Pore characterization of different types of coal from coal and gas outburst disaster sites using low temperature nitrogen adsorption approach

To characterize the pore features of outburst coal samples and investigate whether outburst coal has some unique features or not, one of the authors, working as the member of the State Coal Mine Safety Committee of China, sampled nine outburst coal samples(coal powder and block) from outburst disaster sites in underground coal mines in China, and then analyzed the pore and surface features of these samples using low temperature nitrogen adsorption tests. Test data show that outburst powder and block coal samples have similar properties in both pore size distribution and surface area. With increasing coal rank, the proportion of micropores increases, which results in a higher surface area. The Jiulishan samples are rich in micropores, and other tested samples contain mainly mesopores, macropores and fewer micropores. Both the unclosed hysteresis loop and force closed desorption phenomena are observed in all tested samples. The former can be attributed to the instability of the meniscus condensation in pores,interconnected pore features of coal and the potential existence of ink-bottle pores, and the latter can be attributed to the non-rigid structure of coal and the gas affinity of coal.

玛湖凹陷二叠系风城组页岩油储层特征及高产主控因素

通过岩石薄片、扫描电镜、低温氮气吸附、高压压汞、岩心荧光、激光共聚焦显微镜和产液剖面等实验分析测试资料,对玛湖凹陷二叠系风城组储层特征及页岩油高产主控因素进行了详细研究。研究结果表明:①玛湖凹陷二叠系风城组页岩油储层类型可划分为砂岩类、白云岩类和泥岩类等,粉砂岩类储层以陆源碎屑沉积物为主,泥岩类储层以陆源-内源混积物为主,白云(灰)岩类储层以内源化学沉积为主;玛湖凹陷风城组粉砂岩类、白云岩类和泥岩类储层孔隙喉道尺寸依次减小,孔隙连通性依次变差。②玛湖凹陷风城组粉砂岩类储层含油性最好,其次是泥岩类储层,白云岩类储层含油性最差,孔径较大的孔隙和微裂缝中的游离油含量较高,孔径较小的孔隙中的吸附油含量较高。③玛湖凹陷风城组优质烃源岩和优质储层分别控制着页岩油的高产区域和高产层段,长英质矿物含量、有效孔隙度值、游离油孔隙度值、裂缝密度和脆性指数等均较高的储层是页岩油高产的有利层段。

Experimental Research on Pore Structure and Gas Adsorption Characteristic of Deformed Coal

The pore structure and gas adsorption property of deformed coal with different degrees of metamorphism were tested by low-temperature nitrogen adsorption and isothermal adsorption experiments. The fractal theory and the Langmuir adsorption theory were used to analyze the experimental data. The test results showed that the deformed coal had more heterogeneous pore structures and open pores, and its specific surface area(SSA) and fractal dimension(D) were higher. There is a polynomial relationship between D and specific surface area as well as gas adsorption capacity(VL). The gas adsorption capacity of deformed coal is influenced by pore structure, coal rank, deformation and stress together, among which the pore structure is the main influencing factor for the adsorption capacity of deformed coal. The test pressure could affect the accuracy of the adsorption constants a and b, so the highest experiment pressure should be greater than the actual pressure of coal seam in order to reduce the deviation of adsorption constants.

Full-Sized Pore Structure and Fractal Characteristics of Marine-Continental Transitional Shale: A Case Study in Qinshui Basin, North China

