纳米纤维状白炭黑的孔隙特征

在与传统白炭黑对比研究的基础上,利用TEM和氮吸附法对纳米纤维状白炭黑(MLD为92.73%)进行研究,主要讨论了纳米纤维状白炭黑多孔结构的成因、孔径大小、孔分布及孔类型等特征分析表明:纤蛇纹石中氢氧镁石八面体层被酸溶蚀和硅氧四面体层的塌陷是导致这种白炭黑具有多孔纳米纤维结构的直接原因。这种白碳黑的长度为微米级或纳米级,其孔隙以小于6.5nm的中孔为主,其中又以孔径2.1nm和3.8nm处的孔隙数量最多。它有两种孔隙类型:纤维上的孔隙和纤维的堆积孔隙。纤维上的孔隙包括SiO2微粒间的孔隙、其聚结体间的孔隙、残余纳米管的管道和毛细…     

潜江凹陷潜江组页岩中可溶有机质赋存空间表征及影响因素分析

为揭示潜江凹陷潜江组3_4段第10韵律(Eq3■)页岩中可溶有机质的赋存空间及其影响因素,采用XRD、索氏抽提、低温氮气吸附、高压压汞、扫描电镜、TOC测试、热解等手段,以抽提前后页岩样品的孔隙结构变化特征为基础,揭示页岩中可溶有机质的赋存空间、孔隙类型和孔隙结构,进而探讨影响页岩孔隙结构变化的主要因素。研究表明,研究区页岩孔隙类型主要为粒间孔、黏土矿物层间孔。扫描电镜和能谱分析表明,页岩中可溶有机质主要赋存在粒间孔和黏土矿物层间孔中。低温氮气吸附实验结果显示页岩孔隙结构分为2种类型,一种以四周开放的平板状孔隙为主,孔隙多为宏孔(孔径50 nm),抽提后孔隙结构未发生改变,仅增加了部分介孔-宏孔;另一种孔隙类型较为复杂,多为开放型圆柱状及平板状孔隙,存在较多的宏孔(孔径50 nm),抽提后小孔径(孔径2～10 nm)孔隙增加较多,孔隙结构更为复杂。石英及黏土矿物的存在促进了微孔及介孔的发育,有利于可溶有机质在微孔以及介孔中的赋存,白云石促进了宏孔的发育,有机质主要赋存于生物成因的白云石粒间孔内。     

四川盆地上三叠统须五段页岩微观孔隙结构及其控制因素

为了深入研究四川盆地上三叠统须五段陆相页岩储层微观孔隙结构,运用氩离子抛光扫描电镜(SEM)、低温氮气吸脱附以及相关地球化学分析实验等技术对该地区页岩储层的微观孔隙结构进行了研究,并对控制其纳米孔隙发育的主要因素进行了探讨。结果表明：四川盆地须五段页岩微观孔隙可分为有机孔和无机孔(粒间孔、粒内孔、晶间孔、溶蚀孔),微裂缝可分为构造微裂缝、有机质生排烃缝和成岩收缩缝等;孔隙结构类型以两端连通的圆柱孔、平行平面间的缝状孔和呈锥形的管孔为主;微观孔隙孔径分布区间大(1~80 nm),峰值主要集中于2~8 nm之间;以中孔(2~50 nm)为主,所占比例为6021%(或以黏土矿物孔为主,所占比例为4462%);页岩的有机质丰度和黏土矿物含量是控制纳米孔隙发育的主要因素。     

鄂尔多斯盆地陆相页岩微观孔隙类型及对页岩气储渗的影响

为深入研究鄂尔多斯陆相页岩储层微观孔隙特征及成藏地质意义,特选取了延长矿区本溪组、山西组、延长组长7、长9段的页岩钻井岩心进行了氩离子抛光扫描电镜实验、压汞实验、氦气吸脱附实验以及相关的地化等实验,实现了对孔隙特征从电镜下直观观察到吸脱附实验间接定性反映,以及对孔隙结构从宏孔到微孔的定量测试。研究结果表明,鄂尔多斯陆相页岩存在粒间孔、粒内孔、晶间孔、溶蚀孔、有机孔及微裂缝共6种微观孔隙类型。其中粒间孔、粒内孔普遍存在,且以黏土矿物聚合体粒间孔和层间粒内孔最为发育,粒间孔孔径多在微纳米级,粒内孔多在几十个纳米内;晶间孔和溶蚀孔仅少量存在于某些特定矿物中,孔径多为纳米级;有机孔相对不发育,以赋存于黏附结合态有机质中且呈凹坑状、片麻状有机孔为特征,孔径多在20nm以内;微裂缝少量存在,多为脆性矿物裂开缝或大型贯通式裂缝。另外,分析得出黏土矿物集合体粒间孔和层间粒内孔对研究区页岩气的赋存和运移贡献最大且是储层各向异性(渗透性)的主要控制因素,晶间孔及溶蚀孔次之;有机孔因相对不发育,可能贡献较小。同时微裂缝的影响不容忽视,是沟通宏孔与中孔的主要微通道。     

