Adsorption and strain: The CO2-induced swelling of coal

Enhanced coal bed methane recovery (ECBM) consists in injecting carbon dioxide in coal bed methane reservoirs in order to facilitate the recovery of the methane. The injected carbon dioxide gets adsorbed at the surface of the coal pores, which causes the coal to swell. This swelling in confined conditions leads to a closure of the coal reservoir cleat system, which hinders further injection. In this work we provide a comprehensive framework to calculate the macroscopic strains induced by adsorption in a porous medium from the molecular level. Using a thermodynamic approach we extend the realm of poromechanics to surface energy and surface stress. We then focus on how the surface stress is modified by adsorption and on how to estimate adsorption behavior with molecular simulations. The developed framework is here applied to the specific case of the swelling of CO₂-injected coal, although it is relevant to any problem in which adsorption in a porous medium causes strains.     

Coal Permeability Evolution and Gas Migration Under Non-equilibrium State

Laboratory test of coal permeability is generally conducted under the condition of gas adsorption equilibrium, and the results contribute to an understanding of gas migration in the original coal seams. However, gas flow under the state of non-equilibrium, accompanied by gas adsorption and desorption, is more common in coalbed methane (CBM) recovery and \(\hbox {CO}_{2}\) geological sequestration sites. Therefore, research on gas migration under the non-equilibrium state has a greater significance with regard to CBM recovery and \(\hbox {CO}_{2}\) geological sequestration. However, most permeability models, in which only one gas pressure has been considered, cannot be used to study gas flow under the non-equilibrium state. In this study, a new mathematical model, which includes both fracture gas pressure and matrix gas pressure, and couples the gas flow with the coal deformation, has been developed and verified. With the developed model, the spatial and temporal evolution of gas flow field during gas adsorption and desorption phases has been explored. The results show that the gas pressures present nonlinear distributions in the coal core, and the matrix gas pressure is generally lower than the fracture gas pressure during adsorption, but higher than the fracture gas pressure during desorption. For gas flow during adsorption, the main factor controlling permeability varies at different points. At the initial time, the permeability is dominated by the effective stress, and at the later time, the permeability in the part close to the gas inlet is mainly controlled by the matrix swelling, whereas that in the part close to the gas outlet is still dominated by the effective stress. For gas flow during desorption, from the gas inlet to the gas outlet, the permeability deceases at the initial time, and when the time is greater than 10,000 s, it shows a decreasing and then an increasing trend. The reason is that at the initial time, the permeability is dominated by the increased effective stress caused by the sharp decrease of the fracture gas pressure. Later, desorption of the adsorbed gas results in matrix shrinkage, which further leads to an increase of the permeability.     

Time-Dependent Methane Diffusion Behavior in Coal: Measurement and Modeling

In-depth understanding of how methane diffuses in porous media like coal is critical for enhanced coalbed methane recovery and coal seam methane drainage. However, the classic unipore gas diffusion model can only describe methane diffusion behavior in coal at the early time diffusion stage. Describing the whole methane diffusion behavior in coal has not been reasonably addressed in the coalbed methane field. Considering the large surface-to-volume ratio of coal, the authors proposed a time-dependent gas diffusion model to describe the whole diffusion process. This work first proposed a power–law relationship between diffusion coefficient and time according to previous studies of the time-dependent gas diffusion process in porous media. Then, both the analytical solution and its approximation solution for the time-dependent gas diffusion model were derived. Six methane diffusion tests in crushed coal were conducted to validate the proposed model under different pressures (0.5, 1.5, 2.5 MPa) and temperatures (20 and \(30\,{^{\circ }}\hbox {C}\)). Modeling results show that the time-dependent gas diffusion model is superior to the classic unipore gas diffusion model for describing the whole methane diffusion process in coal. Increasing temperature always accelerates methane diffusion in coal; the higher the temperature the larger the diffusion coefficient.     

