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1.
为揭示不同变质程度煤岩纳米级孔隙特征,运用小角X射线散射方法(SAXS),采集镜质体反射率Rmax在0.31%~6.24%的15个样品,基于散射数据获取的煤岩孔隙率、孔径分布、比表面积和分形维数,讨论了煤化过程对煤岩纳米孔隙(0.3~100 nm)结构的影响,并用低温CO2和N2吸附DFT模型结果对孔径分布进行了验证。结果表明:在Rmax < 0.5 %时,煤岩孔隙率和比表面积随着变质程度的增加而增加,微孔(< 2 nm)含量增长较少,介孔(2~50 nm)和大孔(50~100 nm)含量大幅增加,煤岩表面逐渐光滑;在Rmax=0.5%~1.4%时,孔隙率和比表面积减小,各类孔隙含量均减少,煤岩表面逐渐光滑;在Rmax=1.4%~4.0%时,煤岩孔隙率和比表面积增大,微孔含量大幅增加,介孔和大孔含量近乎稳定,煤岩表面逐渐粗糙;在Rmax > 4.0%后,煤岩孔隙率和比表面积缓慢增加,微孔增长幅度变缓,煤岩表面逐渐光滑。SAXS在0.3~100 nm孔径分布(本次实验范围)中用球形形状因子与低温CO2和N2吸附结果契合度较高,煤中纳米级孔隙率及比表面积主要由微孔贡献。 相似文献
2.
Tennille E. Mares Andrzej P. Radliński Tim A. Moore David Cookson P. Thiyagarajan Jan Ilavsky Jürgen Klepp 《International Journal of Coal Geology》2009,77(1-2):54-68
Small angle scattering techniques (SAXS and SANS) have been used to investigate the microstructural properties of the subbituminous coals (Rmax 0.42–0.45%) from the Huntly Coalfield, New Zealand. Samples were collected from the two thick (> 5 m) coal seams in the coalfield and have been analysed for methane and carbon dioxide sorption capacity, petrography, pore size distribution, specific surface area and porosity.Specific surface area (SSA) available for carbon dioxide adsorption, extrapolated to a probe size of 4 Å, ranged from 1.25 × 106 cm? 1 to 4.26 × 106 cm? 1 with total porosity varying from 16% to 25%. Porosity was found to be predominantly composed of microporosity, which contributed the majority of the available SSA. Although considerable variation was seen between samples, the results fit well with published rank trends.Gas holding capacity at the reservoir pressure (approximately 4 MPa) ranged from 2.63 to 4.18 m3/t for methane on a dry, ash-free basis (daf) and from 22.00 to 23.72 m3/t daf for carbon dioxide. The resulting ratio of CO2:CH4 ranged from 5.7 to 8.6, with an average of 6.7:1.Holding capacities for both methane and carbon dioxide on a dry ash free basis (daf) were found to be correlated with sample microporosity. However, holding capacities for the two gases on an as analysed (aa) basis (that is including mineral matter and moisture), showed no such correlation. Carbon dioxide (aa) does show a negative correlation with both specific surface area and microporosity. As the coals have low inorganic matter content, the reversal is thought to be related to moisture which is likely concentrated in the pore size range 12.5–125 Å. Methane holding capacity, both daf and aa, correlates with macroporosity, thus suggesting that the holding capacity of micropores is diminished by the presence of moisture in the pores. 相似文献
3.
为了定量表征煤的孔隙结构,研究煤孔隙特征与吸附性能的内在联系,采用低温液氮吸附法（LP-N2GA）、CO2吸附法、扫描电镜（SEM）和孔隙-裂隙分析系统（PCAS）对6种不同变质程度煤样进行孔隙相关分析.煤样孔隙分布相似时,煤样对N2和CO2的吸附能力、孔隙率的近似概率密度和孔隙面积（中孔）与煤的挥发分呈负相关,煤样孔隙的分形维数与煤的挥发分呈正相关.煤样的孔隙分布差异较大时,煤样对N2和CO2的最大吸附容量与孔隙分布有关.建立了煤纳米孔结构的联合表征模式,该表征模式能够更有效地研究和分析煤中的孔隙,包括孔隙数目、孔隙面积、孔隙周长、平均形状因子、孔隙率、分形维数和孔径分布,将SEM-PCAS与气体吸附方法相结合对煤的孔隙结构进行定量联合表征的模式是可行的. 相似文献
4.
