The distribution of hydroxyl in coal and its relation to coal structure[J].Fuel,1960,39:147-158.
[14] Bodlily D M,Lee S H D,Wiser W H.Devolatilization of coal and zinc chloride: impregnated coal in a nitric oxide atmosphere[J].American Chemical Society: Division of Fuel Chemistry,1975,Jan:7-11.
[15] Shinn J H.Towards an understanding of the coal structure[J].Fue,1984,63:483-497.
[16] Faulon J L,Hatcher P G,Carlson G A,etc.A computer-aided molecular model for high volatile bituminous coal[J].Fuel Processing Technology.,1993,34:277-293.
[17] Oberlin A.High resolution studies of carbonization and graphitization [J].Chemistry and Physics of Carbon,1992,22:1-14.
[18]Grigoriew H,Cichowska G.Spatial coal structure models[J].Journal of Apply Crystallography,1990,23:209-210.
[19]陈昌国,辜敏,鲜学福,煤的颜色和结构与稠环芳族化合物的电子光谱规律[J].煤炭转化,1999,22(1),1-4.
[20]王继仁,金智新,邓存宝.煤自然量子化学理论.北京:科学出版社,2007,59.
[21]孙茂远,黄盛初.煤层气开发利用手册[M].北京:煤炭工业出版社,1998.
[22]李宝芳.煤层气及生储原理略述[J].中国煤田地质,1996,8(1):89-94.
[23]陈昌国,鲜晓红,张代钧等.微孔填充理论研究无烟煤和炭对甲烷的吸附特性.重庆大学学报,1998,21(2):75-79
[24] Moffat.D H, Weale K E. Sorp tion by coal of methane at high pressure[ J ]. Fuel, 1955 (34) : 417 - 428.
[25] Yang R T, Saunders J T. Adsorp tion of gases on coals and heat - treated coals at elevated temperature and pressure [ J ]. Fuel, 1985 (64) : 314 - 327.
[26] Sing K. S. W. , Everet.D. H. , Haul R. A. W. et al. Reporting physisorp tion data for gas/ solid systems with special reference to the determination of surface area and porosity[ J ]. Puer & App l. Chem, 1985, 57 (4) : 603.
[27]刘常洪,杨思敬.煤低温氮吸附等温线的试验研究[ J ].煤矿安全, 1992 (7) : 19 - 21.
[28] Kraemer E. O. . A Treatise on Physical Chemistry [M ].New York: D. van Nostrand Co. , 1931: 166.
[29] DonohueM. D. , Aranovich G. L. . Adsorp tion Hysteresis in Porous Solids [ J ]. Journal of Colloid And Interface Science, 1998, 205 (1) : 121.
[30] Sangwichien C., Aranovich G L., Donohue M. D. Surface tension gradient driven sp reading of trisiloxane surfactant solution on hydrophobic solid [ J ]. Colloids and Surface, 2002, 206 (31) : 1-3.
[31] Xiaojun Cui, R. Marc Bustin, Gregory Dipp le. Selective transport of CO2 , CH4 , and N2 in coals: insights from modeling of experimental gas adsorp tion data [ J ]. Fuel,2004 (83) : 293 - 303.
[32] Krooss B M, Bergen Fvan, Gensterblum Y. , et al. High pressure methane and carbon dioxide adsorp tion on dry and moisture - equilibrated Pennsylvanian coals[ J ].International Journal of Coal Geology, 2002, 51 ( 2) : 69-92.
[33]唐书恒.晋城地区煤储层特征及多元气体的吸附—解吸特征[D ].徐州:中国矿业大学, 2001.
[34] Arri L. E, Yee D. , Morgan W. D. Modeling coal bed methane p roduction with binary gas sorp tion [ C ]. Caspar Wyoming: SPE RockyMountain RegionalMeeting,1992.
[35] Hall F. E. , Zhou Chunhe Gasem K. A. M. , and Robinson, J r. , R. L. . Adsorp tion of PureMethane, Nitrogen, and Carbon Dioxide and their BinaryMixtures on Wet Fruitland Coal, SPE Paper 29194 [ C ].Charleston, WestVirginia: the 1994 Eastern Regional Conference & Exhibition, 1994.