Based on 10 shale samples collected from 4 wells in Qinshui Basin,we investigate the full-sized pore structure and fractal characteristics of Marine-Continental transitional shale by performing organic geochemistry,mineralogical composition,Nitrogen gas adsorption(N2 adsorption)and Nuclear Magnetic Resonance(NMR)measurements and fractal analysis.Results show that the TOC content of the shale samples is relatively high,with an average value of 2.44wt%,and the thermal evolution is during the mature-over mature stage.The NMR T2 spectrum can be used to characterize the fullsized pore structure characteristics of shale.By combining N2 adsorption pore structure parameters and NMR T2 spectrums,the surface relaxivity of samples are calculated to be between 1.7877 um/s and 5.2272 um/s.On this basis,the T2 spectrums are converted to full-sized pore volume and surface area distribution curves.The statistics show that the pore volume is mainly provided by mesopore,followed by micropore,and the average percentages are 65.04%and 30.83%respectively;the surface area is mainly provided by micropore,followed by mesopore,and the average percentages are 60.8004%and 39.137%respectively;macropore contributes little to pore volume and surface area.The pore structure characteristics of shale have no relationship with TOC,but strong relationships with clay minerals content.NMR fractal dimensions Dmicro and Dmeso have strong positive relationships with the N2 adsorption fractal dimensions D1 and D2 respectively,indicating that Dmicro can be used to characterize the fractal characteristics of pore surface,and Dmeso can be used to characterize the fractal characteristics of pore structure.The shale surface relaxivity is controlled by multiple factors.The increasing of clay mineral content,pore surface area,pore surface fractal dimension and the decreasing of average pore size,will all lead to the decreasing of shale surface relaxivity.

Assessing soil nitrous oxide emission as affected by phosphorus and nitrogen addition under two moisture levels

Agricultural soils are deficient of phosphorus （P） worldwide. Phosphatic fertilizers are therefore applied to agricultural soils to improve the fertility and to increase the crop yield. However, the effect of phosphorus application on soil N2O emissions has rarety been studied. Therefore, we conducted a laboratory study to investigate the effects P addition on soil N2O emissions from P deficient alluvial soil under two levels of nitrogen （N） fertilizer and soil moisture. Treatments were arranged as follows： P （0 and 20 mg P kg-1） was applied to soil under two moisture levels of 60 and 90% water filled pore space （WFPS）. Each P and moisture treatment was further treated with two levels of N fertilizer （0 and 200 mg N kg-1 as urea）. Soil variables including mineral nitrogen （NH4＋-N and NO3--N）, available P, dissolved organic carbon （DOC）, and soil N2O emissions were measured throughout the study period of 50 days. Results showed that addition of P increased N2O emis- sions either under 60% WFPS or 90% WFPS conditions. Higher N2O emissions were observed under 90% WFPS when compared to 60% WFPS. Application of N fertilizer also enhanced N2O emissions and the highest emissions were 141 μg N2O kg-1 h-1 in P＋N treatment under 90% WFPS. The results of the present study suggest that P application markedly increases soil N2O emissions under both low and high soil moisture levels, and either with or without N fertilizer application.

基于氮气吸附-扫描电镜的构造煤孔隙特征研究

煤的孔隙结构特征与瓦斯的吸附和运移密切相关,构造煤的孔隙结构特征由于受到构造应力的破坏而趋于复杂,因此开展构造煤孔隙发育的研究是提升瓦斯治理水平的重要方向。以西山煤田南部东于煤矿三组构造煤和一组原生煤为研究对象,采取低温液氮吸附法和扫描电子显微镜(SEM),联合观测构造煤与原生煤的孔隙特征。研究表明:三组构造煤的氮气吸附量为原生煤的2.04倍、1.49倍和2.90倍,三组构造煤的孔容为原生煤的2.08倍、1.53倍和2.96倍;三组构造煤的孔容大部分由微孔和小孔提供均达到69.71%以上,孔比表面积大部分由微孔提供均达到了79.04%以上;原生煤的孔容大部分由微孔和小孔提供达到了89.38%,孔比表面积微孔占比93.97%;三组构造煤的孔隙结构相比原生煤更加复杂,具有更大的分形维数(2.6985~2.7106);三组构造煤(10000倍)表面分形维数分别为1.962、1.979、1.947均大于原生煤1.945,构造煤与原生煤相比有更为发育的孔隙特征;分形维数D1与总孔比表面积、微孔比表面积成正比;挥发分含量在一定范围内与总孔比表面积、微孔比表面积、小孔比表面积成正比。