文章通过小角X 射线散射（SAXS） 的方法研究了自然演化系列不同煤级煤的纳米孔隙结构和分布特征。结果表明,
随着煤级的增高,孔隙表面分形呈多阶段变化： Ro＜0.89%,壳质组开始逐渐液化,发育大量孔隙,分形维数不断增大;
Ro 为0.9%~1.5%,因挥发分生油充填孔隙和原油沥青的芳构化等作用,而使微孔表面平整光滑,分形维数减小;Ro 为1.5%
~3.5%,镜质组裂解生气发育了大量纳米孔隙,分形维数再次增大;随后逐渐石墨化,表面分形再次降低。煤中纳米级孔
隙主要集中在50~100 nm 范围内。其中细介孔（2~10 nm） 体积百分比占0.21%~3.12%,中介孔（10~25 nm） 体积百分比占
5.06%~11.28%,粗介孔（25~50 nm） 体积百分比占21.06%~26.36%,大孔（50~100 nm） 所占体积百分比最大,高达
64.63%~68.36%。随着煤级升高,煤样的最可几孔径不断减小,最可几孔径由80 nm 减小到10 nm,减小的速度由缓到快;
中介孔和细介孔体积百分比不断增大,与成熟度分别呈对数和线性关系;粗介孔和大孔百分比不断减少,与成熟度呈对数
关系。最可几孔径变化也十分明显,在低煤化烟煤阶段时,随煤化程度增高最可几孔径略有下降（峰值处的孔径范围在
75~71 nm 内）,中高煤化烟煤阶段时,随煤化程度的增高最可几孔径呈较明显的下降趋势（峰值处的孔径范围在78~53 nm
内）,到无烟煤阶段时,其孔径则快速下降（峰值处的孔径范围在72~9 nm）。 相似文献
5.
高煤阶煤与中低煤阶煤在孔隙结构特征方面存在明显差异,分形理论为定量描述高煤阶煤储层孔隙特征提供了有效手段。基于扫描电镜、压汞实验和孔渗测试,以华北地区最大镜质体反射率(Ro,max)在19%~295%之间的9个煤样为研究对象,采用分段回归的方法对各样品进行不同孔径段分形维数计算,并讨论了孔隙结构分形维数与孔隙体积百分比、Ro,max、孔隙度和渗透率的关系。结果表明,高煤阶煤微小孔发育,半封闭孔含量较高,孔隙连通性一般,且孔隙结构具有明显的分段分形特征,同一煤样的超大孔(孔隙半径r＞5 μm)、大孔(05 μm＜r＜5 μm)、中孔(005 μm＜r＜05 μm)和微小孔(r＜005 μm)的分形维数依次减小;各煤样超大孔、大孔、中孔分形维数均随Ro,max增加而增加,随对应孔隙体积百分比增加而减小;孔隙度或渗透率与超大孔、大孔和中孔、微小孔分形维数分别呈二次相关、线性正相关、负相关;各分形区间分形维数分布的偏度和峰度与孔隙度或渗透率分别呈高度正相关和负相关,这为高煤阶煤孔隙度、渗透率提供了理想的线性方程(y=ax+b)预测模型。 相似文献
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研究煤复杂发育的孔隙结构对揭示煤层气体赋存机理及扩散运移规律有重要意义.为了研究煤的纳米孔隙结构,利用SEM、液氮吸附、小角X射线研究了不同煤阶煤的纳米孔隙在形式和分布上的非均匀性.实验煤样煤基质中的孔呈多峰分布,且孔径范围主要集中在2~10 nm.煤样低温液氮吸附实验测得煤样的吸附量为3.676 cm3/g,煤样的比表面积为1.416 m2/g.以最可几孔径作为研究对象,在实验压力范围内,吸附压力越大,最可几孔径变大的越多;瓦斯气体在纳米级孔隙结构中的扩散模式以过渡型扩散为主,微孔更发达的煤样中,扩散更接近Knudsen型扩散,中孔更发达的煤样中,扩散更接近Fick型扩散;Knudsen数与温度呈负相关关系,温度高于250 K后,Knudsen数趋于稳定,与压强呈正相关关系,压强越大,扩散越容易. 相似文献
7.
