用常规黑油模型模拟煤层气开采过程

流体在煤层中的传输机理由两部分组成,气体在煤内表面解吸,并通过基岩和微孔隙扩散进入裂缝网络中。若岩块表面甲烷气体的释放速度比气,水相在煤层割理中的流动速度快得多,那么在模拟煤层气开采过程时,解吸动能可以不考虑,根据这个假设可认为：在给定压力下煤层吸附的甲烷气体量类似于相应压力下溶解在原油中的气体量,煤层中的朗格缪尔等温曲线可视为常规黑油油藏中的溶解气油比曲线。若将煤层表面的吸附气作为不流动油中溶解气来处理,那么可用常规黑油模型描述煤层气,而不需要对模型源码做会何修改,基于上述思路,用黑油模型模拟煤层气开采过程,并与用煤层气模拟软件（COMETPC）的计算结果进行了比较,趋势非常接近。     

晋城无烟煤煤中CH4和CO2运移规律研究

基于三轴应力条件下,煤岩有效应力、吸附膨胀量和渗透率的一体测试,研究了晋城无烟煤吸附甲烷和二氧化碳后,渗透性随有效应力改变和煤岩吸附膨胀效应的变化规律.认为煤岩吸附膨胀量和孔隙压力的关系可用兰氏方程描述;煤岩渗透性同有效应力、吸附膨胀量均呈负指数函数关系,同时结果表明:甲烷和二氧化碳在晋城无烟煤中的扩散方式不同,煤岩对甲烷的吸附膨胀符合单孔气体扩散模型,而对二氧化碳的吸附膨胀符合双孔气体扩散模型,且甲烷的吸附膨胀速率小于二氧化碳的吸附膨胀速率;煤岩饱和吸附后,各孔隙压力条件下的初始渗透率与孔隙压力呈幂函数关系减小.针对晋城无烟煤,同等条件下煤岩吸附甲烷后的渗透率为吸附二氧化碳后渗透率的1.14～1.51倍,大部分在1.30倍左右.     

Time-varying diffusion characteristics of different gases in coal particles

Based on the analytical solution of gas diffusion in spherical coal particles with a constant diffusion coefficient, a calculation method of time-varying diffusion coefficient is proposed by constructing objective function. The time-varying diffusion behavior of methane, nitrogen and carbon dioxide in the coal particles was studied. The results show that with the increase of diffusion time, the diffusion coefficients of methane, nitrogen and carbon dioxide gas in the coal particles exhibit an attenuation characteristic, eventually approaching a limit value individually. The diffusion coefficient of carbon dioxide is larger than methane, and the diffusion coefficient of nitrogen is smallest. Significant phenomenon of limited diffusion was observed for coal of strong adsorption capability. Through the analysis of the diffusion coefficient of gases at different diffusion time, a mathematical model describing the time-varying diffusion characteristic of gases is obtained. The implementation of mixed gases to replace coal bed methane has a very important practical significance.     

煤层气运移分馏机理初探

煤层气的分馏效应是指运移过程中气体组份和同位素值发生变化的现象.分馏机理的探讨对煤层气的运移聚集具有重要指导意义.本文以吸附势理论为指导,以等温吸附实验数据为依据,对甲烷碳同位素和多组分气体分馏机理进行了探讨.确定了4种分馏机理的存在:(1)解吸-扩散-运移不仅造成甲烷碳同位素分馏,而且造成多组分气体分馏.13CH4因其吸附势普遍高于12CH4而具有优先吸附、滞后解吸的特征,12CH4更容易发生运移分馏.二氧化碳与甲烷相比,具有优先吸附、滞后解吸的特征,特别是在高压下,甲烷具有强的分馏效应;(2)发生在地下水径流带的溶解作用使得13CH4被优先溶解并被运移至滞留区聚集,12CH4保留在原地;(3)浅部次生生物气的产生造成甲烷碳同位素变轻的假象;(4)高温裂解气的生成造成甲烷碳同位素变重的假象.4种分馏效应都引起浅部甲烷碳同位素变轻,深部变重,这已为众多的实例所证实.     

Adsorption behaviors of gas molecules on the surface of ZnO nanocrystals under UV irradiation

A UV-activated room temperature chemiresistive gas sensor based on ZnO nanocrystals film was fabricated. Its gas sensing properties under various conditions were also investigated in detail. The results shed new insight into the adsorption behaviors of gas molecules on the surface of Zn O nanocrystals under UV irradiation. The chemisorbed oxygen species(O_2~-(ads)(hv)) induced by UV light govern the adsorption and desorption ways of other gas molecules on the surface of ZnO nanocrystals, which is dependent on the electron affinity of gas molecules. Gas molecules with higher electron affinity than oxygen molecules can be adsorbed on the surface by the competitive adsorption way, extracting electrons from the surface. Gas molecules with lower electron affinity than oxygen molecules are attracted by the adsorbed O_2~-(ads)(hv)layer, releasing electrons to the surface. These processes can influence the gas sensing properties of the sensor. Our findings will pave the way for the fundamental understanding and design of UV-activated gas sensor in the future.     

