泥质岩石纳米孔隙对孔内流体的局限效应

泥页岩以孔隙丰富、孔径细小为特征,纳米孔隙对孔隙流体的局限效应决定了泥页岩中页岩气的赋存形式和扩散性质以及潜在的CO_2处置能力。本文在总结泥质岩石纳米孔隙表征结果的基础上,使用淬火固体密度泛函理论(QSDFT)和分子动力学方法(MD),研究了泥质岩石中纳米孔隙内流体的密度分布、赋存形式以及活动性。结果表明,孔径较小(如1.0nm)时,因孔壁的束缚效应纳米孔隙内甲烷成单层分布,而当孔径增大至2.0nm时,除孔壁表面多层吸附的甲烷外还出现自由态甲烷。相同条件下,孔径较小的孔内吸附态甲烷密度高于孔径较大的孔内吸附态甲烷密度,有机孔内吸附态甲烷的密度高于无机孔内吸附态甲烷的密度。随着温度、压力(深度)的增大,孔隙表面的局限效应减弱,表面束缚的吸附态甲烷比例减小,自由态甲烷相对增加。     

孔隙压力对煤岩基质解吸变形影响的试验研究

煤层气开采过程中,伴随着煤层气不断地吸附、解吸和渗流,煤体产生变形,极易导致煤和瓦斯突出事故。以晋城天地王坡煤矿为例,通过实验室内试验,模拟煤层气在复杂地层漫长的形成和逐渐开采过程,得到了孔隙压力与解吸量、应变的变化关系,并拟合得出其相应关系表达式,揭示了一些新的规律:(1)初期解吸速度较快,解吸量随时间的增长而不断增加,后期解吸速度减缓,解吸量逐渐趋于稳定;(2)孔隙压力与解吸量、应变呈现抛物线曲线关系,随孔隙压力的升高,吸附和膨胀变形占主导,其值均在增大;(3)存在最小孔隙压力值,随孔隙压力的增大,解吸时间增长,孔隙压力越小,吸附解吸规律越不明显,对于晋城天地王坡煤矿3#煤样,该值在1.0MPa左右;(4)不同加载方式对解吸量和变形量影响较大,先部分加载吸附后全部载荷解吸结果同比加全部载荷吸附解吸结果高13%～77%。试验结果可为煤层气(CBM)抽放安全和煤与瓦斯突出防治提供理论依据。     

高压氮气置换甲烷对煤基质孔隙的影响

为探究高压气体吸附-解吸试验对煤基质中孔隙发育规模和结构的影响,选取安鹤矿区鹤壁六矿二1煤层煤样进行了高压氮气置换甲烷吸附-解吸试验,采用低温液氮吸附方法分别测定了高压氮气置换甲烷前后煤的低温液氮吸附解吸曲线,利用BET、BJH和QSDFT 3种分析模型,对煤基质中1.14~300 nm的孔隙规模、分布与结构特征进行了对比分析。分析结果显示煤样的孔容、比表面积和孔隙结构在高压气体置换过程中均发生了变化,孔隙BET比表面积从12.746 0 m2/g降低到7.227 0 m2/g,总孔容从0.009 0 cm3/g降低到0.006 6 cm3/g;孔隙发育规模与孔径分布均发生明显变化,但孔隙形态基本保持不变,孔径分布的变化主要表现为微孔孔容与比表面积的降低为主,而中孔和大孔基本保持不变。      

压裂液对煤岩储层解吸–扩散性能的影响

为预防压裂液自吸侵入煤岩基质孔隙,影响煤岩储层的解吸-扩散性能,以沁水盆地石炭统太原组15号煤为研究对象,开展了低伤害活性水压裂液对煤岩储层解吸-扩散性能的损害评价实验,并基于红外光谱、低温氮气吸附和扫描电镜分析了压裂液作用前后的煤岩表面性质和孔隙结构变化。实验结果表明:压裂液处理后,煤样的甲烷解吸率下降了10.23%,扩散系数损害率为16.67%;煤岩表面亲水性增强,液相滞留效应加剧,煤岩基质孔隙比表面增大、孔隙连通性变差、平均孔径减小,这些变化从根本上揭示了压裂液损害煤岩储层解吸-扩散性能的微观机理。最后,提出了基于纳米颗粒封堵技术和表面活性剂技术的煤岩储层解吸-扩散性能损害预防措施。      