[36] Harpdani S, ParitiU M. Study of coal sorp tion isothermsuing a multicomponent gasmixture[C ]. the 1993 Inter2national CoalbedMethane Symposium. The University of Alabama /Tuscloosa, 1993.
[37]钟玲文.煤的吸附性能及影响因素.地球科学—中国地质大学学报,2004,29(3):327-333.
[38]陈皓侃,李保庆,李文.分子力学和分子动力学方法研究不同变质程度烟煤的分子结构[J].燃料化学学报,2000,28(5):459-462.
[39] Nakamura K. CAMD Study of Coal Model Molecules. 2. Density Simulation for Fou Japanese Coals.Energy & Fuels,1993(7):469-472.
[40] Takanohashi T, Kawashima H.Constuction of a Model Strycture for Upper Freepot Coal Using 13C NMR Chemical Shift Calculations. Energy & Fuels,2002(16):379-387.
[41] Hatcher P G,Faulon J L,Wenzel K A,etc.A structural model for ligninderived vitrinite from high-volatile bituminous coal (coalified wood)[J].Energy&Fuels,1992,6:813-820.
[42] Faulon J L,Carlson G A,Hatcher P G, etc.Statistical models for bituminous coal: A three-dimensional evaluation of structural and physical properties based on computergenerated structures[J].Energy & Fuels,1993,7:1062-1072.
[43] Takanohashi T,Masashi.I,Kazuo.N.Simulation of interaction of coal associates with solvents using the molecular dynamics calculation.Energy & Fuels,1998,12:1168-1173.
[44]邓汉忠,王继仁,邓存宝.O2在—CH2—CH2OH基团上的化学吸附.煤炭转化,2007,30(4):29-33.
[45]王继仁,刘仲田,邓汉忠,邓存宝,张俭.煤表面对多个氧分子的多层吸附机理研究.计算机与应用化学,2008,25(3):281-284.
[46]傅爱萍,冯大诚,邓从豪.水在石墨(0001)面簇模型桥位上吸附的量子化学研究[J].高等学校化学学报,1998,19(5):792-795.
[47]降文萍,崔永君,张群,等.煤表面与CH4、CO2相互作用的量子化学研究[J].煤炭学报,2006,31(2):237-240.
[48]孙培德.煤与甲烷气体相互作用机理的研究[J].Coal,2000,9(l):18-2l.
[49]王宏,杨丽丽,李红,曹立刚.我国煤层气资源开发意义探究[J].辽宁大学学报,2008,35(1):85-88.
[50]张新民,庄军,张遂安主编.中国煤层气地质与资源评价[M].北京:科学出版社,2002.
[51]叶建平,秦勇,林大扬.中国煤层气资源[M ].徐州:中国矿业大学出版社,1999.
[52]张建博,王红岩.中国煤层气地质[M ].北京:地质出版社,2000:15-30.
[53]鲜学福.我国煤层气开采利用现状及其产业化展望[ J ].重庆大学学报.2000,23 (4):23-26.
[54]冯文光.中国应尽快实现低渗煤层气藏工业化生产[ J ].天然气工业, 2001 (1):32-36.
[55]陈永武.中国煤层气产业形成和发展面临的机遇与挑战[ J ].天然气工业, 2000, 20 (4) : 126.
[56]马东民.煤层气吸附解吸机理研究[D].博士学位论文,西安:西安科技大学,2008.
[57] Reznik .A .A , Aingh P K, Foley. W.L. An analysis of the effect of CO2 injection on the recovery of in-situ methane f rom Bituminous coal : an experimental simulation [ J ] . SPE Journal , 1984 , 24 (5) : 521-528.
[58] Zuber M D. Production characteristics and reservoir analysis of coalbed methane reservoirs [ J ] . International Journal of Coal Geology , 1998 , 38 (122) : 27-45.