Gas Sorption and the Consequent Volumetric and Permeability Change of Coal II: Numerical Modeling

The permeability of coalbed methane reservoirs may evolve during the recovery of methane and injection of gas, due to the change of effective stress and gas adsorption and desorption. Experimental and numerical studies were conducted to investigate the sorption-induced permeability change of coal. This paper presents the numerical modeling part of the work. It was found that adsorption of pure gases on coal was well represented by parametric adsorption isotherm models in the literature. Based on the experimental data of this study, adsorption of pure \(\hbox {N}_2\) was modeled using the Langmuir equation, and adsorption of pure \(\hbox {CO}_2\) was well represented by the N-Layer BET equation. For the modeling of CO \(_2\) & N \(_2\) binary mixture adsorption, the ideal adsorbed solution (IAS) model and the real adsorbed solution (RAS) model were used. The IAS model estimated the total amount of mixture adsorption and the composition of the adsorbed phase based on the pure adsorption isotherms. The estimated total adsorption and adsorbed-phase composition were very different from the experimental results, indicating nonideality of the CO \(_2\) –N \(_2\) –Coal-adsorption system. The measured sorption-induced strain was linearly proportional to the total amount of adsorption despite the species of the adsorbed gas. Permeability reduction followed a linear correlation with the volumetric strain with the adsorption of pure \(\hbox {N}_2\) and the tested CO \(_2\) & N \(_2\) binary mixtures, and an exponential correlation with the adsorption of pure \(\hbox {CO}_2\) .     

分形理论在煤层气非平衡吸附模型中的应用

传统的煤层气动力学模型均是建立在欧几里得几何基础上的,难以描述煤层孔隙结构的复杂性及形状的不规则性。本文以分形理论为基础,通过引入分形维数来刻画煤层孔隙结构的复杂性并考虑煤层的吸附特性、双重介质特征及介质的变形,建立基于Fick第二定律的分形介质煤层气非稳态渗流数学模型。由于流动方程的强非线性,结合各类边界条件用正则摄动法和Laplace变换得到模型在拉氏空间上的近似解析解,再利用Laplace数值反演求得实空间上的数值解。对参数进行敏感性分析并绘制了典型压力曲线,这些结果为煤层气开采提供了理论依据和试井方法。     

TRANSIENT WELL TEST MODEL FOR THE WELL WITH GAS AND WATER DISTRIBUTED IN COALBED

煤层气是一种高效清洁的非常规天然气资源,其开采过程是一个排水降压采气的过程. 由于煤层气主要是以吸附态的形式存在于煤层中,当煤层压力降低到临界解吸压力以下时煤层气从煤层中解吸出来并与水一起采出,因此煤层中流体是气水两相分布的. 本文根据煤层气藏排采过程中的解吸特征,通过考虑气水两相分布的渗透率关系,提出了一种与解吸区域大小相关的煤层气井不稳定试井模型. 该模型较好地描述了煤层气排采过程中煤层内气水的流动状态,采用分区模式对气水两相进行描述. 通过有限体积方法求解了所建立的试井模型,计算得到了煤层气井气水两相分布不稳定试井理论曲线,分析了煤层气解吸系数、解吸复合半径、气水饱和度分布等对试井理论曲线的影响.     

Recovery of Methane From Gas Hydrates in a Porous Medium by Injection of Carbon Dioxide

This paper presents a mathematical model for methane hydrate–carbon dioxide replacement by injection of carbon dioxide gas into a porous medium rich in methane and its gas hydrate. Numerical solutions describing the pressure and temperature variation in a reservoir of finite length are obtained. It is shown that the replacement process is accompanied by a decrease in pressure and an increase in temperature of the porous medium. It is established that during the time of complete replacement of methane from a reservoir decreases with increasing permeability of the porous medium and the pressure of the injected gas.     

CH4/CO2混合气体爆燃特性研究进展

掌握甲烷与二氧化碳混合气体的爆燃特性对高含二氧化碳天然气的勘探、开发和利用具有安全保 障作用,对涉及甲烷和二氧化碳的其他工业过程如煤炭气化、惰化、抑爆、泄爆等应急处置和安防设计具有指 导价值。为推动相关学科的进步,分类回顾了甲烷与二氧化碳混合气体爆燃特性的实验和理论研究进展,涉 及爆燃范围、爆燃压强、惰化等爆燃特性的实验研究以及爆燃范围领域的理论研究,系统分析和评价了各个研 究领域取得的成果、存在的问题,并从提高实验数据的完整性、可比性和适用面,理论预测方法可靠性的评价 方法与指标,理论预测方法的适用面从常温常压条件向更复杂的情形扩展3个方面展望了未来的研究重点。     

Formation of hydrate in injection of liquid carbon dioxide into a reservoir saturated with methane andwater

Injection of liquid carbon dioxide into a depleted natural gas field is investigated. A mathematical model of the process which takes into account forming CO₂ hydrate and methane displacement is suggested. An asymptotic solution of the problem is found in the one-dimensional approximation. It is shown that three injection regimes can exist depending on the parameters. In the case of weak injection, liquid carbon dioxide boils up with formation of carbon-dioxide gas. The intense regime is characterized by formation of CO₂ hydrate or a mixture of CO₂ and CH₄ hydrates. Critical diagrams of the process which determine the parameter ranges of the corresponding regimes are plotted.     