不同变质变形煤储层吸附/解吸特征及机理研究进展

不同变质变形煤储层包括低煤级、中煤级和高煤级变质变形环境中的脆性变形煤、韧性变形煤和过渡型变形煤,不同变质、变形程度和机制对煤层气的吸附/解吸影响较大。干燥煤和平衡水煤的甲烷吸附量随变质程度的增强呈现出不同的变化趋势,干燥煤呈横"S"形且易于解吸,而平衡水煤呈倒"U"字形且吸附/解吸强度皆低于干燥煤样,且解吸过程较干燥煤滞后。构造变形导致煤的大分子结构和纳米级孔隙发生不同程度的改变,进而影响气体的吸附/解吸能力,脆性变形主要增加煤的大、中孔,其基本结构单元堆砌度略有增大,甲烷吸附/解吸程度有所增强;韧性变形主要增加煤的微孔-超微孔,其基本结构单元堆砌度增加较快,煤层气吸附能力增强,降压时韧性变形煤比脆性变形煤具有较高的瞬时解吸速率。由此可见,不同变质变形环境中的煤储层吸附/解吸能力差异较大,这主要是由煤储层内部结构及其影响因素对其制约所决定的。     

低煤阶煤储层孔隙结构特征及其扩散方式

采用数值模拟、扫描电镜、低温氮吸附曲线对呼和湖凹陷不同构造位置煤岩储集空间类型和孔隙结构特征进行系统研究,分析构造作用对孔隙系统的控制作用,探讨不同压力下甲烷气体在纳米级孔隙中扩散方式。研究表明:1洼槽区以原生孔隙和内生裂缝为主;斜坡带构造相对活跃,以反映构造行迹的碎粒孔和张性、剪性裂缝为主,裂缝数量明显增多,规模扩大,对改善渗透性意义较大。2煤岩孔隙的比表面积与孔体积具有较好的正相关关系,与平均孔径呈负相关性,斜坡带孔隙遭到破坏,微孔数量增多,比表面积和孔体积较洼槽区成倍增长,煤岩对甲烷的吸附能力增强。利用吸附、脱附曲线特征对煤岩孔隙结构特征进行评价,斜坡带相对于洼槽区孔隙系统复杂,利于吸附,难于解吸。3斜坡带和洼槽区在采气初期甲烷以分子扩散为主,随着压力的降低,由于孔隙结构的差异性,开采后期洼槽区甲烷分子逐渐由过渡区流动取代分子扩散,斜坡区扩散方式则变化不大。综合分析认为,斜坡带是呼和湖凹陷煤层气勘探的有利区块。     

干酪根对页岩基质中甲烷运移规律的影响

微/纳米孔隙内甲烷的运移研究是进行页岩气藏开发预测及评价的前提和基础.页岩中分布大量的微/纳米孔隙,其中干酪根中的纳米级孔隙分布广泛.由于气体在不同尺度孔隙中的运移机理大不相同,且在有机孔中存在明显的吸附/解吸现象.因而,甲烷在页岩中的运移机理仍需完善.本研究综合物理模拟及数学分析方法,对甲烷渗流规律进行研究.研究结果表明:（1）温度升高,单位质量页岩的产量减少,达到平衡的时间缩短,总体体现在甲烷在高温下的吸附/解吸-扩散速率大.（2）相同生产压力下,随入口压力升高,甲烷运移速率增大,达到产量平衡的时间增长.（3）数学模型充分考虑干酪根中甲烷扩散对气体运移过程的影响,并与实验结果及不考虑干酪根影响的模型进行对比分析,结果显示,本文建立的数学模型能更准确地描述甲烷在页岩基质中的运移动态.      