[59] Clarkson C R and Bustin R M. Binary gas adsorp tion /desorp tionisotherms: effect of moisture and coal conposition upon carbon dioxide selectivity over methane [ J ]. International Journal of Coal Geology,2000, 41 (4) : 241-272.
[60] Busch A, Gensterblum Y, Krooss B M, et al. Methane and carbon dioxide dsorp tion-diffusion experiments on coal: up scaling and modeling [ J ]. International Journal of Coal Geology, 2004, 41:151-168.
[61]高远文,姚艳斌,郭广山.注气提高煤层气采收率研究进展.资源与产业,2007,9(6):105-108.
[62]吴世跃,赵文.自然降压开采和注气开采煤层气的效果评价.中国矿业,2004,13(10):76-79.
[63]李希建,蔡立勇,常浩.注气驱替煤层气作用机理的探讨.矿业快报,2007,8:20-22.
[64]孙可明.煤层气注气开采多组分流体扩散模型数值模拟.辽宁工程技术大学学报,2005,24(3):305-308.
[65]谢振华,陈绍杰.水分及温度对煤吸附甲烷的影响.北京科技大学学报,2007,29(2):42-44.
[1]彭立才,韩德馨,邵文斌等.柴达木盆地北缘侏罗系烃源岩干酪根13C核磁共振研究[J].石油学报,2002,23(2):34-37.
[2] Trewhella M J,Poplett L J F,Grint A.Structure of Green River oil shale kerogen determcnation using solid state 13C-NMR spectroscopy[J].Fuel,1986,65:541-546.
[3]王丽,张蓬洲,郑敏.用固体核磁共振和电子能谱研究我国高硫煤的结构.燃料化学学报,1996,24(6):539-543.
[4]傅家谟,刘德汉,盛国英等.煤成烃地球化学[M].北京:科学出版社,1990,245.
[5] Kidena K,Tani Y,Murata S,etc.Quantitative elucidation of bridge bonds and side chains in brown coals[J].Fuel,2004,83:1697-1702.
[5] Kawashima H,Takanohashi T.Modification of model structures of upper freeport coal extracts using 13C NMR chemical shift calculations[J].Energy & Fuels,2001,15:591-598.
[6] Takanohashi T,Iino M,Nakamura K.Simulation of interaction of coal associates with solvents using the molecular dynamics calculation[J].Energy & Fuels,1998,12:1168-1173.
[7] Frenkel D,Smith B.分子模拟-从算法到应用,汪文川等译[M].北京:化学工业出版社,2002.
[8]谢克昌,煤的结构与反应性[M].北京:科学出版社,2002.
[1]陈昌国,魏锡文,鲜学福.用从头计算研究煤表面与甲烷分子相互作用.重庆大学学报(自然科学版),2000,23(3):77-83.
[2]陈文萍,崔永君,张群,李育辉.煤表面与CH4、CO2相互作用的量子化学研究.煤炭学报,2006,31(2):237-240.
[3]于洪观,范维唐,孙茂远,叶建平.高压下煤对CH4/CO2二元气体吸附等温线的研究.煤炭转化,2005,28(1):43-47.
[4]唐书恒,马彩霞,叶建平,等.注二氧化碳提高煤层甲烷采收率的实验模拟[J].中国矿业大学学报,2006,(35)5:607-612.
[1]张天军,许鸿杰,李树刚,任树鑫.温度对煤吸附性能的影响.煤炭学报,2009,34(6):802-805.
[2]崔永君,张群,张泓,等.不同煤级煤对CH4、N2和CO2单组分气体的吸附[J].天然气工业,2005,25(1):61-65.
[3]傅献彩,沈文霞,姚天扬.物理化学(下册)[M].北京:高等教育出版社,1993,950.
[4] Ruppel T C,Grein C T,Bienstock D.Adsorption of methane on dry coal at elevated pressure[J].Fuel,1974,53(3):152-162.
[5] Day S,Sakurovs R,Weir S.Supercritical gas sorption on moist coals [J].International Journal of Coal Geology,2008,74:203-214.
[6] Mahajan O P,Walker Jr. P L.Water adsorption on coals[J].Fuel,1971,50(3):308-317.
