A comparison of results from two different flash pyrolysis methods on a solid bitumen sample

A Cambrian solid bitumen from northwestern Sichuan Basin, southern China was analyzed using two different flash pyrolysis methods coupled with gas chromatography–mass spectrometry analysis, including Pyroprobe® and analytical laser micropyrolysis. Results show that pyrolysis products from a Pyroprobe® (model 5000) analysis are dominated by mono-, di- and tricyclic aromatic hydrocarbons, whilst those from laser micropyrolysis are dominated by aliphatic hydrocarbons (n-alk-1-ene/n-alkane doublets), which is consistent with the results from an FT-IR spectrum of the solid bitumen. According to the molecular compositions of the pyrolysates from two types of pyrolysis, results from a 532 nm continuous wave laser may be more suitable for pyrolysis research of bitumen/asphaltene. Thus, differences in pyrolysis techniques must be considered when used to characterize oil asphaltenes or source rock kerogens.     

Investigation on foaming properties of some organics for oily bubble bitumen flotation

Studies have shown that using organic coated bubbles (“oily” bubbles) could increase bitumen recovery rate in flotation. One way to coat bubbles is that used in the air-assisted solvent extraction process where solvent foam is formed and injected through a capillary to release solvent coated bubbles in a controlled manner into the aqueous system. To investigate adapting this approach, the foaming properties of some organics (Hexane, Heptane, Hexadecane, Petroleum Ether, Toluene, Benzene and Kerosene and their binary mixtures) of potential interest in oily bubble bitumen flotation were investigated. Silicone oil was found to be a good foaming agent in some cases. Bubble stability and film thickness experiments were carried out to help select candidate organics. Surface tension and dynamic viscosity measurements were conducted to examine the mechanism of foaming. Attachment studies showed that droplets of the selected organics readily attached to a bitumen surface compared to air bubbles. From a combination of criteria, 25:75 Hexadecane/Heptane appears to be a promising candidate.     

单质硫和含硫矿物对固体沥青中生物标志物热演化过程的影响

含硫物质与地质体中有机质的形成、演化过程密切相关,但在地质演化过程中它们对沉积有机质中生物标志物的影响较少报道。对四川盆地固体沥青样品开展在单质硫(S0)和含硫矿物(黄铁矿、硫酸亚铁、硫酸铁和硫酸钙)存在条件下的加水热模拟实验,进而探讨上述含硫物质在固体沥青热演化过程中对其赋存生物标志物的影响。研究表明,单质硫和含硫矿物对固体沥青中可溶有机质产率均有不同程度的影响,它们的影响程度顺序是:S⁰>Fe₂(SO₄)₃>FeSO₄>CaSO₄>FeS2。对于反映成熟度的生物标志物参数,单质硫和含硫矿物对甾烷C29-αββ/(αββ+ααα)、C29-20S/(20S+20R)和藿烷C31H-22S/(22S+22R)的比值均无显著影响,但对甾烷(S21+S22)/C27–29、藿烷Ts/(Ts+Tm)和规则甾烷系列比值有影响。单质硫和含硫矿物会显著改变反映生源的生物标志物参数,不同含硫物质对甾烷S21/S22、藿烷C29H/C30H、三环萜...     

基于辐射传输方程的低损耗介质微波介电常数反演

微波介电常数是分析和研究微波与介质之间相互作用的重要基础参数之一。笔者设计了一种针对低损耗介质微波介电常数的反演方法。引入并改进了辐射传输方程,将介质介电常数的实部和虚部与其微波亮温相关联。在温度均匀分布且表面光滑的条件下,利用改进的辐射传输方程,构造了低损耗介质微波介电常数的反演模型。基于模拟月壤物质,进行了反演模型的验证。结果表明,反演的介电常数的实部与北京师范大学提供的检测结果吻合良好,虚部与阿波罗14号月壤样品的平均测量值吻合良好。     

