液态水影响不同煤级煤吸附甲烷的差异及其机理

以IS100等温吸附解吸仪和MTS815型电液伺服岩石实验系统为主要实验平台,应用已建立的模拟储层条件下煤样注水和注水试样等温吸附实验方法,对3种不同煤级的煤储层样品开展了高压（8～20 MPa）注水和等温吸附实验,发现储层条件下煤层中的液态水（注水煤样）对不同煤级（0.46%<Ro,max<1.72%）煤吸附甲烷影响有差异,其含水量随煤级升高呈L型降低,而吸附量则线性增加。笔者认为液态水造成吸附差异的原因是煤体润湿性的差异,对于中低煤级的煤样来说,煤表面的物理化学性质起着控制作用,直接影响着煤体润湿性,吸附势和含水量的曲线都说明了这一点。     

不同煤级煤层气吸附扩散系数分析

应用扩散理论模型模拟吸附扩散过程,根据四种煤级煤样的平衡水和注水等温吸附实验数据计算吸附扩散系数,研究吸附扩散的规律。研究表明：煤的孔隙结构是影响煤吸附扩散过程的主要因素。液态水对煤的润湿性随煤级增高而降低,对吸附扩散过程的影响逐渐减小,大孔和中孔发育的煤扩散速率较快,扩散系数高,过渡孔和微孔发育的煤相对扩散速率较慢,扩散系数低。     

水分和粒度对煤吸附甲烷性能的实验研究

为了研究水分含量和粒度对煤吸附甲烷性能的影响,取山西西山杜儿坪矿2号煤干燥样、平衡水样和注水样进行了等温吸附实验。基于分子间作用力对水含量影响机理进行分析,并运用维里方程拟合等温吸附实验结果来验证。实验结果发现,在未达到平衡水分之前,水含量对高煤级吸附能力影响小且注水煤样中的液态水影响增加了甲烷吸附量;同一种煤的高含水煤样对液态水的亲和能力要远比平衡水煤样对气态水的亲和能力强。     

低煤阶煤中甲烷扩散性能分析

甲烷在煤基质中的扩散性能是影响煤层气产出的重要储层参数。采用云南东南部地区新近系中新统小龙潭组褐煤样品,开展了低煤阶煤中甲烷等温吸附实验。基于等温吸附实验获得的吸附量与时间的关系数据,应用一元孔隙结构气体非稳态扩散模型,计算了煤中甲烷气体扩散系数,揭示了煤中甲烷扩散规律和控制机理。研究结果表明,低煤阶煤中气体扩散规律服从Langmuir方程,煤中甲烷有效扩散系数和扩散系数随着压力的增高而增大;吸附时间常数随着压力的增高而减小,服从负指数函数规律。4个实验煤样Langmuir有效扩散系数和扩散系数分别是（1.71~5.46）×10-4 s-1和（2.17~6.91）×10-12 m2/s,Langmuir压力为0.63~1.97 MPa。在相同温度和压力条件下,干燥煤样的有效扩散系数和扩散系数大于平衡水分煤样,随着温度的增高,其有效扩散系数和扩散系数增加,煤中气体扩散性能增强。      

煤基质中甲烷扩散动力学特性研究

甲烷在煤基质中的质量传递过程可用费克第一定律或费克第二定律来模拟。本文通过等温吸附-解吸实验的动力学数据,以费克第二定律为理论基础,对煤基质球形单元模型建立了试验求取扩散特性的方法。晋城煤样等温吸附及解吸实验的数据处理结果表明,吸附-解吸速率均随压力及煤样气含量的增加而增加;吸附速率与解吸速率随压力的变化曲线基本相同。      

煤的比表面积 孔体积及其对煤吸附能力的影响

在液氮温度下，通过测试煤样在气体饱和蒸气压力范围内对N2的吸附过程及吸附量，用BET降BJH理论模型计算出煤的孔体积和孔表面积。同时，对煤样进行等温吸附CH4试验，根据试验结果,探讨了煤的孔体积，孔比表面积及与孔类型的关系，及其对煤吸附能力的影响，即煤对CH4的吸附能力与总孔体积，总孔比表面积，微孔比表面积呈正相关。     