[7] Allardice D J,Evans D G.The-brown coal/water system: Part 2. Water sorption isotherms on bed-moist Yallourn brown coal[J].Fuel,1971,50(3):236-253.
[1] Clarkson C R,Bustin B M.Binary gas adsorption/desorption isothems: effect of moisture and coal composition upon carbon dioxide selectivity over methane[J].International Journal of Coal Geology,2000,42:241-271.
[2]唐书恒,汤达祯,杨起.二元气体等温吸附实验及其对煤层甲烷开发的意义[J].地球科学—中国地质大学学报,2004,29(2):219-223.
[3] Nodzeński A.Sorption and desorption of gases(CH4, CO2) on hard coal and active carbon at elevated pressures[J].Fuel,1998,77(11):1243-1246.
[4] Majewska Z,Ceglańrska-Stefaska G,Majewski S,etc.Binary gas adsorption/desorption isothems effect of moisture and coal composition upon carbon dioxide selectivity over methane[J].International Journal of Coal Geology,2009,77:90–102.
[5]降文萍,崔永君,钟玲文等.煤中水分对煤吸附甲烷影响机理的理论研究[J].天然气地球科学,2007,18(4):576-580.
[6]张庆玲,张群,崔永君,杨杰.煤对多组分气体吸附特征研究.天然气工业,2005,25(1):57-60
[2]曾凡桂,张通,王三跃,谢克昌.煤超分子结构的概念及其研究途径与方法.煤炭学报,2005,30(1):85-89
[3] Carlson G A.Granoff B.Am Chem Soc Div Fuel Chem Preprints,1989,34(3):38.
[4]沈家骢等.超分子层状结构—组装与功能.北京:科学出版社,2004
[5]张希,沈家骢.超分子科学:认识物质世界的新层面.科学通报,2003,14:1477.
[6]谢克昌,煤的结构与反应性[M].北京:科学出版社,2002,115.
[7]陈昌国.煤的物理化学结构和和吸附(解吸)甲烷机理的研究[D].博士学位论文.重庆:重庆大学,1995.
[8] Hirsch P B.X-ray scattering from coals [J].Proceedings of the Royal Society (London),A226(1954):143-169
[9] T Green,J Kovac,D Brenner,etc.Coal Structure. ed. by R.A. Meyers [M].Academic Press, New York:1982,199.
[10] Given P H,Marzec A,Barton W A,.etc.The concept of a mobile or molecular phase within the macromolecular network of coal: A debate[J].Fuel,1986,65:155-163.
[11] Nishioka M.The associated molecular nature of bituminous coal[J].Fuel,1992,71:941-948.
[12] Van Krevelen D W,Chermin H A.Chemical Structure and Properties of Coal[J].Fuel,1954,33:79-87.
[13] Given P H.The distribution of hydroxyl in coal and its relation to coal structure[J].Fuel,1960,39:147-158.
[14] Bodlily D M,Lee S H D,Wiser W H.Devolatilization of coal and zinc chloride: impregnated coal in a nitric oxide atmosphere[J].American Chemical Society: Division of Fuel Chemistry,1975,Jan:7-11.
[15] Shinn J H.Towards an understanding of the coal structure[J].Fue,1984,63:483-497.
[16] Faulon J L,Hatcher P G,Carlson G A,etc.A computer-aided molecular model for high volatile bituminous coal[J].Fuel Processing Technology.,1993,34:277-293.
[17] Oberlin A.High resolution studies of carbonization and graphitization [J].Chemistry and Physics of Carbon,1992,22:1-14.
[18]Grigoriew H,Cichowska G.Spatial coal structure models[J].Journal of Apply Crystallography,1990,23:209-210.
[19]陈昌国,辜敏,鲜学福,煤的颜色和结构与稠环芳族化合物的电子光谱规律[J].煤炭转化,1999,22(1),1-4.
[20]王继仁,金智新,邓存宝.煤自然量子化学理论.北京:科学出版社,2007,59.
[21]孙茂远,黄盛初.煤层气开发利用手册[M].北京:煤炭工业出版社,1998.