中国油气储层中纳米孔首次发现及其科学价值

油气储层孔隙可分为毫米级孔、微米级孔、纳米级孔3种类型,常规储层孔隙直径一般大于1μm。北美地区页岩气储层纳米级孔径范围为5~160nm,主体为80~100nm。在对中国非常规油气储层研究中,应用场发射扫锚电子显微镜与纳米CT重构技术,首次发现了小于1μm的油气纳米孔。其中,致密砂岩油气储层中纳米级孔隙以颗粒内孔、自生矿物晶间孔及微裂缝为主,喉道呈席状、弯曲片状,孔隙直径范围10~1000nm,主体为300~900nm;页岩气储层纳米级孔隙以有机质内孔、颗粒内孔及自生矿物晶间孔为主,孔隙直径范围5~300nm,主体为80~200nm。纳米级孔是致密储层连通性储集空间的主体。纳米级孔隙系统的发现,改变了微米级孔隙是油气储层唯一微观孔隙的传统认识,为认识常规油气局部富集,非常规油气连续聚集的地质特征、研究连续型油气聚集机理、增加资源潜力具有重要的科学意义。     

基于图像分析技术的页岩微观孔隙特征定性及定量表征

在有限的条件下,为了更经济有效地评价页岩微观孔隙特征,同时利用扫描电镜(SEM)、氩离子抛光场发射扫描电镜(FESEM)方法对四川盆地彭水地区龙马溪组页岩孔隙特征进行了定性观察,并借助专业的图像分析软件Iamge J2x提取页岩SEM和FESEM图像蕴含的孔隙定量信息,结合统计学方法分析页岩全孔径分布特征,计算页岩孔隙分形维数,探讨孔隙结构特征以及分析维数与有机碳含量、矿物成分、孔隙吸附能力等的相关性,研究发现:扫描电镜下,彭水地区龙马溪组页岩微米级孔隙发育,主要孔隙类型有粒间孔、黏土矿物层间孔、粒内孔以及微裂缝等;氩离子抛光场发射扫描电镜下,可见大量纳米级孔隙,主要发育有机质孔、无机矿物孔(黄铁矿晶间孔、粒内孔、黏土矿物层间孔、粒间孔等)和微裂缝,两者综合分析更有利于页岩孔隙定性表征;页岩孔隙全孔径分布特征呈4个主峰,主要分布区间为3~9 nm,10~40 nm,100~400 nm,1~4μm;页岩有机质孔隙形状系数分布区间为0.9~1,孔隙呈圆形、近圆形,无机矿物孔形状系数分布在0.5~0.7,多呈三角形、多边形、狭缝形等,孔隙形状较有机质孔复杂,主要受页岩孔隙成因不同所致;彭水地区龙马溪组页岩孔隙符合分形特征,有机质孔隙分形维数较无机矿物孔分形维数小,孔隙结构相对简单;分形维数与有机质含量、矿物成分、孔隙度及吸附气含量都有一定的相关性,随有机质含量的增加,孔隙分形维数增加,孔隙结构复杂化,随分形维数增加,页岩孔隙的最大吸附气含量也随之增加,孔隙吸附能力增强。     