孔径结构、水分对低阶煤煤层气赋存的影响——以新疆地区侏罗系西山窑组褐煤为例

通过对新疆伊犁盆地和准噶尔盆地侏罗系西山窑组主力煤层样品进行了压汞法及低温液氮法实验,分析了煤岩的孔隙结构特征;利用煤样的甲烷等温吸附实验,研究了孔隙结构、水分对吸附气赋存的影响。实验和综合分析结果表明:低煤阶煤以中孔、大孔为主的孔隙特征决定了煤层气主要以游离状态赋存其中,水分是影响吸附气的重要因素。     

不同煤级煤对H2S气体的吸附差异及吸附模型

为了研究不同煤级煤对H₂S气体的吸附差异及吸附模型,采集新疆气煤,山西潞安瘦煤、晋城无烟煤3个煤样进行了工业分析、煤岩分析和平衡水条件下的等温吸附实验。采用Langmuir,BET,D-R和D-A吸附模型,利用拟合软件对等温吸附实验数据进行了非线性回归拟合,并检验拟合程度。结果表明:煤对H₂S的吸附量随着煤化程度的加深而增加,为第Ⅰ类等温吸附线;其中Langmuir模型的拟合效果最好,n=1的D-A模型的拟合效果次之,BET模型的拟合效果较差,模型对实验数据的拟合效果与吸附模型中参数个数无明显关系;煤吸附H₂S可用单分子层吸附理论来解释。      

中阶构造煤等温吸附/解吸特征及机理

选择四个不同变形程度的中阶煤样品作为研究对象,通过开展煤样的等温CH4吸附/解吸实验、X射线衍射(XRD)和傅里叶变换红外光谱(FT-IR)测试分析,研究了构造煤等温吸附/解吸性随煤变形程度的演化特征及其地球化学机理.结果表明,构造煤等温CH4吸附和解吸曲线随压力升高均呈现先快速增大后逐渐稳定的变化趋势,符合I型等温线...     

河北开滦矿区晚古生代煤对CO2 和CH4 气体吸附模型探讨

对河北开滦矿区不同变质程度的煤进行了纯CO2和纯CH4气体等温吸附实验,并用Langmuir模型、三参数BET模型和吸附势理论模型（DR,DA）对煤的吸附实验数据进行了拟合,检验了各模型的拟合程度。结果表明：中煤阶烟煤的马家沟矿9号煤（Ro, ran = 1.21%）对CH4和CO2吸附能力比低煤阶烟煤的林南仓矿11号煤（Ro, ran = 0.58%）的吸附能力大;在相同压力下,同一煤样对CO2的吸附能力明显大于对CH4的吸附能力。马家沟矿9号煤对CO2和CH4的等温吸附线具有典型的I型特征,各模型对其吸附行为拟合误差相差很小,可用Langmuir方程描述;林南仓矿煤等温吸附线较复杂,因用Langmuir描述误差较大,应优先选择误差较小的吸附势理论DA模型来描述其吸附行为。9号煤对CH4和11号煤对CO2和CH4的吸附均以单分子层吸附为主。     

On the effects of petrographic composition on coalbed methane sorption

The effect of petrographic composition on the methane sorption capacity has been determined for a suite of coals and organic-rich shales. Subbituminous and bituminous coals were separated into bright and dull lithotypes by hand-picking. The methane sorption capacities range between 0.5 and 23.9 cm³/g at a pressure of 6 MPa. The low volatile bituminous Canmore coal and the anthracite sample have the highest capacities with the “natural coke” having the lowest. For low-rank coals there is no significant difference between bright and dull samples except for one coal with the dull sample having a greater sorption capacity than its bright equivalent. For higher-rank coals, the bright samples have a greater methane capacity than the dull samples and the difference between sample pairs increases with rank. The boghead coal samples have the highest sorption capacities in the liptinite-rich coals suite and are higher than subbituminous to medium volatile bituminous samples. Pore size distribution indicates that methane is held as solution gas in liptinite-rich coals and by physical sorption in micropores in liptinite-poor coals. These contrasting processes illustrate that liptinite-rich samples need to be independently assessed. The positive relationship between reactive inertinite content and methane sorption capacity occurs within the subbituminous to medium volatile bituminous coals because the reactive inertinite is structurally similar to vitrinite and have a higher microporosity than non-reactive inertinite. Reactivity of inertinite should be assessed in CBM studies of dull coals to provide a better understanding of petrographic composition effects on methane capacity.     