[22]李宝芳.煤层气及生储原理略述[J].中国煤田地质,1996,8(1):89-94.
[23]陈昌国,鲜晓红,张代钧等.微孔填充理论研究无烟煤和炭对甲烷的吸附特性.重庆大学学报,1998,21(2):75-79
[24] Moffat.D H, Weale K E. Sorp tion by coal of methane at high pressure[ J ]. Fuel, 1955 (34) : 417 - 428.
[25] Yang R T, Saunders J T. Adsorp tion of gases on coals and heat - treated coals at elevated temperature and pressure [ J ]. Fuel, 1985 (64) : 314 - 327.
[26] Sing K. S. W. , Everet.D. H. , Haul R. A. W. et al. Reporting physisorp tion data for gas/ solid systems with special reference to the determination of surface area and porosity[ J ]. Puer & App l. Chem, 1985, 57 (4) : 603.
[27]刘常洪,杨思敬.煤低温氮吸附等温线的试验研究[ J ].煤矿安全, 1992 (7) : 19 - 21.
[28] Kraemer E. O. . A Treatise on Physical Chemistry [M ].New York: D. van Nostrand Co. , 1931: 166.
[29] DonohueM. D. , Aranovich G. L. . Adsorp tion Hysteresis in Porous Solids [ J ]. Journal of Colloid And Interface Science, 1998, 205 (1) : 121.
[30] Sangwichien C., Aranovich G L., Donohue M. D. Surface tension gradient driven sp reading of trisiloxane surfactant solution on hydrophobic solid [ J ]. Colloids and Surface, 2002, 206 (31) : 1-3.
[31] Xiaojun Cui, R. Marc Bustin, Gregory Dipp le. Selective transport of CO2 , CH4 , and N2 in coals: insights from modeling of experimental gas adsorp tion data [ J ]. Fuel,2004 (83) : 293 - 303.
[32] Krooss B M, Bergen Fvan, Gensterblum Y. , et al. High pressure methane and carbon dioxide adsorp tion on dry and moisture - equilibrated Pennsylvanian coals[ J ].International Journal of Coal Geology, 2002, 51 ( 2) : 69-92.
[33]唐书恒.晋城地区煤储层特征及多元气体的吸附—解吸特征[D ].徐州:中国矿业大学, 2001.
[34] Arri L. E, Yee D. , Morgan W. D. Modeling coal bed methane p roduction with binary gas sorp tion [ C ]. Caspar Wyoming: SPE RockyMountain RegionalMeeting,1992.
[35] Hall F. E. , Zhou Chunhe Gasem K. A. M. , and Robinson, J r. , R. L. . Adsorp tion of PureMethane, Nitrogen, and Carbon Dioxide and their BinaryMixtures on Wet Fruitland Coal, SPE Paper 29194 [ C ].Charleston, WestVirginia: the 1994 Eastern Regional Conference & Exhibition, 1994.
[36] Harpdani S, ParitiU M. Study of coal sorp tion isothermsuing a multicomponent gasmixture[C ]. the 1993 Inter2national CoalbedMethane Symposium. The University of Alabama /Tuscloosa, 1993.
[37]钟玲文.煤的吸附性能及影响因素.地球科学—中国地质大学学报,2004,29(3):327-333.
[38]陈皓侃,李保庆,李文.分子力学和分子动力学方法研究不同变质程度烟煤的分子结构[J].燃料化学学报,2000,28(5):459-462.
[39] Nakamura K. CAMD Study of Coal Model Molecules. 2. Density Simulation for Fou Japanese Coals.Energy & Fuels,1993(7):469-472.
[40] Takanohashi T, Kawashima H.Constuction of a Model Strycture for Upper Freepot Coal Using 13C NMR Chemical Shift Calculations. Energy & Fuels,2002(16):379-387.
[41] Hatcher P G,Faulon J L,Wenzel K A,etc.A structural model for ligninderived vitrinite from high-volatile bituminous coal (coalified wood)[J].Energy&Fuels,1992,6:813-820.