煤层气吸附作用是发生在煤基质内表面的物理过程,而煤岩复杂孔裂隙网络为高压甲烷吸附提供了丰富的空间。开展沁水盆地南部高阶煤30℃高压甲烷等温吸附实验,结合煤岩煤质参数与孔隙特征参数,通过改进的D-R模型分析了煤岩性质、孔隙特征与吸附参数的相关性。煤岩性质对最大吸附能力和吸附热参数的影响是多因素叠加的综合效应,而最大吸附能力与微孔体积,吸附体积校正参数与大中孔比表面积呈较好的正相关性,表明甲烷分子在煤基质内表面会根据孔径尺度大小呈现不同的吸附方式。据此提出高压甲烷在煤基质微孔中呈紧密堆积状态而在大中孔中呈多层分子堆叠状态的新认识,为进一步研究煤层气吸附机理提供了新的思路。 相似文献
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9.
华北南部构造煤纳米级孔隙结构演化特征及作用机理 总被引：16，自引：2，他引：14
构造煤是在构造应力作用下,煤体发生变形或破坏的一类煤,在世界主要产煤国家皆有分布。构造变形不同程度的改变着煤的大分子结构和化学成分,而且也影响到构造煤的纳米级孔隙结构(<10 0 nm ) ,它是煤层气的主要吸附空间。通过构造煤显微组分和镜质组油浸最大反射率的测定,采用液氮吸附法对不同变质变形环境、不同变形系列构造煤的纳米级孔隙分类、孔隙结构特征进行了深入系统的研究,并结合高分辨透射电子显微镜和X射线衍射对大分子结构和孔隙结构的分析,结果表明:不同类型构造煤纳米级孔径结构自然分类,可将孔径结构划分为过渡孔(15～10 0 nm )、微孔(5～15 nm )、亚微孔(2 .5～5 nm )和极微孔(<2 .5 nm ) 4类。低煤级变形变质环境中随着构造变形的增强,不同类型构造煤过渡孔孔容明显降低,微孔及其下孔径段孔容明显增多,可见亚微孔和极微孔,过渡孔的比表面积大幅度降低,而亚微孔的却增加得较快。从脆韧性变形煤至韧性变形煤,总孔体积、累积比表面积、N2 吸附量随着构造变形的增强,这些结构参数均迅速增加,但中值半径进一步下降。非均质结构煤孔隙参数与弱脆性变形煤相当。中、高煤级变形变质环境形成的各种类型构造煤与低煤级变质变形环境相比,孔隙参数的变化基本一致。但不同类型构造煤的变化又有所区别 相似文献
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为了查明产甲烷菌群对不同变质程度煤厌氧发酵所产生的生物增透效应,利用显微CT对生物降解前后的煤样进行三维重建,分析煤的孔隙结构变化特征,通过扫描电镜观察产甲烷菌群在煤表面的吸附特征,探讨不同煤阶煤生物改造效果差异的原因。实验结果发现,厌氧发酵后煤样的孔隙率和吼道总长度增加,孔隙的连通性增强,表明在厌氧发酵过程中煤被微生物降解,促进煤中新孔隙的形成、扩展和贯通,从而实现煤的生物增透效应。随着煤的变质程度降低,煤中孔隙结构明显改善,主要原因在于产甲烷菌群更倾向于吸附在低阶煤的表面。研究结果可为煤层气生物工程的现场应用提供理论指导。 相似文献
11.