中煤级煤吸附甲烷的物理模拟与数值模拟研究

基于184个中煤级（镜质组最大反射率Ro,max介于0.65%~2.50%）煤在平衡水条件下的等温吸附实验成果,模拟了中煤级煤的朗格缪尔体积和压力与煤级的关系,建立了不同埋深（温度、压力）条件下不同煤级煤饱和吸附气量量板,探讨了压力和温度对中煤级煤吸附甲烷能力的综合效应,对比分析了中煤级煤吸附特征与低、高煤级煤的差异,提出了中煤级煤吸附气量预测的方法。     

http://www.sciencedirect.com/science/article/pii/S1674987112000308

The Panguan Syncline contains abundant coal resources,which may be a potential source of coalbed methane.In order to evaluate the coalbed methane production potential in this area,we investigated the pore-fracture system of coalbed methane reservoirs,and analyzed the gas sorption and seepage capacities by using various analytical methods,including scanning electron microscopy（SEM）,optical microscopy,mercury-injection test,low-temperature N₂ isotherm adsorption/desorption analyses,lowfield nuclear magnetic resonance and methane isothermal adsorption measurements.The results show that the samples of the coal reservoirs in the Panguan Syncline have moderate gas sorption capacity.However, the coals in the study area have favorable seepage capacities,and are conductive for the coalbed methane production.The physical properties of the coalbed methane reservoirs in the Panguan Syncline are generally controlled by coal metamorphism:the low rank coal usually has low methane sorption capacity and its pore and microfractures are poorly developed;while the medium rank coal has better methane sorption capacity,and its seepage pores and microfractures are well developed,which are sufficient for the coalbed methane’s gathering and exploration.Therefore,the medium rank coals in the Panguan Syncline are the most prospective targets for the coalbed methane exploration and production.     

热-力作用原煤变形特征与力学性质演化试验研究

开展原煤在热-力作用下煤热膨胀与吸附瓦斯解吸研究对于深入理解深部煤岩失稳破坏机制有重要意义。通过对四川白皎矿和徐州张双楼矿的原煤施加不同温度-应力条件,获取煤的热变形、解吸气体运移以及煤的力学性质的热响应。试验结果表明:白皎煤在低于35℃条件下表现为膨胀变形;在高于35℃恒温环境下,煤体变形表现为先膨胀后收缩趋势。张双楼煤在低于60℃条件下表现为先膨胀后会出现收缩;在高于60℃恒温环境下,煤样趋向整体膨胀。其结果说明,煤岩在热环境中的变形行为取决于煤基质的热膨胀与解吸收缩之间的竞争结果。煤吸热升温后孔隙中解吸气体数量增多,煤样在受载压缩变形过程中显现出复杂解吸气体排放特征,包括煤中原生孔隙裂隙压缩闭合排出气体,煤体内不均匀变形导致气体流动,煤体开裂导致气体回流。力学测试结果表明,煤样的单轴抗压强度以及弹性模量随着环境温度上升均表现出下降趋势。其结果为深入理解深部煤层在热-力耦合下渗透率与强度变化机制提供试验依据。     

Methane and CO2 sorption and desorption measurements on dry Argonne premium coals: pure components and mixtures