[42] Faulon J L,Carlson G A,Hatcher P G, etc.Statistical models for bituminous coal: A three-dimensional evaluation of structural and physical properties based on computergenerated structures[J].Energy & Fuels,1993,7:1062-1072.
[43] Takanohashi T,Masashi.I,Kazuo.N.Simulation of interaction of coal associates with solvents using the molecular dynamics calculation.Energy & Fuels,1998,12:1168-1173.
[44]邓汉忠,王继仁,邓存宝.O2在—CH2—CH2OH基团上的化学吸附.煤炭转化,2007,30(4):29-33.
[45]王继仁,刘仲田,邓汉忠,邓存宝,张俭.煤表面对多个氧分子的多层吸附机理研究.计算机与应用化学,2008,25(3):281-284.
[46]傅爱萍,冯大诚,邓从豪.水在石墨(0001)面簇模型桥位上吸附的量子化学研究[J].高等学校化学学报,1998,19(5):792-795.
[47]降文萍,崔永君,张群,等.煤表面与CH4、CO2相互作用的量子化学研究[J].煤炭学报,2006,31(2):237-240.
[48]孙培德.煤与甲烷气体相互作用机理的研究[J].Coal,2000,9(l):18-2l.
[49]王宏,杨丽丽,李红,曹立刚.我国煤层气资源开发意义探究[J].辽宁大学学报,2008,35(1):85-88.
[50]张新民,庄军,张遂安主编.中国煤层气地质与资源评价[M].北京:科学出版社,2002.
[51]叶建平,秦勇,林大扬.中国煤层气资源[M ].徐州:中国矿业大学出版社,1999.
[52]张建博,王红岩.中国煤层气地质[M ].北京:地质出版社,2000:15-30.
[53]鲜学福.我国煤层气开采利用现状及其产业化展望[ J ].重庆大学学报.2000,23 (4):23-26.
[54]冯文光.中国应尽快实现低渗煤层气藏工业化生产[ J ].天然气工业, 2001 (1):32-36.
[55]陈永武.中国煤层气产业形成和发展面临的机遇与挑战[ J ].天然气工业, 2000, 20 (4) : 126.
[56]马东民.煤层气吸附解吸机理研究[D].博士学位论文,西安:西安科技大学,2008.
[57] Reznik .A .A , Aingh P K, Foley. W.L. An analysis of the effect of CO2 injection on the recovery of in-situ methane f rom Bituminous coal : an experimental simulation [ J ] . SPE Journal , 1984 , 24 (5) : 521-528.
[58] Zuber M D. Production characteristics and reservoir analysis of coalbed methane reservoirs [ J ] . International Journal of Coal Geology , 1998 , 38 (122) : 27-45.
[59] Clarkson C R and Bustin R M. Binary gas adsorp tion /desorp tionisotherms: effect of moisture and coal conposition upon carbon dioxide selectivity over methane [ J ]. International Journal of Coal Geology,2000, 41 (4) : 241-272.
[60] Busch A, Gensterblum Y, Krooss B M, et al. Methane and carbon dioxide dsorp tion-diffusion experiments on coal: up scaling and modeling [ J ]. International Journal of Coal Geology, 2004, 41:151-168.
[61]高远文,姚艳斌,郭广山.注气提高煤层气采收率研究进展.资源与产业,2007,9(6):105-108.
[62]吴世跃,赵文.自然降压开采和注气开采煤层气的效果评价.中国矿业,2004,13(10):76-79.
[63]李希建,蔡立勇,常浩.注气驱替煤层气作用机理的探讨.矿业快报,2007,8:20-22.
[64]孙可明.煤层气注气开采多组分流体扩散模型数值模拟.辽宁工程技术大学学报,2005,24(3):305-308.
[65]谢振华,陈绍杰.水分及温度对煤吸附甲烷的影响.北京科技大学学报,2007,29(2):42-44.
[1]彭立才,韩德馨,邵文斌等.柴达木盆地北缘侏罗系烃源岩干酪根13C核磁共振研究[J].石油学报,2002,23(2):34-37.