Adsorption and desorption on coals for CO2 sequestration

Adsorption and desorption of carbon dioxide, methane and other gases on coals has been investigated experimentally using representative Zhongliangshan coals. Gas adsorption is one of the major concerns for both CO2 sequestration and methane recovery processes. The experiments were carried out using both single and multi-component mixtures at 25 ℃ and 30 ℃ with the highest pressure of 12 MPa. The coal was under moisture equilibrated conditions. This provides experimental data from which a predictive assessment of CO2 sequestration and/or methane recovery can be conducted. The results show that for pure gasses the CH4 adsorption capacity is higher than the N2 adsorption capacity but lower than the CO2 adsorption capacity. Injection of CO2 or other gases into the coal significantly affects CH4 desorption. This allows the enhancement of CH4 recovery from the coals, thus supplying more clean energy while sequestering significant amounts of CO2 thereby reducing the greenhouse effect from human beings.     

Temperature influence on macro-mechanics parameter of intact coal sample containing original gas from Baijiao Coal Mine in China

Investigation of temperature effect on mechanical parameters of coal is very important for understanding the mechanical response of coal bed at high temperature. It is especially beneficial for mitigating the thermal-induced disasters occurred in those coal mines suffering from heat hazard. In this work, coal samples, obtained from the No. 2442 working face of Baijiao Coal Mine, were subjected to uniaxial compression ranging from 20 to 40 °C with an interval of 5 °C. The apparatus used was designed to obtain deformation of a stressed sample, as well as the emission of gases desorbing from coal matrix. The adsorbed gas desorption caused by heating is measured during the entire testing. It is evident that the concentrations of releasing gas (containing methane, carbon dioxide and ethane) slightly rise with increasing temperature. Gas movement observed is closely related to the deformation of coal sample. Both uniaxial compressive strength and elastic modulus of coal samples tend to reduce with temperature. It reveals that increasing temperature can not only result in thermal expansion of coal, but also lead to desorption of preexisting gas in coal which can in turns harden coal due to shrinks of the coal matrix. Even though desorption of adsorbed gas can contribute to the hardening effect for the heated coal, by comparison to the results, it could be inferred that the softening of coal resulted from thermal expansion still predominates changes in mechanical characters of coal sample with temperature at the range from 20 to 40 °C.     

液态水对煤吸附甲烷影响的机理分析

为了研究液态水对煤吸附甲烷影响的机理,进行了不同煤级干燥煤样、平衡水煤样和注水煤样等温吸附实验,基于分子间作用力对液态水影响机理进行分析,并用维里方程拟合等温吸附实验结果来验证.结果表明,煤基质的润湿程度是液态水影响煤吸附甲烷的主要因素.干燥煤样中煤与甲烷分子间作用力远大于甲烷分子间作用力,第二维里系数较低,吸附能力强;平衡水煤样中煤与水分子氢键能高于范德华力,气态水分子竞争吸附,第二维里系数偏高,煤基质吸附能力弱;注水煤样中煤与甲烷分子之间长程作用力和甲烷与水分子之间短程作用力之和较小,与甲烷分子间作用力相当,第二维里系数最高,煤基质吸附能力很低.煤级增高,煤基质表面极性及其润湿程度降低,第二维里系数随之降低.     

Spontaneous coal combustion producing carbon dioxide and water

Gas products from the process of coal oxidization and spontaneous combustion have been studied at different temperatures with FTI spectroscopic tests. With temperatures rising to about 30～100 ℃, water and carbon dioxide gas were formed and from about 105～150 ℃, carbon monoxide was produced. Using the DFT B3LYP method with a 6-311G basis set, the reaction system, where spontaneous combustion between coal and oxygen occurs and produces water and monoxide, has been studied, with the geometric configuration for all stagnation points on the potential reaction energy surface optimized. With a frequency analysis and an IRC method, transient formations were tested. Our results indicate that in the reaction of coal oxidization and spontaneous combustion producing carbon dioxide and water, oxygen molecules attack carbon atoms of the terminal of the propyl alcohol group on the lateral chain of benzene rings, which causes this propyl alcohol group to produce the acid (-CH2-CH2-COOH) group and water. This acid group continues its break up into carbon dioxide and the (-CH2-CH3) ethyl group. We have come to the conclusion that this water-and-carbon dioxide-production reaction is spontaneous, based on the observation of the energy released by the reaction.     