To better understand the characteristics of coal pores and their influence on coal reservoirs, coal pores in eight main coalfields of North China were analyzed by mercury porosimetry and scanning electron microscopy (SEM). Fractal characteristics of coal pores (size distribution and structure) were researched using two fractal models: classic geometry and thermodynamics. These two models establish the relationship between fractal dimensions and coal pores characteristics. New results include: (1) SEM imaging and fractal analysis show that coal reservoirs generally have very high heterogeneity; (2) coal pore structures have fractal characteristics and fractal dimensions characteristic of pore structures are controlled by the composition (e.g., ash, moisture, volatile component) and pore parameters (e.g., pore diameter, micro pores content) of coals; (3) the fractal dimensions (D1 and D2) of coal pores have good correlations with the heterogeneity of coal pore structures. Larger fractal dimensions correlate to higher heterogeneity of pore structures. The fractal dimensions (D1 and D2) have strong negative linear correlations with the sorted coefficient of coals (R2=0.719 and 0.639, respectively) that shows the heterogeneity of coal pores; (4) fractal dimension D1 and petrologic permeability of coals have a strong negative exponential correlation (R2=0.82). However, fractal dimension D2 and petrologic permeability of coals have no obvious correlation; and (5) the model of classic geometry is more accurate for fractal characterization of coal pores in coal reservoirs than that of thermodynamics by optimization. 相似文献
12.
煤孔隙结构是煤层气勘探开发与煤矿安全研究中的关键问题之一。构造煤相比于原生结构煤非均质性强,是煤储层研究中的热点和难点。采用原子力显微镜,结合NanoScope Analysis和Gwyddion分析软件,对脆性变形序列构造煤的孔隙结构和表面粗糙度特征进行研究。结果表明:构造作用整体上促进了脆性变形煤孔隙的发育,但不同脆性变形构造煤受构造作用影响的程度存在明显差异。根据煤受构造作用影响的程度,脆性变形煤孔隙结构演化可划分为强弱2个阶段:弱脆性变形阶段(原生结构煤—碎裂煤—片状煤—碎斑煤)构造作用对煤体的孔隙结构影响较小,平均孔数量缓慢增长,平均孔径缓慢减小,该阶段构造作用主要促进了100~200 nm大孔的发育;强脆性变形阶段(碎斑煤—碎粒煤—薄片煤)构造作用对煤体孔隙结构产生了显著影响,平均孔数量迅速增长,平均孔径迅速减小,这一阶段构造作用主要促进了10~50 nm介孔和50~100 nm大孔的发育。这表明脆性变形构造煤孔隙结构并非简单的线性演变。不同脆性变形煤的算术平均粗糙度和均方根粗糙度参数分别为3.00~6.05 nm和3.94~7.62 nm,其中,弱脆性变形阶段粗糙度整体较高且无明显变化,而强脆性变形阶段粗糙度迅速降低。通过AFM剖面分析,建立了煤表面孔隙形态的数学模型。基于该模型的算术平均粗糙度模拟结果表明,大孔是煤表面粗糙度的主要贡献者,构造作用主要通过影响煤中的孔隙结构,进而影响煤的表面粗糙度。 相似文献
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低阶煤甲烷吸附特性研究对瓦斯含量预测、瓦斯抽采及危害防治有着重要意义,为此,选取陕西6个典型矿井低阶煤样,进行低温氮吸附、低压二氧化碳吸附及甲烷等温吸附实验,获得低阶煤吸附孔结构特征。利用微孔填充及单分子层吸附理论定量表征甲烷吸附特征参数与吸附孔结构参数之间的关系,明确吸附孔中甲烷吸附机理。结果表明：吸附孔的比表面积主要由微孔提供,甲烷吸附能力主要受吸附孔孔容大小控制,微孔孔容对吸附孔总孔容的贡献率在74.71%～88.97%。甲烷极限吸附量与吸附孔平均孔径呈线性负相关,与吸附孔孔容、比表面积呈线性正相关,Langmuir压力常数随吸附孔平均孔径、孔容和比表面积的增加仅在小范围内波动,无明显线性相关。6个低阶煤样的分形特征明显,综合分形维数为2.573～2.720,平均值为2.647,说明低阶煤吸附孔非均质性强,甲烷极限吸附量随分形维数增加先增加后减小,整体呈上升趋势。基于微孔填充和单分子层吸附理论可以定量表征低阶煤吸附孔结构与甲烷吸附能力之间的关系,甲烷极限吸附量计算值与实验测试值相对误差较小,长焰煤相对误差为4.47%～6.65%,不黏煤为13.77%～16.02%。研究成果可为后... 相似文献
14.