煤体结构差异的吸附响应及其控制机理

为了研究不同煤体结构煤的吸附行为差异和作用机理, 以焦作煤田为研究区, 对煤体破坏严重的糜棱煤和原生结构煤的岩石学组成、吸附性和孔隙性进行了测试, 结果表明: 煤体破坏后, 吸附、解吸能力增大; 温度增加, 煤的吸附能力均为下降, 解吸能力增加.相比于原生结构煤, 随着温度增加, 糜棱煤吸附能力下降趋势和解吸能力增大趋势比原生结构煤更为明显.研究认为: 煤体破坏后, 不同孔径段的孔隙数量均有增大, 使得煤样容纳气体的能力增大.特别是大中孔含量的增大, 导致了糜棱煤样更容易发生解吸.另外, 煤体破坏后的煤级增高、镜质组含量增大和惰质组含量减小也对吸附能力增大具有重要作用, 而灰分含量不是决定两类煤吸附性差异的主要因素.      

基于Ono-Kondo格子模型的页岩气超临界吸附机理探讨

页岩气吸附机理的研究对于页岩气成藏和储量评价具有重要意义.甲烷在地层温度和压力条件下处于超临界状态,页岩气的吸附实际上为超临界吸附,但其机理目前尚不明确.在建立Ono-Kondo格子模型的基础上,结合低温氮气吸附和高压甲烷等温吸附实验,对龙马溪组页岩的微观孔隙结构和超临界吸附曲线进行了分析.结果表明,页岩中发育的孔隙尺度较小,比表面积较大,吸附气主要赋存于微孔和中孔中;页岩的等温吸附曲线在压力较大时,必然存在下降的趋势,这并非异常现象,而是超临界甲烷过剩吸附量的本质特征.Ono-Kondo格子模型对页岩高压等温吸附曲线的拟合效果很好,相关系数均在0.99以上,说明该模型可以表征页岩纳米孔隙中超临界甲烷的吸附特征.基于拟合得到的吸附相密度可将过剩吸附量转换为绝对吸附量,并直接计算地层温度和压力下甲烷的吸附分子层数,计算层数均小于1,表明甲烷分子并没有铺满整个孔隙壁面.因此受流体性质、吸附剂吸附能力和孔隙结构3个方面的影响,页岩气的吸附机理为单层吸附,不可能为双层甚至多层吸附.      

低温氮吸附法判识构造煤的实验研究

煤体结构是煤与瓦斯突出防治和煤与瓦斯共采的重要地质因素之一。为了区分煤体结构在地应力作用下的破坏程度,采集了淮北矿业股份有限公司桃园煤矿8283采煤工作面煤样,基于自相似原理和实验室内对煤样的加压模拟实验,通过煤基质纳米级孔隙在低温氮吸附-解吸曲线上的响应对比分析,建立了低温氮吸附法判识煤体结构的方法,并对淮北矿业股份有限公司桃园煤矿10号煤层内1026和1035工作面煤体宏观结构及微观孔隙发育特征进行了对比研究。结果表明,煤体微观孔隙结构变化与构造煤发育程度密切相关;随着煤体破坏程度的提高,在吸附-解吸曲线上表现为吸附量明显增大,纳米级孔隙的比表面积和比孔容明显增加,平均孔径略有增加;构造煤解吸曲线上有明显的陡降点,而原生结构煤的解吸曲线不具有这个特征。     

Adsorption Mechanism and Kinetic Characterization of Bituminous Coal under High Temperatures and Pressures in the Linxing‐Shenfu Area