锁阳城土遗址孔隙结构及其分形特征研究

在风化因子的持续作用下,土遗址微观结构持续劣化并最终导致宏观病害的发育。微观结构的特征反映了土遗址材料内在的劣化程度,为研究土遗址风化程度与微观孔隙结构变化的关系,采取锁阳城土遗址不同方位城墙土样,采用低温液氮吸附试验测定了土样的比表面积和孔容孔径分布,并基于FHH分形模型计算样品的分形维数;结果表明,锁阳城土遗址不同样品比表面积偏差率高,比表面积数值和分布具有明显差异;孔隙容积变异系数高,离散程度大,存在差异性劣化行为;土样的孔隙形态呈狭缝状、楔形、“墨水瓶”孔、管状孔等多种复杂形态,小于2.765 nm的孔隙大都为封闭透气孔。结合分形维数可知,锁阳城土样具有明显的分形特征,孔隙空间结构不规则,非均质性强,表面粗糙程度大,且分形维数和锁阳城土遗址劣化程度具有一定相关性。本研究关于土样孔隙的定量表征对于土遗址风化劣化研究有着重要意义。

松辽盆地古龙页岩孔隙结构及分形特征

松辽盆地古龙凹陷青山口组页岩为陆相纯页岩型储层,具有有机质丰度高、成熟度高、黏土矿物含量高等特征。为揭示研究区页岩的孔隙结构特征及非均质性,运用扫描电镜、XRD(全岩矿物分析)、氮气吸附等技术方法,分析了研究区页岩微纳米孔隙及裂缝储集空间类型和孔隙结构,对页理缝进行了分类,并通过FHH模型对研究区页岩储层的分形特征进行研究。结果表明:古龙页岩矿物组成以黏土矿物、石英、长石为主。页理缝主要分为长条状贯穿缝、短簇状尖灭缝、分叉状穿层缝和有机质充填缝,以短簇状尖灭缝为主。古龙页岩具有典型的分形特征,大孔隙的分形维数为2.528~2.555,中小孔的分形维数为2.791~2.829。古龙页岩中2~50 nm的介孔是主要储集空间,平均孔隙体积占比79.85%,有机碳含量与比表面积、孔隙体积、分形维数具有正相关性,平均孔径与分形维数具有负相关性,有机碳与黏土矿物含量是影响分形结构特征的主要控制因素。页岩孔隙结构及分形特征的研究对于页岩含油气性和开发储量的评价有重要意义。

Pore Structure Characteristics of Taiyuan Formation Shale in Qinshui Basin

Qinshui Basin is located in the southeast of Shanxi Province, China. Taking the shale of Taiyuan Formation in Qinshui Basin as the research object, the study analyzed the pore size of the shale of Taiyuan formation in detail from micropore to macropore by the methods of mercury injection, liquid nitrogen analysis and combination of liquid nitrogen and mercury injection. The results show that: 1) the visible pores and macropores are poorly developed and distributed unevenly in the shale of Taiyuan formation, and the micropores are well developed in the shale, and there are more open pores in the pore diameter range, and the pore connectivity is good;2) the liquid nitrogen experiment shows that the pores of Taiyuan Shale are relatively developed between 15 nm and 20 nm, and the formation of hysteresis loop may be caused by some narrow slit pores with similar layered structure;3) the comprehensive analysis of liquid nitrogen and mercury injection experiments shows that the shale of the Taiyuan formation mainly develops micropores, the Mesopores is not developed, the pore volume at 10 - 100 nm is more developed than other parts, and the specific surface is mainly contributed by micropores, which can improve the efficiency of shale gas resolution;at the same time, it provides a channel for Shale gas migration, which is beneficial to the development of shale gas.

鄂尔多斯盆地志靖—安塞地区延长组7段致密砂岩微观孔隙结构评价

储层微观孔隙结构的研究对油气勘探开发具有重要意义。本文采用氮气吸附、铸体薄片观察、扫描电子显微镜(SEM)观察、X射线衍射(XRD)和核磁共振等实验手段研究志靖—安塞地区延长组7段致密砂岩的微观孔隙结构,计算孔隙结构参数,观察微孔分布,分析微孔隙类型,探讨并分析影响微孔发育的矿物成分、粒度及分选等相关参数。结果表明:研究区长7段的岩性主要为长石砂岩;致密砂岩微孔隙结构复杂,主要以黏土粒间溶孔、长石溶孔等形式存在;长7段主要发育小孔喉,微孔体积平均值为6.19×10^(-3)mL/g,孔隙发育差;长7油层组砂岩样品中,长7段的BET(Brunauer-Emmett-Teller)比表面积平均值为4.252 m^(2)/g,总孔体积平均值为0.0183 mL/g,最大孔径平均值为185.9 nm;砂岩孔隙以介孔为主,宏孔和微孔次之。