以煤田地质学和煤岩学研究为基础,以场发射扫描电镜为主要观测手段,对不同地区、不同地质时代、不同变质程度的煤进行纳米级气孔研究。结果表明,煤中气孔是煤变质过程中煤层气（瓦斯）生成、聚集与气体逸散后留下的孔隙,属次生孔隙,孔径以纳米级为主,形状多为圆形,密疏不等,分布很不均匀,多个气孔密集,常组成气孔群、气孔带、气孔窝。气孔发育受多个因素影响,显微组分是主要内在因素,变质速率是重要外在因素,变质程度也是影响因素之一。根据镜下可见度,将气孔发育程度描述为发育和不发育,前者密集状气孔多见,后者偶见或仅见稀疏状气孔。根据气孔的发育程度,可以评价煤储层的生气方式和潜力,气孔发育程度越高,指示生气潜力越大。 相似文献
15.
Lawrence M. Anovitz Gary W. Lynn Gernot Rother William A. Hamilton Man-Ho Kim 《Geochimica et cosmochimica acta》2009,73(24):7303-922
In this paper we report the results of a study using small angle and ultra-small angle neutron scattering techniques (SANS and USANS) to examine the evolution of carbonates during contact metamorphism. Data were obtained from samples collected along two transects in the metamorphosed Hueco limestone at the Marble Canyon, Texas, contact aureole. These samples were collected from the igneous contact out to ∼1700 m. Scattering curves obtained from these samples show mass fractal behavior at low scattering vectors, and surface fractal behavior at high scattering vectors. Significant changes are observed in the surface and mass fractal dimensions as well as the correlation lengths (pore and grain sizes), surface area to volume ratio and surface Gibbs Free energy as a function of distance, including regions of the aureole outside the range of classic metamorphic petrology. A change from mass-fractal to non-fractal behavior is observed at larger scales near the outer boundary of the aureole that implies significant reorganization of pore distributions early in the metamorphic history. Surface fractal results suggest significant smoothing of grain boundaries, coupled with changes in pore sizes. A section of the scattering curve with a slope less than −4 appears at low-Q in metamorphosed samples, which is not present in unmetamorphosed samples. A strong spike in the surface area to volume ratio is observed in rocks near the mapped metamorphic limit, which is associated with reaction of small amounts of organic material to graphite. It may also represent an increase in pore volume or permeability, suggesting that a high permeability zone forms at the boundary of the aureole and moves outwards as metamorphism progresses. Neutron scattering data also correlate well with transmission electron microscopic (TEM) observations, which show formation of micro- and nanopores and microfractures during metamorphism. The scattering data are, however, quantifiable for a bulk rock in a manner that is difficult to achieve using high-resolution imaging (e.g. TEM). Thus, neutron scattering techniques provide a new approach to the analysis and study of metamorphism. 相似文献
16.
二氧化氯在作为煤储层压裂破胶剂的同时,兼具降低煤的亲甲烷能力和化学增透作用。查明二氧化氯对煤储层物性改变的内在机理,对深部煤储层改造摒弃传统活性水改用高粘压裂液有重要意义。通过对二氧化氯改性前后的不同变质程度煤样的压汞和Raman光谱测试,对比分析了煤样改性前后的孔隙结构和化学结构的变化特征。测试结果表明:煤样改性后孔隙度和孔容不同程度增加,比表面积降低;改性后煤的脂肪链的支链化程度和芳香环的缩合程度均降低,煤结构单元缺陷增加,芳碳总量相对减少。可见,煤储层物性改变的机理在于煤孔隙结构及其大分子结构发生了相应变化。 相似文献
17.