利用纳米透射X射线显微成像技术研究页岩有机孔三维结构特征

页岩纳米级孔隙的三维结构特征直接决定页岩气微观渗流机理,是完善页岩储层流动模型亟需解决的核心问题。本文以龙马溪组页岩有机孔样品(直径约7μm)为研究对象,分别利用同步辐射纳米CT和实验室纳米CT重建有机孔三维空间结构,针对两个装置获得的孔隙结构参数进行对比研究,结果表明:(1)龙马溪组页岩有机孔样品呈蜂窝状,孔隙度约60%,连通性较好;孔径分布呈双峰模式,集中于60~150nm和500~1400 nm;孔径大于500 nm的孔隙对样品的总孔隙度贡献较大。(2)同步辐射纳米CT与实验室纳米CT结果相较,孔隙度和孔隙总数两参数基本一致,喉道总数和喉道半径偏差较大;孔径分布和配位数分布规律虽然类似,但具体数值存在明显差异,值得进一步深入比较分析和研究。(3)纳米CT方法在页岩纳米孔隙三维结构表征方面存在阈值划分难度大与扫描视场过小的问题,可从切片重构算法、三维数据处理、表征单元体三方面进行改进。     

利用纳米CT研究石柱龙马溪组页岩有机孔三维结构特征

页岩纳米级孔隙的三维结构特征直接决定页岩气微观渗流机理,是完善页岩储层流动模型亟需解决的核心问题。本文以龙马溪组页岩有机孔样品(直径约7μm)为研究对象,分别利用同步辐射纳米CT和实验室纳米CT重建有机孔三维空间结构,针对两个装置获得的孔隙结构参数进行对比研究,结果表明:(1)龙马溪组页岩有机孔样品呈蜂窝状,孔隙度约60%,连通性较好;孔径分布呈双峰模式,集中于60~150nm和500~1400nm;孔径大于500nm的孔隙对样品的总孔隙度贡献较大。(2)同步辐射纳米CT与实验室纳米CT结果相较,孔隙度和孔隙总数两参数基本一致,喉道总数和喉道半径偏差较大;孔径分布和配位数分布规律虽然类似,但具体数值存在明显差异,值得进一步深入比较分析和研究。(3)纳米CT方法在页岩纳米孔隙三维结构表征方面存在阈值划分难度大与扫描视场过小的问题,可从切片重构算法、三维数据处理、表征单元体三方面进行改进。     

河南省南襄盆地泌阳凹陷古近系核桃园组湖相页岩油储集层特征

尽管对南襄盆地泌阳凹陷古近系核桃园组湖相页岩采用大型压裂初产已获高产油气流,但是对该湖相页岩储集层特征尚未进行系统研究。文中应用薄片分析及全岩X衍射分析,结合陆相页岩矿物组成特点,将泌阳凹陷湖相页岩划分为块状泥岩、纹层状黏土质页岩、纹层状粉砂质页岩、纹层状灰质页岩及纹层状云质页岩5种类型。根据页岩岩心样品氩离子抛光扫描电镜分析结果,探讨了研究区湖相页岩的储集特征:(1)主要发育溶蚀孔、晶间孔、粒间孔、构造缝、层间页理缝和微裂缝等储集空间类型;(2)孔隙发育具有各向异性;(3)孔隙以中孔体积为主,微孔次之,孔径平均为4.76 nm,有2个峰值区,分别是2～3 nm和71 nm左右。进一步分析表明,岩石类型控制了储集层的储集空间发育特征,研究区以纹层状灰质页岩的溶蚀孔、晶间孔、有机质孔、层间缝等孔隙最为发育,其亦对页岩油储集最为有利。     

柴北缘盆地YQ-1井中侏罗统石门沟组泥页岩纳米孔隙特征及影响因素

柴达木北缘(柴北缘)盆地侏罗纪是典型的陆相湖沼盆地,是目前具有页岩气潜力的盆地之一。本文运用氮气吸附、有机碳含量、有机质成熟度、全岩X衍射分析等方法,对柴北缘鱼卡地区YQ - 1井中侏罗统石门沟组泥页岩的纳米孔隙特征及控制因素进行研究。结果表明,石门沟组泥页岩纳米孔隙结构复杂,根据吸附回线及孔径分布特征可划分为两类,第一类以一端不透气性孔和开放性平行板状狭缝孔为主,孔径主要集中在3～5 nm范围内,呈单峰状分布;第二类则以一端不透气性孔和开放性倾斜板狭缝孔为主,孔径主要分布在3～5 nm和8～14 nm范围内,呈双峰状分布。孔径小于50 nm的微孔和介孔是比表面积和孔体积的主要贡献者;黏土矿物含量与微孔、介孔、总孔体积呈正相关;在较低的成熟度制约下,泥页岩有机质孔隙基本不发育,有机质丰度较高的石门沟组上段H9泥页岩TOC含量与微孔、介孔、总孔体积呈负相关性,有机质丰度较差的下段H8泥页岩TOC含量与孔体积相关性则不甚明显;孔隙结构及孔径分布受沉积环境水动力条件影响;黏土矿物是石门沟组泥页岩纳米孔隙的主要提供者,是孔隙发育的主控因素,TOC含量与沉积环境也会对泥页岩孔隙发育产生一定影响。     