基于低温液氮浸溶处理的淮南矿区松软中阶煤孔隙特征

为了研究低温液氮浸溶处理对淮南矿区中阶煤孔隙结构及其分形特征影响,采用不同液氮浸溶时间处理煤样,通过压汞法和液氮吸附法对煤体的孔隙结构加以测定,结合分形理论从多角度分析不同浸溶时间下煤体孔隙的发育规律及其尺度特征。结果表明:随着液氮浸溶时间的增加,煤体总孔容由198.089×10^(-3) cm^(3)/g上升至371.553×10^(-3) cm^(3)/g,总比表面积则由4.984m^(2)/g下降至4.496 m^(2)/g,效果显著;煤体吸附孔减小,渗流孔增加,吸附孔的孔隙连通性增加形成更大级别的孔隙,逐渐向渗流孔转变;渗流孔分形维数和吸附孔分形维数与液氮浸溶时间呈现负线性相关,液氮浸溶对于渗流孔分形维数比对吸附孔分形维数的影响程度更为显著;渗流孔分形维数和吸附孔分形维数随着液氮浸溶时间的增大逐渐降低,表明了煤体内部孔隙随着液氮浸溶时间的增大结构复杂程度降低,孔隙之间的贯通性增强,煤体孔隙度和渗透性的增加;综合分形维数随着煤体平均孔径和总孔体积的增加而减小,随着总比表面积的增加而增加,随着液氮浸溶时间的增加,煤体综合分形维数下降,煤体的吸附能力有所减弱,渗流能力有所增强,有助于提升淮南矿区低渗煤层煤层气抽采效果。

长宁地区低阻页岩孔隙结构精细表征及分形研究

为明确四川盆地长宁地区龙马溪组低电阻页岩储层孔隙发育差异性,采用低阻页岩与常规页岩相对比的研究手段,开展了有机碳分析、氮气吸附实验、XRD矿物组分分析和扫描电镜等一系列实验,阐明了长宁低阻页岩储层孔隙结构及其分形特征,并明确了它们的控制因素。结果显示,长宁地区大多数低阻页岩孔隙发育程度明显差于常规页岩,其中,孔体积发育的差异主要体现在2~20 nm孔径范围内,比表面积差异则主要集中在小于1.5 nm和大于1.8 nm段。页岩储层孔隙结构随电阻率的降低有变差的趋势,对低电阻页岩储集能力影响更明显的是有机质含量和成熟度。相较于常规电阻页岩,低电阻页岩在小孔隙段具有更加复杂的孔径及孔壁发育。黏土矿物和黄铁矿对分形维数的影响在不同电阻率页岩中是一致的,而有机质对2类页岩分形维数的影响相反。有机质对分形维数的影响与过演化页岩石墨化后的有机孔变化密切相关。

向斜构造中煤体孔隙结构发育规律研究

为探究向斜构造中煤体孔隙结构发育规律,以长城三矿1311S工作面向斜构造为研究对象,从向斜构造区域不同位置选取煤样,通过低温氮气吸附实验,对煤体孔隙结构特征进行分析。结果表明,向斜构造区域内煤体孔隙结构呈现规律性分布,比表面积与总孔体积从轴部向两翼逐渐减小,平均孔直径则逐渐增大;最可几孔径均分布在2 nm左右,向斜轴部最可几孔径小于两翼;通过对比分析分形维数得出,随着两翼距离向斜轴部越近,分形维数数值呈现线性增大趋势。通过对同一向斜不同位置煤体的孔隙结构特征进行分析,总结出向斜构造中煤体孔隙结构发育规律。

不同变质程度煤体微孔多重分形特征研究

为研究不同变质程度煤体微孔孔径多重分形的特征,根据低温液氮吸附实验数据,运用多重分形理论对4种不同变质煤体样品微孔的多重分形特征、以及孔隙特征与变质程度之间的关联展开研究。结果表明:4种煤样微孔均具备了多重分形的典型特征,变质程度越高煤样的微孔分布非均质性越强,其微小孔拥有更大的比表面积,将会为瓦斯气体提供更多的吸附位,拥有更大的解吸量;4种煤样的微孔孔径多分布在孔隙空间较为狭小的区域中,约为7~9 nm;微孔结构在弱变形作用下的非均质性明显,在此区域内,较大的孔径分布均一;但从整体看,其连通性与变质程度关系不明显且孔隙以聚集和分布不均匀为主导。