The majority of coalbed methane(CBM) in coal reservoirs is in adsorption states in coal matrix pores. To reveal the adsorption behavior of bituminous coal under high-temperature and high-pressure conditions and to discuss the microscopic control mechanism affecting the adsorption characteristics, isothermal adsorption experiments under hightemperature and high-pressure conditions, low-temperature liquid nitrogen adsorption-desorption experiments and CO2 adsorption experiments were performed on coal samples. Results show that the adsorption capacity of coal is comprehensively controlled by the maximum vitrinite reflectance(Ro, max), as well as temperature and pressure conditions. As the vitrinite reflectance increases, the adsorption capacity of coal increases. At low pressures, the pressure has a significant effect on the positive effect of adsorption, but the effect of temperature is relatively weak. As the pressure increases, the effect of temperature on the negative effect of adsorption gradually becomes apparent, and the influence of pressure gradually decreases. Considering pore volumes of pores with diameters of 1.7-100 nm, the peak volume of pores with diameters 10-100 nm is higher than that from pores with diameters 1.7-10 nm, especially for pores with diameters of 40-60 nm, indicating that pores with diameters of 10-100 nm are the main contributors to the pore volume. The pore specific surface area shows multiple peaks, and the peak value appears for pore diameters of 2-3 nm, indicating that this pore diameter is the main contributor to the specific surface area. For pore diameters of 0.489-1.083 nm, the pore size distribution is bimodal, with peak values at 0.56-0.62 nm and 0.82-0.88 nm. The adsorption capability of the coal reservoir depends on the development degree of the supermicroporous specific surface area, because the supermicroporous pores are the main contributors to the specific pore area. Additionally, the adsorption space increases as the adsorption equilibrium pressure increases. Under the same pressure, as the maximum vitrinite reflectance increases, the adsorption space increases. In addition, the cumulative reduction in the surface free energy increases as the maximum vitrinite reflectance increases. Furthermore, as the pressure increases, the surface free energy of each pressure point gradually decreases, indicating that as the pressure increases, it is increasingly difficult to adsorb methane molecules.     

An Experimental Study on the Conductivity Changes in Coal during Methane Adsorption-Desorption and their Influencing Factors

During the processes of methane adsorption and desorption, the internal structure of coal changes, accordingly leading to changes in electrical conductivity. In this paper, using low rank coal seams of the Yan’an Formation in the Dafosi field as the research subject, the relationship between coal resistivity, methane adsorption quantity, and equilibrium pressure is analyzed through proximate analysis, mercury injection tests, low temperature liquid nitrogen adsorption tests, and coal resistivity measurements during methane adsorption and desorption. The results show that during the process of pressure rise and methane adsorption, the conductivity of coal increases, resulting from heat release from methane adsorption, coal matrix swelling and adsorbed water molecules replaced by methane, but the resistivity reduction gradually decreases. The relationship between coal resistivity and methane adsorption quantity and equilibrium pressure can be described by a quadratic function. During the processes of depressurization and desorption, the resistivity of coal rebounds slightly, due to decalescence of methane desorption, coal matrix shrinkage and water-gas displacement, and the relationship coincides with a linear function. Methane adsorption leads to irreversible changes in coal internal structure and enhances the coal conductivity, and resistivity cannot be restored to the initial level even after methane desorption. The resistivity and reduction rate of durain are higher than those of vitrain, with relatively greater homogeneous pore throat structure and fewer charged particles in the double electric layer. In addition, moisture can enhance the conductivity of coal and makes it change more complexly during methane adsorption and desorption.     

贵州金佳矿区煤储层孔隙结构及等温吸附特征

采用扫描电镜、压汞试验、等温吸附实验分析贵州金佳矿区8个主要煤层孔隙发育特征。煤储层发育较多的原生孔、气孔及张性裂隙,次生孔隙主要为粒间孔,矿物溶蚀孔、矿物铸模孔相对较少;压汞试验表明,3#煤层开放孔较多,压汞曲线为Ⅱ型,孔隙连通性较好; 1#、7#煤层以微小孔为主,压汞曲线为Ⅰ型,孔隙连通性中等;其余煤层压汞曲线为Ⅲ型,孔隙连通性差;煤储层孔隙度、孔容、比表面积与变质程度呈正相关;甲烷等温吸附实验显示3#、24#煤甲烷吸附速率快,吸附能力最强;矿区煤储层孔隙结构对甲烷吸附性的影响有限;对比分析矿区3#煤层有利于煤层气的开发。     

Retention and release of methane in underground coal workings

Summary During an investigation to study the gas flow characteristics of coal, adsorption and desorption rates of methane from powdered coal samples were measured. From adsorption tests, it was found that the capacity of coal to hold methane varies significantly with gas pressure. For pressures up to 4.14 MPa (600 psi) the amount of gas adsorbed was still rising and monomolecular saturation was not reached. Results of desorption tests were used to test three equations suggested by previous investigators to measure the quantity of desorbed gas. It was confirmed that no single equation would define adequately the complete desorption process. Changes of regime appeared to exist at desorption times of 100 s and, to a lesser extent, 1000 s following the initial release of ambient gas pressure. A hypothesis was advanced that initial flow was inhibited or choked by an efflux of desorbing gas molecules. This was followed by a short transitional period and a longer term regime of free flow with reduced resistance offered by the flow paths.     