Porous Properties of Nano-fibriform Silica from Natural Chrysotile

With the TEM and physical gas adsorption techniques, porous properties of nano-ribriform silica （MLD： 92.73%） from natural chrysotile are studied in this paper. The results indicate that porous nano-fibriform silica results from brucite octahedral sheets of nature chrysotile dissolved completely and Si-O tetrahedral sheets collapsed by acid leaching. Its length is at a micron or nanometer scale. There are two types of pores： pores among neighboring fibers and pores in nanoriber. These pores （less than 6.5 nm in diameter, mostly 2.1 nm and 3.8 nm） all belong to mesopores. The pores in fibers consist of those among SiO2 particles, those among aggregates, remnant nanotubes and capillary tubes. Nanoribriform silica proves better than the traditional silica as a carrier of catalyzer and a filler for reinforce rubber and plastics.     

利用粉煤灰制备多孔氧化硅的实验

利用相分离原理,以粉煤灰经硅铝分离后所得的硅酸凝胶为原料,选用聚乙烯醇为造孔剂,硝酸为催化剂,成功地制备了多孔氧化硅。实验结果表明:制备的多孔氧化硅的孔道发育良好,含有三级孔道。扫描电镜分析显示:大孔孔径为1～2 μm,比表面积为12.03 m²/g,这与实际应用的硅藻土助滤剂制品大致相当。对实验制品在啤酒液中的稳定性实验结果显示:多孔氧化硅制品在浸泡于啤酒过程中几乎没有Ca²⁺、Fe³⁺离子溶出,浸泡后的啤酒液的pH值基本不变。上述结果表明:实验制备的多孔氧化硅制品作为硅藻土助滤剂的替代品具有良好的实际应用前景。     

水热条件对纤蛇纹石纳米管合成的影响研究

采用水热法在不同反应条件下合成了一系列纤蛇纹石纳米管.利用红外吸收光谱、扫描电镜和透射电镜系统地研究了水热反应中,反应温度、Si/Mg比、反应时间等不同反应参数对合成纤蛇纹石纳米管的晶体生长及其结构的影响.结果表明,温度的升高、Si/Mg比趋近0.68及反应时间的延长均有利于纤蛇纹石的生长,并获得最佳条件下合成的纤蛇纹石条件.     

Hydrate phase equilibria in porous media: effect of pore size and salinity

ABSTRACT Considering the ever-increasing importance of marine gas hydrates, it is crucial to gain a better understanding of clathrate formation and decomposition in porous media. It is well established that, due to capillary effects, small-diameter pores – similar to those found in natural sediments – act to inhibit hydrate stability. However, accurate data constraining these effects are still lacking. Here, we present experimental methane clathrate dissociation data for 3.5 mass% methanol aqueous solutions in confined silica glass pores of narrow distribution (30.6, 15.8, and 9.2 nm mean diameters). These data have been used to validate a thermodynamic model for clathrate stability porous media. Experimental data show a marked improvement on literature data – which we attribute to the experimental and interpretative methods used – and are in good agreement with the model predictions. Results suggest that mass transfer of inhibitors (methanol) and dissolved gas during clathrate formation/dissociation within the porous network plays an important role in controlling gas hydrate equilibria.     

基于复杂网络理论的页岩纳米孔隙连通性表征

页岩孔隙结构的表征是页岩气储层评价的基础性工作。钻取岩芯,采集鄂尔多斯盆地上三叠系延长组页岩。使用纳米CT观测10 μm3、20 μm3、30 μm3、39 μm3空间内页岩的孔隙结构,获取孔隙、喉道数量,以及连通性数据,重构孔隙结构三维模型。将孔隙结构抽象为球-棍物理模型,采用复杂网络理论建立关于孔隙结构连通性的结点-边数学模型。依据无标度网络的数学特性,使用Matlab软件生成10 μm3空间内孔隙连通性网络。引入网络连通熵的概念,用于计算不同空间范围内孔隙连通性网络的网络连通熵,评价孔隙结构的异质性。结果表明:10 μm3、20 μm3、39 μm3空间内孔隙连通性网络度分布符合幂律分布;30 μm3空间内孔隙连通性网络度分布符合指数分布;网络连通熵增加,孔隙和喉道网络的连通性减小。该方法可用于评价页岩孔隙的连通性,进而评价页岩气储层的孔渗特性。     