基于压汞和低温氮吸附试验的致裂煤孔隙结构及分形特征研究

为了研究致裂作用对煤岩孔隙微观结构的影响,采用低温氮吸附法与压汞法对致裂前后煤样的孔隙形貌、孔径分布等特性进行研究;基于低温氮和压汞数据并结合分形理论,计算不同范围孔隙分形维数。结果表明:经过致裂作用后,煤样孔容都有所增大,致裂煤的大孔孔容是原煤的1.4~2.2倍,微孔孔容是原煤的3.7~8.2倍;在压力小于13.8 MPa的低压区,原煤渗流孔、吸附孔分形维数均大于致裂煤,在压力大于13.8 MPa而小于137.9 MPa的高压区,原煤扩散孔分形维数均小于致裂煤。

活性焦孔结构与含氮官能团协同构筑对低温NO还原特性影响

低温NH_(3)-SCR是排烟温度低的非电力行业烟气脱硝的重要技术选择,低成本、结构可调性好的碳材料是最具潜力的低温NH_(3)-SCR催化剂之一,但面临脱硝效率低的瓶颈。本文以低成本、大储量准东煤为原料,基于一步催化活化工艺制备了具有典型孔隙配组与含氮官能团的活性焦催化剂,探究了活性焦孔隙配组与表面官能团对不同烟气条件下低温NH_(3)-SCR的影响。研究结果表明分级孔与含氮官能团对NH_(3)-SCR均有显著促进作用,兼具分级孔与含氮官能团的氮掺杂分级孔活性焦由于同时改善了传质通道与反应动力学,具有最优的NH_(3)-SCR性能,160℃条件下的脱硝效率高达83.5%,相比氮掺杂微孔活性焦、无掺杂分级孔焦和微孔活性焦分别提升了14.0%、26.5%和110.9%;在SO_(2)或H_(2)O存在条件下,分级孔和含氮官能团对NH_(3)-SCR性能的提升作用更加明显,微孔活性焦脱硝效率会由39.6%衰减至13.8%和34.9%,而氮掺杂分级孔焦脱硝效率有所提升,达86.4%和86.7%,这可能与官能化分级孔环境强化不同烟气组分间的协同效应有关。探明了碳基低温NH3-SCR性能与碳材料理化结构之间的依存关系,为发展高性能碳基低温NH3-SCR技术提供了新思路。

黄土水泥复合材料的孔隙结构演化与强度特征研究

黄土作为一种孔隙结构发育的特殊土壤,具有渗透性、湿陷性、崩解性等特性,容易引发地面裂缝、地表的不均匀沉降等问题。通过氮气吸附、硬度测试和SEM等室内试验对不同掺量水泥黄土孔隙结构和强度特征进行研究。结果表明:随着水泥掺量的逐渐增大,黄土水泥复合材料总孔容逐渐降低,水泥掺量为25%时总孔容较水泥掺量为10%时降低了40%;黄土水泥复合材料压痕硬度和强度与水泥掺量存在明显的正相关性,通过SEM从微观角度直观分析得出黄土水泥复合材料是通过改变土体颗粒大小、形状、连接方式,胶结物填充状态等来改变原土体的物理力学性质。研究可为黄土地区注浆材料的研发提供技术参考。