煤层气藏与常规天然气藏地质及开采特征比较

煤层气是一种与煤岩同生共体以甲烷为主要成分,主要以吸附状态赋存在沉积盆地煤层之中的可燃气体,也就是煤矿生产中有名的瓦斯气。煤层气藏作为一种非常规常气藏,从地质成因与特征,储集与开采特征以及储量评价多个方面,与常规气藏有着不同之处,因此对两种类型的气藏进行详细的比较与总结十分必要,同时也为煤层甲烷气开发与开采中的各项研究如煤层气藏工程,煤层气井试井,完井,煤层气藏模拟等奠定了基础。     

Improved analytic methods for coal surface area and pore size distribution determination using 77 K nitrogen adsorption experiment

77 K nitrogen adsorption was the most widely used technique for determining surface area and pore size distribution of coal. Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) model are commonly used analytic methods for adsorption/desorption isotherm. A Chinese anthracite coal is tested in this study using an improved experimental method and adsorption isotherm analyzed by three adsorption mechanisms at different relative pressure stages. The result shows that the micropore filling adsorption predominates at the relative pressure stage from 6.8E−7 to 9E−3. Theoretically, BET and BJH model are not appropriate for analyzing coal samples which contain micropores. Two new analytic procedures for coal surface area and pore size distribution calculation are developed in this work. The results show that BET model underestimates surface area, and micropores smaller than 1.751 nm account for 35.5% of the total pore volume and 74.2% of the total surface area. The investigation of surface area and pore size distribution by incorporating the influence of micropore is significant for understanding adsorption mechanism of methane and carbon dioxide in coal.     

Monte Carlo simulation of methane molecule adsorption on coal with adsorption potential

The paper presents a Monte Carlo simulation to study the adsorption characteristics of methane molecule on coal slit pores from different aspects. Firstly, a physical model of adsorption and desorption of methane molecules on micropores was established. Secondly, a grand canonical ensemble was introduced as the Monte Carlo simulation system. Thirdly, based on the model and system, the molecule simulation program was developed with VC++6.0 to simulate the isothermal adsorption relationship between the amount of molecule absorption and the factors affecting it. Lastly, the numerically simulated results were compared with measured results of adsorption coal samples of two different coal mines with a laboratory gas absorption instrument. The results show that the molecule simulations of the adsorption constants, the adsorption quantity, and the isothermal adsorption curve at the same and different coal temperatures were in good agreement with those measured in the experiments, indicating that it is feasible to use the established model and the Monte Carlo molecule simulation to study the adsorption characteristics of methane molecules in coal.     

吸附平衡时间对瓦斯吸附常数测值的影响

煤的瓦斯吸附常数是煤矿瓦斯防治的重要基础参数,它的准确测定对煤矿瓦斯预测、瓦斯抽采和瓦斯突出防治均有重要的意义.煤炭行业标准MT/T 752—1997《煤的甲烷吸附量测定方法(高压容量法)》要求测定过程中煤对瓦斯吸附的平衡时间为7 h,但研究发现大部分煤样在7 h内并不能达到吸附平衡.选用无烟煤、贫煤和气肥煤3类不同煤阶的煤样,进行了不同吸附时间下的瓦斯吸附常数的对比测试.结果表明,吸附时间对瓦斯吸附常数影响非常明显;对固定煤阶煤样,吸附时间越长,吸附常数a值有增大的趋势;煤阶越高,瓦斯吸附常数a值受吸附时间的影响程度越大,煤对瓦斯的饱和吸附平衡时间越长.因此,对于高阶煤样,吸附时间应适当延长,从而提高测值可信度和工程应用价值.     

超临界CO2增透煤热流固耦合模型与数值模拟

针对中国绝大多数高瓦斯煤层渗透性低以及低渗透煤层强化抽采瓦斯效果不理想的现状,结合超临界CO₂强扩散和溶解增透孔隙介质等独特优点,依据超临界CO₂作用后煤微观孔裂隙的演化特征,得到煤微观孔隙率和渗透率演化方程,根据孔隙率的变化确定损伤变量,考虑体积应力、温度、孔隙压力及超临界CO₂溶解增透作用的影响,建立超临界CO₂作用后煤的热流固耦合力学模型,利用ABAQUS软件提供的场变量子程序,结合PYTHON脚本和子程序二次开发功能,实现低渗透煤层注超临界CO₂增透规律数值模拟。结果显示：超临界CO₂注入后,注气孔周围煤体内体积应力、温度及孔隙压力变化明显,随着距注气孔距离的增加,影响程度逐渐减弱,并趋于稳定;经超临界CO₂作用后,注气孔周围煤体内不断萌生新的孔裂隙,并与原有的孔裂隙相互贯通,随注气时间的延长各级孔裂隙不断向煤体纵深演化发展,煤微观孔隙率较注气前提高了2个数量级;超临界CO₂的致裂增透作用引起煤体不同程度的损伤,距注气孔越近,损伤程度越大,损伤增加越快,注气时间越长,损伤增加的幅度越大;煤微观孔裂隙的有效发育为煤层气的扩散渗流提供了更多的运移通道,使煤体渗透系数较注气前提高了3个数量级。     