川东北地区长兴组-飞仙关组固体沥青的形貌特征与成因分析

利用扫描电镜观察川东北某地区上二叠统、下三叠统储层固体沥青时,发现固体沥青与显微镜下的无定形、它形充填构造不同,按其外形可分为皮壳状、葡萄状、瘤状、蠕虫状和柿饼状5种类型。其中皮壳状、葡萄状沥青分布在飞仙关组,瘤状、蠕虫状和柿饼状沥青分布在长兴组。根据固体沥青内部鳞片状结构和球粒中间相结构推测其已达高演化阶段。     

多金属矿物的介电特性算法研究

获取介质的介电特性是微波加热应用中分析和设计的基础。在微波冶金中,矿物的介电特性直接关系到矿物加热速率和能量利用效率,以及新工艺的开发等关键问题。多金属矿物的宏观介电特性与各种颗粒的比例、成分、尺寸以及局部微结构有关,介电特性获取困难。本文提出了一种基于结构抽象化伪两相算法模型来计算多金属矿物的介电特性,以6种矿物单元组成的多金属矿物为研究对象,计算了矿物的介电常数和介电损耗。结果表明,其介电常数和介电损耗值与Maxwell-Garnett理论公式计算值相一致,证明了该算法模型能够逼近矿物的介电特性。多金属矿物的伪两相介电特性算法模型在微波冶金中具有潜在的应用价值。     

四川盆地东北部海、陆相储层沥青组成特征及来源

本研究系统采集了四川盆地东北部大普光、元坝地区上三叠统须家河组、下三叠统飞仙关组、上二叠统长兴组和鄂西渝东地区中石炭统黄龙组储层固体沥青样品,进行了岩石热解、有机元素、碳同位素和饱和烃、芳烃组分GC/MS的分析,以确定其成因、性质和来源。这些沥青总体上具有低溶性(多数氯仿抽提物/TOC<8%)、高反射率(换算的Ro>1.4%)、低H/C原子比(<0.6)的性质,属焦沥青类,是古油藏原油或运移烃经热裂解成气的残留物。其中,飞仙关组、长兴组碳酸岩储层沥青的S/C原子比值普遍较高(主要在0.025~0.085范围),且硫同位素δ³⁴S值(主要在12‰~24‰)接近硬石膏,说明可能包含有部分TSR成因的沥青。这些高热演化沥青中饱和烃生物标志物的组成和分布出现了异常变化,基本失去了其常规应用意义。芳烃中2,6-/2,10-DMP(二甲基菲)、1,7-/1,9-DMP和4-/1-MDBT(甲基二苯并噻吩)比值,可用来指示沥青烃源岩的有机质生源构成和沉积环境性质。须家河组陆相沥青中这些芳烃比值较高,表征其烃源母质中陆源有机质占优势,且形成于氧化性的环境;而飞仙关组、长兴组及黄龙组海相沥青中这些参数值低得多,意味着其烃源岩有机质生源应以水生生物为主,并沉积于还原性环境。经沥青/烃源岩的碳同位素和二苯并噻吩系列组成对比,认为须家河组储层沥青来源于本层位烃源岩,飞仙关组和长兴组沥青同源于二叠系烃源层。鄂西渝东地区的黄龙组沥青碳同位素偏重(δ¹³C值为-23.2‰~-26.4‰),原始烃源可能主要来自中、下志留统韩家店组及小河坝组地层。     

Secondary hydrocarbon generation potential from heavy oil, oil sand and solid bitumen during the artificial maturation