煤层气三孔双渗流动模型及压力分析

通过对美国Antrim页岩气藏及一些别的低阶煤层的研究表明,在基质颗粒中也有相当一部分自由气存在。本文建立了低阶煤层中单相煤层气三孔双渗流动的试井模型,并获得了模型在拉氏空间上的解析解以及模型的数值解,讨论了储层外边界条件、弹性储容比、窜流系数以及吸附系数等参数对于压力动态响应的影响。结果表明：外边界条件决定着早期过渡段出现的早晚;窜流系数和弹性储容比影响窜流阶段出现的早晚;而吸附系数对晚期过渡段影响明显。     

A Computational Approach to Determine Average Reservoir Pressure in a Coalbed Methane (CBM) Well Flowing Under Dominant Matrix Shrinkage Effect

Desorption of gas from coal matrix alters the pore volume of fracture network. Consequently, cleat porosity and permeability of reservoir changes as pressure depletes. The method of standard pressure analysis calculations produces incorrect results in the case of coalbed methane reservoirs producing under dominant matrix shrinkage effect. The change in cleat porosity and permeability due to shrinkage of coal matrix following gas desorption with pressure depletion invalidates the underlying assumptions made in the derivation of diffusivity equation. Consequently, equations of pseudo-steady state commonly used in conventional reservoirs no longer remain valid as the porosity and permeability values change with pressure depletion. In this paper, effort has been made to describe pseudo-steady-state flow in coalbed methane reservoirs in the form of a new equation that accounts for pressure dependency of cleat porosity and permeability due to shrinkage of coal matrix. The concept of Al-Hussainy et al. (1966) has been extended to define a new pseudo-pressure function which assimilates within itself the pressure dependence of porosity and permeability Palmer and Mansoori (1998). Equation has been used to relate the cleat porosity with pressure. The equation-based computational method suggested in this paper finds its usefulness in estimating average reservoir pressure for any known flowing bottom hole pressure and thus reducing the frequency of future pressure buildup tests. The new equation is also useful in predicting reservoir pressure under the situation when coal matrix shrinks below desorption pressure. The equation used in the computational method has been validated with the help of numerical simulator CMG-GEM.     

煤系页岩瓦斯吸附?解吸迟滞效应核磁共振谱实验研究

煤系页岩瓦斯主要以吸附态和游离态形式存在, 其解吸过程相对吸附过程具有普遍滞后现象, 因此从微细观角度定量研究其吸附?附解吸迟滞规律对页岩气井后期稳产增产具有重要意义. 在前人研究基础上结合核磁共振谱理论推导出能够准确表征煤系页岩瓦斯吸附?解吸迟滞效应微细观评价模型, 并采用核磁共振谱测试技术, 以双鸭山盆地东保卫煤矿三采区36# 煤层底板煤系页岩为研究对象, 进行煤系页岩瓦斯吸附?解吸迟滞效应核磁共振谱实验, 模拟不同储层原位应力状态煤系页岩瓦斯迟滞效应发生全过程, 进一步对吸附态瓦斯、游离态瓦斯以及微细观方法测定的宏观瓦斯迟滞规律进行定量化研究, 并对其发生机理以及其对深部煤系页岩瓦斯开采影响进行了初步探究. 结果表明: 应力状态下吸附态和游离瓦斯均有滞后效应; 瓦斯宏观迟滞系数与平均有效应力呈幂函数关系, 而瓦斯宏观迟滞效应中由吸附态或游离态瓦斯引起的迟滞系数与平均有效应力关系均可采用二次多项式拟合; 孔裂隙应力损伤和微孔隙瓦斯扩散受限耦合或许是煤系页岩瓦斯吸附?解吸迟滞效应产生根本原因之一.      