[2] Trewhella M J,Poplett L J F,Grint A.Structure of Green River oil shale kerogen determcnation using solid state 13C-NMR spectroscopy[J].Fuel,1986,65:541-546.
[3]王丽,张蓬洲,郑敏.用固体核磁共振和电子能谱研究我国高硫煤的结构.燃料化学学报,1996,24(6):539-543.
[4]傅家谟,刘德汉,盛国英等.煤成烃地球化学[M].北京:科学出版社,1990,245.
[5] Kidena K,Tani Y,Murata S,etc.Quantitative elucidation of bridge bonds and side chains in brown coals[J].Fuel,2004,83:1697-1702.
[5] Kawashima H,Takanohashi T.Modification of model structures of upper freeport coal extracts using 13C NMR chemical shift calculations[J].Energy & Fuels,2001,15:591-598.
[6] Takanohashi T,Iino M,Nakamura K.Simulation of interaction of coal associates with solvents using the molecular dynamics calculation[J].Energy & Fuels,1998,12:1168-1173.
[7] Frenkel D,Smith B.分子模拟-从算法到应用,汪文川等译[M].北京:化学工业出版社,2002.
[8]谢克昌,煤的结构与反应性[M].北京:科学出版社,2002.
[1]陈昌国,魏锡文,鲜学福.用从头计算研究煤表面与甲烷分子相互作用.重庆大学学报(自然科学版),2000,23(3):77-83.
[2]陈文萍,崔永君,张群,李育辉.煤表面与CH4、CO2相互作用的量子化学研究.煤炭学报,2006,31(2):237-240.
[3]于洪观,范维唐,孙茂远,叶建平.高压下煤对CH4/CO2二元气体吸附等温线的研究.煤炭转化,2005,28(1):43-47.
[4]唐书恒,马彩霞,叶建平,等.注二氧化碳提高煤层甲烷采收率的实验模拟[J].中国矿业大学学报,2006,(35)5:607-612.
[1]张天军,许鸿杰,李树刚,任树鑫.温度对煤吸附性能的影响.煤炭学报,2009,34(6):802-805.
[2]崔永君,张群,张泓,等.不同煤级煤对CH4、N2和CO2单组分气体的吸附[J].天然气工业,2005,25(1):61-65.
[3]傅献彩,沈文霞,姚天扬.物理化学(下册)[M].北京:高等教育出版社,1993,950.
[4] Ruppel T C,Grein C T,Bienstock D.Adsorption of methane on dry coal at elevated pressure[J].Fuel,1974,53(3):152-162.
[5] Day S,Sakurovs R,Weir S.Supercritical gas sorption on moist coals [J].International Journal of Coal Geology,2008,74:203-214.
[6] Mahajan O P,Walker Jr. P L.Water adsorption on coals[J].Fuel,1971,50(3):308-317.
[7] Allardice D J,Evans D G.The-brown coal/water system: Part 2. Water sorption isotherms on bed-moist Yallourn brown coal[J].Fuel,1971,50(3):236-253.
[1] Clarkson C R,Bustin B M.Binary gas adsorption/desorption isothems: effect of moisture and coal composition upon carbon dioxide selectivity over methane[J].International Journal of Coal Geology,2000,42:241-271.
[2]唐书恒,汤达祯,杨起.二元气体等温吸附实验及其对煤层甲烷开发的意义[J].地球科学—中国地质大学学报,2004,29(2):219-223.
[3] Nodzeński A.Sorption and desorption of gases(CH4, CO2) on hard coal and active carbon at elevated pressures[J].Fuel,1998,77(11):1243-1246.
[4] Majewska Z,Ceglańrska-Stefaska G,Majewski S,etc.Binary gas adsorption/desorption isothems effect of moisture and coal composition upon carbon dioxide selectivity over methane[J].International Journal of Coal Geology,2009,77:90–102.
[5]降文萍,崔永君,钟玲文等.煤中水分对煤吸附甲烷影响机理的理论研究[J].天然气地球科学,2007,18(4):576-580.
[6]张庆玲,张群,崔永君,杨杰.煤对多组分气体吸附特征研究.天然气工业,2005,25(1):57-60
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