煤矿乏风甲烷分离富集过程的数值研究

建立了吸附床内煤矿乏风二维气体流动、吸附传质的数学模型,以轴向流吸附床为研究对象,对活性炭富集分离煤矿乏风甲烷过程进行了模拟,得到了各个循环步骤下床内详细的流动、浓度和吸附量分布;详细分析了活性炭吸附床对煤矿乏风甲烷的吸附富集特性,并对回收时间进行优化,模拟结果与实验结果符合较好.另外,还对不同原料气浓度工况进行了对比研究.     

有机氮化物在镍钼硫催化剂的表面吸附

加氢精制过程中,有机含氮化合物的存在会使得贵金属催化剂或酸性催化剂中毒,同时抑制加氢脱硫（HDS）催化剂的活性,因此研究含氮化合物在催化剂表面的吸附行为有助于了解含氮化合物对HDS反应的作用机理.本研究构建一个周期性的镍钼硫（NiMoS）催化剂超晶胞模型,应用密度泛函理论的方法计算了平行吸附和垂直吸附状态下的吡啶、喹啉、咔唑和吲哚在NiMoS催化剂表面的吸附构型和吸附能.结果表明：碱性分子吡啶和喹啉通过Ni-N键吸附在催化剂的表面上,主要表现为垂直吸附;而非碱性分子吲哚通过吡咯环的β-C键吸附在催化剂表面上,咔唑则主要通过苯环吸附在催化剂表面上,两者均以平行吸附为主.比较两类不同吸附构型的吸附能发现,在NiMoS催化剂表面碱性氮化物的吸附能比非碱性氮化物的吸附能高.氮化物在催化剂表面的吸附过程为放热过程.     

The study of adsorption gas sensor based carbon nanotube film

The carbon nanotube is a hollow canaliculus like rolling up hexagon network graph- eme sheets, which is similar to the structure of the graphite. Its outer diameter is from a few nanometers to several decade nanometers. There are two kinds of them: single wall carbon nanotubes (SWNTs) and multi-wall nanotubes (MWNTs), all of which have the helix structure. People have paid great attention to them due to their interesting physical properties[1―3]. The elementary study results show that the…     

煤层气的赋存运移机理及产出特征

煤层气是储集在煤层中的非常规天然气.煤层中发育有微孔隙系统和裂隙系统,煤层气主要以物理吸附的形式赋存于煤的内表面上,当压力降低时,煤层气发生解吸、扩散和渗流,最后由井筒中产出.了解煤层气的赋存、运移机理及产出特征,对进行煤层气的可采性评价十分重要.     

Some parameters of coal methane system that cause very slow release of methane from virgin coal beds(CBM)

In some worldwide hard coal basins recovery of methane from virgin coal beds is difficult. In general,mentioned difficulties are related to geo-mechanical, petrographical and physical-chemical properties of coals in question, occurring for example in the Bowen Basin(Australia) or the Upper Silesian Coal Basin(Poland). Among numerous properties and parameters, the following are very essential: susceptibility of coal beds to deformation connected with coal stress state change and contemporary shrinkage of the coal matrix during methane desorption. Those adverse geo-mechanical and physical-chemical effects are accompanied by essential change of the porous coal structure, which under these disadvantageous conditions is very complex. This study aims to show difficulties, which occur in phase of recognition of the methane-reach coal deposit. Volume absorbed methane(not surface adsorbed) in sub-micropores having minimal size comparable with gas molecule diameter must possess energy allowing separation of the nodes and methane release to micropores.     

排采连续性对煤层气开采的影响

排采连续性对煤层气开发至关重要.但是,在排采过程中关井现象不可避免,重新开井后如何排采、制定合理的排采制度是提高产量的关键.通过对煤层气生产阶段理论进行分析,结合关井前后矿场数据,同时借助数值模拟方法,对关井过程中储层参数变化进行了研究.结果表明,关井明显改变储层物性参数,造成井筒附近煤层含水饱和度增加,井底压力升高,...