页岩气吸附解吸规律研究

页岩中天然气的吸附解吸规律是页岩气开发的基础。根据物质平衡原理,自行设计了页岩气吸附解吸实验装置。用该装置对取自鄂尔多斯盆地的三个页岩岩样在不同温度(30～90℃)、不同压力(0.1～10MPa)条件下,进行页岩气吸附及解吸规律研究。实验结果表明,吸附量随有机碳含量的增加而增大;随压力的增加吸附量增大,而随温度的增大吸附量减小。同一温度压力条件下,相对吸附过程而言,解吸过程有滞后现象,解吸不够彻底。对粘土含量较大的页岩,朗格缪尔模型拟合效果较差,而利用修正的双朗格缪尔模型可以得到较好的拟合结果。     

Experimental Method to Simulate Coal Fines Migration and Coal Fines Aggregation Prevention in the Hydraulic Fracture

A simple and effective experimental method is proposed to simulate coal fines migration through the proppant pack; such migration inevitably occurs during the process of fracturing fluid flowback or dewatering and gas production in coalbed methane (CBM) reservoirs. The damage to conductivity caused by coal fines migration in the pack and the factors affecting such migration are analyzed. A dispersion agent of coal fines applicable to hydraulic fracturing in CBM is optimized, consequently solving the problem of coal fines aggregation and retention in the proppant pack. Discharging coal fines with water or water-based fracturing fluid from the proppant pack can be difficult because of the adsorption and hydrophobicity of coal fines. Thus, coal fines are likely to aggregate and be retained in the proppant pack, thereby resulting in pore throat plugging, which causes serious damage to fracture conductivity. Two percent coal fines can reduce propped fracture conductivity by 24.4 %. The mobility and retention of coal fines in the proppant pack are affected by proppant size, proppant type, flowback rate, and coal fines property. When flowback rate exceeds the critical value, coal fines can be discharged from the pack, consequently reducing damage to propped fracture conductivity. More importantly, the steady discharging of coal fines requires steady dewatering and gas production to avoid flow shock, which causes pressure disturbance to drive coal fines in a remote formation. The optimized dispersant FSJ-02 employed in this paper can effectively change the wettability and surface potential of coal fines to improve their suspension and dispersion in water-based fracturing fluid. The recovery rate of coal fines increased by 31.5 %, whereas conductivity increased by 13.3 %.     

Damage Evolution and Post-peak Gas Permeability of Raw Coal Under Loading and Unloading Conditions

Coalbed methane, a naturally occurring gas in coal, is regarded as a relatively clean-burning and eco-friendly resource. During mining, coalbed methane may be leaked to the environment, leading to potential coal mine catastrophes such as coal and gas outbursts, and gas explosions. In the interest of mine stability, and to enhance resource recovery and utilisation, it is fundamentally important to understand the permeability characteristics of coal, in particular its post-peak permeability behaviour. In this paper, an in-house developed tri-axial apparatus with the ability to investigate coupled thermal–hydrological–mechanical behaviour under servo-controlled seepage has been used to carry out a series of gas permeation experiments in coal samples. The coal samples were subjected to tri-axial tests, including the simulation of coal extraction by unloading the confining pressure applied on the test specimens. The deformation and permeability characteristics of raw coal during these tests were recorded. The volume changes of the coal samples during the tests were observed to occur in three stages: Stage 1: contraction, Stage 2: little or no volume change, and Stage 3: dilation. Corresponding to the volume changes, the gas seepage can also be divided into three stages: seepage decrease, steady seepage, and accelerated seepage. Based on the observed behaviour of coal samples during the tri-axial permeation tests, an analytical model to simulate damage evolution and its effect on the permeability of coal containing gas is proposed in this paper. It may be used to study the evolution of permeability with stress changes, and to provide insights into coal and gas outbursts in practice.     

Laboratory Investigation of LNAPL Migration in Double-Porosity Soil Under Fractured Condition Using Digital Image Analysis

Gas production from shale gas reservoirs plays a significant role in satisfying increasing energy demands. Compared with conventional sandstone and carbonate reservoirs, shale gas reservoirs are characterized by extremely low porosity, ultra-low permeability and high clay content. Slip flow, diffusion, adsorption and desorption are the primary gas transport processes in shale matrix, while Darcy flow is restricted to fractures. Understanding methane diffusion and adsorption, and gas flow and equilibrium in the low-permeability matrix of shale is crucial for shale formation evaluation and for predicting gas production. Modeling of diffusion in low-permeability shale rocks requires use of the Dusty gas model (DGM) rather than Fick’s law. The DGM is incorporated in the TOUGH2 module EOS7C-ECBM, a modified version of EOS7C that simulates multicomponent gas mixture transport in porous media. Also included in EOS7C-ECBM is the extended Langmuir model for adsorption and desorption of gases. In this study, a column shale model was constructed to simulate methane diffusion and adsorption through shale rocks. The process of binary \(\hbox {CH}_{4}{-}\hbox {N}_{2}\) diffusion and adsorption was analyzed. A sensitivity study was performed to investigate the effects of pressure, temperature and permeability on diffusion and adsorption in shale rocks. The results show that methane gas diffusion and adsorption in shale is a slow process of dynamic equilibrium, which can be illustrated by the slope of a curve in \(\hbox {CH}_{4}\) mass variation. The amount of adsorption increases with the pressure increase at the low pressure, and the mass change by gas diffusion will decrease due to the decrease in the compressibility factor of the gas. With the elevated temperature, the gas molecules move faster and then the greater gas diffusion rates make the process duration shorter. The gas diffusion rate decreases with the permeability decrease, and there is a limit of gas diffusion if the permeability is less than \(1.0\,\times \,10^{-15}\, \hbox { m}^{2}\). The results can provide insights for a better understanding of methane diffusion and adsorption in the shale rocks so as to optimize gas production performance of shale gas reservoirs.     