The zeta-potentials of natural and synthetic chrysotiles

Different specimens of the asbestos mineral chrysotile show widely different zeta-potentials. Strongly positive values are found with samples containing an excess of magnesia in the form of brucite, Mg(OH)₂. Synthetic chrysotile and natural samples containing little or no brucite give moderately positive ζ-values over the pH range 3–11. Feebly positive or weakly negative natural chrysotiles are materials which have suffered weathering; and deliberate acid-leaching of any chrysotile ultimately leaves a strongly negative pseudomorph of silica gel.Since the pH and the ambient concentration of Mg²⁺ ions near the surface are the main factors controlling ζ, and since chrysotile is readily susceptible to leaching in practically all aqueous media and does not come to a true ionic equilibrium in any practical time, the zeta-potential of an ideal chrysotile surface is a hypothetical concept.The results also explain the temporary colloidal stability of very dilute suspensions of chrysotile in weakly acidic media and the mutual coagulation of chrysotile and amosite slurries.     

Sulfation of calcitic and dolomitic lime mortars in the presence of diesel particulate matter

The sulfation of four types of calcitic and dolomitic lime mortars exposed to SO₂ in the presence of particulate matter from diesel vehicle exhaust emissions has been investigated. The binders mineralogy and mortars texture are the main factors influencing the formation of deleterious sulfate salts. The type of binder also influences the pore size distribution and the total porosity of the mortars: for equal aggregate (quartz or dolomite), dolomitic lime mortars have smaller pores and higher porosity than calcitic ones. During the first 24 h exposure to SO₂, calcitic lime mortars undergo a higher weight increase than dolomitic ones due to rapid formation of gypsum on their surface. However, at the end of the sulfation test (10 days), dolomitic mortars show a higher weight increase due to massive formation of epsomite and gypsum, which is facilitated by their higher porosity and the high reactivity of Mg phases in the porous and partially carbonated binder. Control samples (not covered with diesel particulate matter) also develop calcium and magnesium sulfates upon long term exposure to SO₂. This is due to the presence of uncarbonated Ca and Mg hydroxides that promote SO₂ fixation as sulfates. However, the amount and size of sulfate crystals are significantly smaller than those observed on samples covered with diesel particulate matter. These results show that diesel particulate matter enhances the sulfation of lime mortars and demonstrate that sulfation of dolomitic lime is an important mechanism for the in situ formation of highly soluble and deleterious hydrated magnesium sulfates (epsomite and hexahydrite). The use of dolomitic limes in the conservation of monuments exposed to air pollution in urban environments may therefore pose a significant risk.     

ON THE MORPHOLOGY OF THE OUTER WALLS OF REGULAR ARCHAEOCYATHIDS

The types of outer wall structure in regular archaeocyathids can be grouped into six classes: a) walls with simple pores; b) walls with additional formations around the pore apertures; c) walls with knee-shaped curvature of the pore canals; d) walls with an additional porous sheath; e) reticulate walls; and f) walls with branching pore canals. Examples of each class are described with figures. Forms with simple walls predominate in older archaeocyathid-bearing strata, and forms with complex outer wall structure predominate in younger strata. The significance of the observations of outer wall structure in the systematics of the archaeocyathids is discussed and one new genus and two new species of forms with unusual wall structure are described. --A. R. Palmer.     

鄂尔多斯盆地延长组泥页岩储层SiO2赋存状态研究

鄂尔多斯盆地泥页岩储层纯页岩段黏土矿物含量高,储集空间体积小。因此,黏土矿物转化释放的二氧化硅缺乏足够的空间,不能生长成自生石英,只能以非晶态存在于黏土矿物之间;而其粉砂质泥岩夹层中常见微米级孔洞。孔洞由长石溶蚀和黏土矿物转化形成,内部则发育晶形完好的自生石英、绿泥石及含铁方解石。此外,粉砂质泥岩的碎屑颗粒间常发育结块状非晶态二氧化硅,碎屑石英颗粒周围则以次生加大边的形式发育粒状和席状(或片状)非晶态二氧化硅。二氧化硅主要来源于黏土矿物转化与石英碎屑颗粒溶蚀。