Sorption and desorption behaviour of methane, carbon dioxide, and mixtures of the two gases has been studied on a set of well-characterised coals from the Argonne Premium Coal Programme. The coal samples cover a maturity range from 0.25% to 1.68% vitrinite reflectance. The maceral compositions were dominated by vitrinite (85% to 91%). Inertinite contents ranged from 8% to 11% and liptinite contents around 1% with one exception (Illinois coal, 5%). All sorption experiments were performed on powdered (−100 mesh), dry coal samples.Single component sorption/desorption measurements were carried out at 22 °C up to final pressures around 51 bar (5.1 MPa) for CO₂ (subcritical state) and 110 bar (11 MPa) for methane.The ratios of the final sorption capacities for pure CO₂ and methane (in molar units) on the five coal samples vary between 1.15 and 3.16. The lowest ratio (1.15) was found for the North Dakota Beulah-Zap lignite (VR_r=0.25%) and the highest ratios (2.7 and 3.16) were encountered for the low-rank coals (VR_r 0.32% and 0.48%) while the ratio decreases to 1.6–1.7 for the highest rank coals in this series.Desorption isotherms for CH₄ and CO₂ were measured immediately after the corresponding sorption isotherms. They generally lie above the sorption isotherms. The degree of hysteresis, i.e. deviation of sorption and desorption isotherms, varies and shows no dependence on coal rank.Adsorption tests with CH₄/CO₂ mixtures were conducted to study the degree of preferential sorption of these two gases on coals of different rank. These experiments were performed on dry coals at 45 °C and pressures up to 180 bar (18 MPa). For the highest rank samples of this sequence preferential sorption behaviour was “as expected”, i.e. preferential adsorption of CO₂ and preferential desorption of CH₄ were observed. For the low rank samples, however, preferential adsorption of CH₄ was found in the low pressure range and preferential desorption of CO₂ over the entire pressure range.Follow-up tests for single gas CO₂ sorption measurements consistently showed a significant increase in sorption capacity for re-runs on the same sample. This phenomenon could be due to extraction of volatile coal components by CO₂ in the first experiment. Reproducibility tests with methane and CO₂ using fresh sample material in each experiment did not show this effect.     

不同煤级煤及其萃余物吸附性能的研究

采用不同溶剂对褐煤、焦煤、低级无烟煤(Ro,max2.62%)以及中级无烟煤(Ro,max3.74%)等四个煤级煤样进行分级超声萃取,然后对原煤和萃余物进行平衡水预湿的方法,进行了等温吸附实验,并结合孔隙结构测试和水分含量变化,分析了溶剂萃取后萃余物的吸附性能变化及其影响因素。研究发现:(1)平衡水条件下,原煤对甲烷的吸附能力要大于萃余物,萃取后,尽管煤的组成和孔隙结构发生了变化,但并不能改变不同煤级煤吸附甲烷的能力的对比关系;(2)原煤和各级萃余物都发生了到某一压力后,吸附量随着压力增加而下降的现象,褐煤及其萃余物甚至出现负值,这可能是由超临界状态下吸附相的体积忽视后带来的效应和煤基质在压力、水分作用发生膨胀以及随着压力增加,水分在吸附孔隙中占据吸附点位的增多,造成甲烷有效吸附点位的减少等综合作用的结果。研究认为,在讨论影响不同煤化作用的煤吸附能力的因素时,应该首先考虑到煤级对吸附能力的影响;对煤化程度相近的煤,其他因素如孔隙结构和水分的变化对吸附的影响才显现,但对不同煤级煤吸附性的主要影响因素也不尽相同。在煤层气吸附研究中,吸附量下降现象应该是一个共性,其机理的解释和寻求正确的吸附相体积校正,以及一定压力下,煤基质在水分作用下发生膨胀对吸附性的影响的规律描述,都是亟待解决的重要问题。     

Methane and carbon dioxide sorption on a set of coals from India

Complete sorption isotherm characteristics of methane and CO₂ were studied on fourteen sub-bituminous to high-volatile bituminous Indian Gondwana coals. The mean vitrinite reflectance values of the coal samples are within the range of 0.64% to 1.30% with varying maceral composition. All isotherms were conducted at 30 °C on dry, powdered coal samples up to a maximum experimental pressure of ~ 7.8 MPa and 5.8 MPa for methane and CO₂, respectively.The nature of the isotherms varied widely within the experimental pressure range with some of the samples remained under-saturated while the others attained saturation. The CO₂ to methane adsorption ratios decreased with the increase in experimental pressure and the overall variation was between 4:1 and 1.5:1 for most of the coals. For both methane and CO₂, the lower-ranked coal samples generally exhibited higher sorption affinity compared to the higher-ranked coals. However, sorption capacity indicates a U-shaped trend with rank. Significant hysteresis was observed between the ad/desorption isotherms for CO₂. However, with methane, hysteresis was either absent or insignificant. It was also observed that the coal maceral compositions had a significant impact on the sorption capacities for both methane and CO₂. Coals with higher vitrinite contents showed higher capacities while internite content indicated a negative impact on the sorption capacity.     