Modeling of Coal Fine Migration During CBM Production in High-Rank Coal

During CBM (coalbed methane) production, the interaction of coal fracture surface with water flow commonly generates and starts coal fine flow. Part of flowing coal fines deposit in coal fracture system due to water production reduction and methane production increase. The fine sedimentation results in the reduction of coal permeability and well productivity. Despite the increasing awareness of the importance of fine migration, limited research has been carried out on the flow model of coal fine coupled with water and gas. In this paper, a flow model of coal fine is established coupled with water and gas flow, taking coal fine generation, migration and sedimentation process into consideration. Then, case simulations are conducted to illustrate effects of water production schedule, permeability performance and gas content on production performance in flow model. The simulation results indicate that methane rate with the lowest initial water rate is observed to have the highest production in late production period. This is mainly due to the reason that the low water flow cannot generate and start the flow of coal fine. Further, the case with high initial water production has faster gas and water flow rate, thus higher coal fine generation rates, which can improve well productivity at earlier production period. As water production declines quickly, both permeability and production performance decrease, which leads to the loss of well productivity. Meanwhile, higher gas content will lead to a faster water production decline at late production period. This indicates that a portion of coal fines plugged in the fracture as water production deceases and the CBM reservoir with high gas content should not adopt a high initial water production schedule.     

Effective accelerated purification of carbon dioxide and methane for 14C measurements

Summary The existing methods for ultrapurification of carbon dioxide and methane often suffer from a waste of time caused by the use of reagents requiring high temperatures and repeated regeneration.In the case of carbon dioxide the normally employed reduced copper in filings and calcium oxide can be successfully replaced by reduced finely divided copper fixed on a silica-magnesium oxide support (BTS catalyst). The experimental conditions then are very mild and several purifications can be done without any regeneration. The low reaction temperature allows to avoid quartz furnaces.In the methane purification BTS is also used, after synthesis, for removal of excess hydrogen. During the same operation residual carbon dioxide is separated from methane by selective adsorption on a molecular sieve.     

Injection of liquid carbon dioxide into a reservoir partially saturated with methane hydrate

A mathematical model is proposed to describe methane–carbon dioxide replacement in gas hydrate by injecting liquid carbon dioxide into a porous medium initially saturated with methane and its hydrate. Self-similar solutions of the axisymmetric problems are constructed that describe the distribution of the main parameters of the reservoir. It is shown that there exist solutions according to which the process can occur both with and without boiling of carbon dioxide. Diagrams of the existence of each type of solution are constructed.     

Effect of acoustic field on CO2 desorption in a fluidized bed of fine activated carbon

Adsorption using solid sorbents has the potential to complement or replace current absorption technology, because of its low energy requirements. Among the commercially available adsorbent materials, attention is focused on activated carbons because they are easily regenerable by reason of their low heat of adsorption. These sorbents are generally available in the form of fine powders. Sound-assisted fluidization can process large amounts of fine powders, promoting and enhancing CO₂ capture on fine sorbents, because it maximizes gas–solid contact. Temperature swing adsorption (TSA), consisting of inducing sorbent regeneration and CO₂ recovery by appropriate temperature increase and gas purge, is one of the most promising techniques. This study investigates the CO₂ desorption process by TSA in a sound-assisted fluidized bed of fine activated carbon. Desorption tests were performed under ordinary and sound-assisted fluidization conditions to assess the capability of sound to promote and enhance the desorption efficiency in terms of CO₂ recovery, CO₂ purity, and desorption time. The results show that the application of sound results in higher desorption rates, CO₂ recovery and purity. Regular and stable desorption profiles can be obtained under sound-assisted fluidization conditions. This stability makes it possible to successfully realize a cyclic adsorption/desorption process.