为分析准噶尔盆地南缘（简称准南）低煤阶煤储层可动流体、束缚流体以及孔径分布特征,对准南6个矿区6个煤样进行了高速离心和低场核磁共振实验。实验结果表明:准南低煤阶煤以吸附孔发育最优,其次为渗流孔和裂隙。建立束缚水状态的最佳离心力为1.380 MPa;结合饱和水状态和束缚水状态的核磁共振T2谱,得到可动流体孔隙度为0.45%~1.89%,平均1.29%;束缚流体孔隙度为1.03%~7.45%,平均4.18%,可动流体孔隙度与渗透率呈幂指数关系（R2=0.935 8）。根据"离心-T2C法"得到准南低阶煤孔隙半径主要分布在0.01~1 μm,平均孔隙半径为1.771 μm。 相似文献
18.
A high rank coal was tested in terms of loading and unloading to characterize changes in the permeability and effective porosity of tectonically deformed coals. The coal sample, an anthracite, is subdivided into four types according to its structure, namely, the primary structure coal, cataclastic coal (the weakest deformation coal), granulated coal (the moderate deformation coal), and mylonitic coal (the intensest deformation coal); the latter three types are considered to be tectonic deformation coals. Permeability of tectonically deformed coals shows a negative exponential relation to stress. The intenser the structural deformation in coal is, the lower the permeability. Two evaluation parameters, namely, loss rate m (0.8318–0.9476) and damage rate n (0.447–0.6556), which are related to changes in permeability, increase with increasing structural deformation in coal. The cleat compressibility factor declines with increasing difference in effective stress and increases with increasing structural deformation in coal. This study proposes a calculation method for evaluating the porosity damage. Similar to the loss ratio and damage rate, this parameter (η) increases with increasing structural deformation in coal and reveals the relationship between the porosity damage and the structural deformation in coal. 相似文献
19.
煤的微观孔隙结构特征是煤储层特征的重要研究内容之一。选取黄陇侏罗纪煤田转角勘查区4个典型低阶煤样品为研究对象,以煤质特征研究为基础,进行压汞和液氮吸附实验,获取了不同测试方法的煤孔隙结构参数。根据两种测试方法的优缺点在孔径50nm处采用曲线拼接法进行联合,分析了全孔径段的比表面积和孔隙体积分布。结果显示:煤的比表面积主要分布在微孔、小孔和中孔三个区间,呈现“三峰”特征,表现为微孔>小孔>中孔>大孔的分布特征;孔隙体积主要分布在微孔、小孔和大孔。灰分含量和阶段孔径比表面积和孔隙体积具有较好的相关关系,但相关性强弱不同,总体显示和微孔、小孔及中孔呈正相关关系,而与大孔孔隙呈负相关关系,灰分含量与微孔、小孔的影响最大。显微组分中的镜质组和壳质组含量与大孔比表面积和孔隙体积呈正相关关系,与微孔、小孔呈负相关关系;惰质组含量与大孔孔隙比表面积和孔隙体积呈负相关关系,和微孔、小孔呈正相关关系。 相似文献
20.
为了综合分析盘江矿区月亮田矿煤层气勘探开发地质条件与潜力,研究采用多种测试手段,系统分析了该矿煤储层在孔隙度及孔隙结构、渗透性和储层压力在垂向分布的特征与差异。结果表明,盘江矿区月亮田矿二叠系龙潭组煤储层孔隙度较低,小孔体积占明显优势并且比例接近,微孔和小孔比表面积占优势但变化较大,主要发育狭缝状孔和细径广体的墨水瓶状孔。该区煤层渗透率在垂向上的变化较大,且并非为应力主控,受多种地质条件的综合影响。龙潭组煤储层压力属于异常低-异常高压范围,随埋藏深度的增加而增大,推测区内龙潭组煤系地层在垂向上至少存在2个独立含煤层气系统。针对龙潭组煤储层物性垂向分布特征的研究,期望可以为月亮田矿煤层气开发提供新的地质参考。 相似文献