瓦斯压力对煤系页岩瓦斯吸附特性影响核磁共振谱试验研究

瓦斯压力是影响煤系页岩瓦斯吸附特性的关键因素。以阜新高瓦斯矿井清河门矿煤系页岩为研究对象,采用低场核磁共振（NMR）谱技术,通过向放有试样的夹持器中不断充入瓦斯,模拟煤系页岩瓦斯集聚赋存过程。以核磁共振T2谱幅值积分作为反映瓦斯吸附量定量化指标,从微细观角度定量研究瓦斯压力对吸附态和游离态瓦斯量影响规律。试验结果表明,（1）两个截止阈值确定了吸附态和游离态瓦斯T2谱曲线范围;（2）瓦斯压力对煤系页岩吸附态和游离态瓦斯增量均有显著影响。吸附态瓦斯增量变化受控于煤系页岩和瓦斯分子间作用力,而游离态瓦斯增量则主要与煤系页岩孔隙结构有关;（3）吸附态瓦斯量与瓦斯压力间关系符合朗格缪尔等温吸附方程,而游离态瓦斯与瓦斯压力呈3次函数关系;（4）以瓦斯T2谱均值变化幅度定量描述孔隙平均半径扩胀变形程度,随瓦斯压力增加,煤系页岩中～大孔隙结构均发生显著扩胀,平均半径增加1.47倍,而微孔隙结构尺寸未见明显变化。     

煤体结构对煤层气吸附-解吸及产出特征的影响

煤的孔隙、物理化学结构差异对煤层气的吸附-解吸及产出特征有巨大影响。基于对不同煤体结构煤的孔隙、结构、力学性质的认识,利用现场实测资料,分析了煤体结构对煤层气产出的影响。结果表明:构造变形使煤的孔容和比表面积增大,吸附能力增强。含气量和损失量呈正相关关系;在含气量相同的情况下,逸散速率相对大小依次为:原生结构煤<碎裂煤<碎粒煤<糜棱煤。原生结构煤和碎裂煤的临界解吸压力大于糜棱煤。在0~45 min、45~95 min、95~185 min,平均解吸速率关系为:原生结构煤<碎裂煤<糜棱煤,而在185~485 min内,平均解吸速率关系反生改变,即:糜棱煤<原生结构煤<碎裂煤。在含气量大致相等时,原生结构煤和碎裂煤的解吸量及解吸时间明显大于糜棱煤。      

荷载对重塑煤体吸附特性的影响

碎软煤的完整原样制取困难,需要加工制成重塑煤体,为了研究不同压制荷载对煤体物性特征的影响,以重塑煤体为研究对象,基于低温液氮的孔隙测试实验和高压容量法的甲烷吸附实验,探讨不同成型荷载而成的重塑煤体的微小孔结构及其吸附特性的差异。结果表明:不同成型荷载压制而成的重塑煤体,其微孔和小孔的孔容随着成型荷载的增大而略微减少,孔比表面积随着成型荷载的增大而略微增加,总孔体积减少和孔比表面积增加的幅度不大;通过分形理论发现无论高压段还是低压段,孔隙结构具有明显的分形特征,且在高压段的分形维数普遍低于低压段,不同荷载压制而成的重塑煤体的分形维数差别不大;等温吸附线均符合第Ⅰ类等温吸附曲线,Langmuir模型适用于描述重塑煤体的等温吸附,成型荷载对煤的吸附常数有一定的影响,其对吸附常数b值的影响大于对a值的影响。研究不同成型荷载下重塑煤体的吸附特性,为不同条件下型煤制作及冷冻取心实验提供参考。