高煤级煤储层含水性特征及其对吸附能力的影响

为了研究高煤级煤储层含水性对吸附能力的影响,对阳泉-寿阳区块8件代表性煤样开展了镜质体反射率、显微组分、孔隙度、压汞、核磁共振和甲烷等温吸附等实验,分析了煤储层孔径分布、核磁共振T2谱响应特征、核磁孔隙度以及煤岩吸附能力,同时对煤储层含水性和煤储层吸附能力的相互关系进行了分析。研究结果表明：高煤级煤储层孔隙以微孔发育为主,孔隙含水性以微小孔中的束缚水赋存状态为主,且其含水量随最大镜质体反射率(Ro,m)的增大而增加。在影响高煤级煤储层吸附能力的多种因素中,煤储层含水性对煤岩吸附能力起着决定性的作用,尤其体现在微小孔中的束缚水对吸附能力的影响,束缚水含量越高,煤岩吸附能力越差。     

CBM and CO2-ECBM related sorption processes in coal: A review

This article reviews the state of research on sorption of gases (CO₂, CH₄) and water on coal for primary recovery of coalbed methane (CBM), secondary recovery by an enhancement with carbon dioxide injection (CO₂-ECBM), and for permanent storage of CO₂ in coal seams.Especially in the last decade a large amount of data has been published characterizing coals from various coal basins world-wide for their gas sorption capacity. This research was either related to commercial CBM production or to the usage of coal seams as a permanent sink for anthropogenic CO₂ emissions. Presently, producing methane from coal beds is an attractive option and operations are under way or planned in many coal basins around the globe. Gas-in-place determinations using canister desorption tests and CH₄ isotherms are performed routinely and have provided large datasets for correlating gas transport and sorption properties with coal characteristic parameters.Publicly funded research projects have produced large datasets on the interaction of CO₂ with coals. The determination of sorption isotherms, sorption capacities and rates has meanwhile become a standard approach.In this study we discuss and compare the manometric, volumetric and gravimetric methods for recording sorption isotherms and provide an uncertainty analysis. Using published datasets and theoretical considerations, water sorption is discussed in detail as an important mechanisms controlling gas sorption on coal. Most sorption isotherms are still recorded for dry coals, which usually do not represent in-seam conditions, and water present in the coal has a significant control on CBM gas contents and CO₂ storage potential. This section is followed by considerations of the interdependence of sorption capacity and coal properties like coal rank, maceral composition or ash content. For assessment of the most suitable coal rank for CO₂ storage data on the CO₂/CH₄ sorption ratio data have been collected and compared with coal rank.Finally, we discuss sorption rates and gas diffusion in the coal matrix as well as the different unipore or bidisperse models used for describing these processes.This review does not include information on low-pressure sorption measurements (BET approach) to characterize pore sizes or pore volume since this would be a review of its own. We also do not consider sorption of gas mixtures since the data base is still limited and measurement techniques are associated with large uncertainties.     

Impact of experimental parameters for manometric equipment on CO2 isotherms measured: Comment on “Inter-laboratory comparison II: CO2 isotherms measured on moisture-equilibrated Argonne premium coals at 55°C and up to 15 MPa” by Goodman et al. (2007)

Modelling the sorption properties of coals for carbon dioxide under supercritical conditions is necessary for accurate prediction of the sequestering ability of coals in seams. We present recent data for sorption curves of three dry Argonne Premium coals, for carbon dioxide, methane and nitrogen at two different temperatures at pressures up to 15 MPa. The sorption capacity of coals tends to decrease with increasing temperature. An investigation into literature values for sorption of nitrogen and methane by charcoal also show sorption capacities that decrease dramatically with increasing temperature. This is inconsistent with expectations from Langmuir models of coal sorption, which predict a sorption capacity that is independent of temperature. We have successfully fitted the isotherms using a modified Dubinin–Radushkevich equation that uses gas density rather than pressure. A simple pore-filling model that assumes there is a maximum pore width that can be filled in supercritical conditions and that this maximum pore width decreases with increasing temperature, can explain this temperature dependence of sorption capacity. It can also explain why different supercritical gases give apparently different surface sorption capacities on the same material. The calculated heat of sorption for these gases on these coals is similar to those found for these gases on activated carbon.