基于液氮吸附实验的高阶煤微观孔隙结构特征研究——以川南筠连地区上二叠统乐平组为例

川南筠连地区作为中国南方首个煤层气商业生产基地,产气层位为上二叠统乐平组,系统开展储层微观孔隙结构特征研究对明确煤层气赋存成藏特征具有重要意义。针对乐平组煤层气评价井煤岩心样品进行了扫描电镜观察和液氮吸附实验,从孔隙成因类型、孔隙结构、孔隙形态及其甲烷吸附性能等方面对微纳米级孔隙发育特征进行了系统分析。结果表明:煤岩微观孔隙可划分为植物组织孔、气孔、矿物铸模孔和晶间孔等4种成因类型。液氮吸附实验BET总孔比表面积平均为2.638 m^(2)/g,BJH总孔体积平均为0.003 7 cm^(3)/g,且两者具有良好的正相关性。BJH平均孔径为5.775~17.842 nm,对总孔比表面积起到主要贡献的为孔径<5 nm的孔隙,对总孔体积具有明显贡献的主要为孔径≥10 nm的孔隙。根据孔径将孔隙划分为:微孔(<5 nm)、小孔(5~10 nm)、中孔(10~100 nm)、大孔(≥100 nm),微孔和小孔是煤中气体吸附的主要空间,进一步推测吸附孔和渗流孔的孔径分界为10 nm。液氮吸附回线可划分为重叠型、半分离半重叠缓降型、半分离半重叠骤降型等3类,并依据回线特征将纳米孔隙形态理想化为开放孔、半封闭孔和墨水瓶状孔等3种模型,各类孔在高阶煤中均有发育。基于具有不同孔隙形态的干燥无灰基煤样甲烷等温吸附实验得到,墨水瓶状孔的甲烷吸附能力最大,半封闭孔和开放孔的吸附能力近似,但都低于墨水瓶状孔。

低渗透煤层微观孔隙结构与煤层气解吸规律

为研究低渗透煤层微观孔隙结构与气体解吸规律的关系,运用直接观测法、核磁共振法、液氮吸附法等实验手段,对鄂尔多斯盆地伊陕斜坡8号煤层煤样的含气量、孔隙度、渗透率、孔径分布等进行测定。结果显示:煤层气解吸特征与煤的孔径分布、孔的形态、孔的连通性以及比表面积、煤岩成分等因素有关;研究区相隔小于10 m的2套煤层,其孔隙特征、气体解吸规律差异均较大。其中,亮煤的微孔形态以一端开口的圆筒形孔和墨水瓶孔为主,微孔及吸附孔占比为39.2%,煤体微裂缝相对发育,但微孔与介孔的连通性较差,暗淡煤的微孔形态以一端开口的圆筒形孔为主,微孔及吸附孔占比为33.2%,微裂缝不发育,不同孔间连通性差。亮煤气体解吸初期产量大,后期衰减快,气体产出具有明显的阵发式特征;暗淡煤气体解吸初期产量小,约为亮煤的1/2,后期产量递减相对平缓。低渗煤层的开发对策应充分考虑煤层的孔隙结构、孔型、渗透性,应力敏感性、裂缝充填物种类等因素,在精细表征孔隙结构的基础上,根据煤层气不同解吸期特征,结合地质、开发条件制订合理的开发方案。该研究对认识煤层气产气机理及其控制因素,提高煤层气开采效率具有重要的指导意义。

清洁压裂液作用前后煤孔隙结构及分形特征研究

煤孔隙结构特征及分形特征是揭示瓦斯在煤体中的赋存机理及解吸运移规律的重要手段。以沈阳某煤矿的煤样为研究对象进行了清洁压裂液浸泡试验,分别采用扫描电子显微镜、孔隙-裂隙分析系统、氮气吸附和煤表面分形特征对煤表面的孔隙结构进行表征,对清洁压裂液处理前后煤孔隙结构的变化进行了对比分析,结果表明:经清洁压裂液处理后,煤样的孔隙结构得到了较好的发育,煤样表面孔隙数量约为原煤的2.9倍、平均面积约为原煤的2.66倍、平均周长增加了23.06%、平均形状因子增加了30.91%;煤样氮气吸附量从1.5036 mL/g增至2.8255 mL/g,增加的孔隙半径小于10 nm,孔隙连通性增强;清洁压裂液能使吸附孔分形维数增大、渗流孔分形维数减小,煤样内部结构更加简单,孔隙之间的连通性增强,其中吸附孔分形维数从2.331增至2.845,增幅为22.05%;渗流孔分形维数从2.865减至1.756,减幅为38.71%。孔隙结构的定量表征结果显示,清洁压裂液对煤孔隙的发育有一定的促进作用。