Secondary hydrocarbon generation potentials from natural bitumen, oil sand and heavy oil, representing different residual oil accumulations, were determined by artificial maturation in a closed pyrolysis system. Simulated results indicate that their thermal behavior and reactivity are similar to those of kerogen, and that they can generate hydrocarbons once subjected to suitable geological processes. Overall differences in oil and gas generation potentials among the samples result from differences in the chemical structure of precursor components, physical compaction status, and mineral matrices. Hydrogen rich precursors, such as oil sand and heavy oil, have greater potential to generate hydrocarbons than hydrogen poor ones. Naturally compacted oil sand has slightly higher conversion efficiency than artificially compacted heavy oil as indicated by lower residual bitumen content. However, total gas and liquid oil recovery from oil sand is lower than from heavy oil due to the poor release of pyrolytic products from well compacted and cemented networks in the experiments. Mineral matrices of previous oil deposits also affect further hydrocarbon generation potential. Carbonate matrices inhibit total oil and gas generation, which consequently retains high gas potential at the postmature stage. Traditional oil generation models mainly consider the thermal alteration of kerogen; this study provides supplemental information for superimposed basins where previous oil accumulations may have been destroyed and reburied to serve as secondary sources of oil and gas. Consideration of previous oil residues as potential source rock allows better estimates of available oil resources and the risks associated with their exploration.     

Sterane distribution of solid bitumen pyrolyzates. Changes with biodegradation of crude oil in the Ouachita Mountains,Oklahoma

Solid bitumens (grahamite and impsonite) of southeastern Oklahoma have been shown to originate from near-surface alteration of crude oil (Curiale, 1981; Curiale and Harrison, 1981). Pyrolysis of these solids has been employed to compare the sterane distribution of geographically proximate oils to that of the bitumens. The ratio of rearranged to regular steranes is higher in the pyrolyzates than in the oils, a finding consistent with a bitumen origin due to biodegradation of oil. The remaining presence of steranes, particularly regular steranes, in the bitumens suggests that sterane occlusion may have occurred prior to or during the alteration process, thus removing tetracyclic compounds from the influence of microbial attack. These data suggest that pyrolysis-$\text{GC}\text{MS}$ offers a viable approach to correlation problems involving solid bitumens.     

The thermodynamic properties of reciprocal solid solutions

A multisite solid solution of the type (A, B) (X, Y) has the four possible components AX, AY, BX, BY. Taking the standard state to be the pure phase at the pressure and temperature of interest, the mixing of these components is shown not to be ideal unless the condition: $$\Delta G^0 = (\mu _{AX}^0 + \mu _{BY}^0 - \mu _{AY}^0 - \mu _{BX}^0 = 0$$ applies. Even for the case in which mixing on each of the individual sublattices is ideal, ΔG ⁰ contributes terms of the following form to the activity coefficients of the constituent components: $$RT\ln \gamma _{AX} = - X_{B_1 } X_{Y_2 } \Delta G^0$$ (X _Ji refers to the atomic fraction of J on sublattice i). The above equation, which assumes complete disorder on (A, B) sites and on (X, Y) sites is extended to the general n-component case. Methods of combining the “cross-site” or reciprocal terms with non-ideal terms for each of the individual sites are also described. The reciprocal terms appear to be significant in many geologically important solid solutions, and clinopyroxene, garnet and spinel solid solutions are all used as examples. Finally, it is shown that the assumption of complete disorder only applies under the condition: $$\Delta G^0 \ll zn_1 RT$$ where z is the number of nearest-neighbour (X, Y) sites around A and n ₁ is the number of (A, B) sites in the formula unit. If ΔG ⁰ is relatively large, then substantial short range oder must occur and the activity coefficient is given by (ignoring individual site terms): $$\gamma _{AX} = \left( {\frac{{1 - X'_{Y_2 } }}{{1 - X_{Y_2 } }}} \right)^{zn_1 }$$ where X′_Y2 is the equilibrium atomic fraction of Y atoms surrounding A atoms in the structure. The ordered model may be developed for multicomponent solutions and individual site interactions added, but numerical methods are needed to solve the simultaneous equations involved.     

Thermodynamic properties of almandine-grossular garnet solid solutions

The mixing properties of Fe₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ garnet solid solutions have been studied in the temperature range 850–1100° C. The experimental method involves measuring the composition of garnet in equilibrium with an assemblage in which the activity of the Ca₃Al₂Si₃O₁₂ component is fixed. Experiments on the assemblage garnet solid solution, anorthite, Al₂SiO₅ polymorph and quartz at known pressure and temperature fix the activity of the Ca₃Al₂Si₃O₁₂ component through the equilibrium: 1 $$\begin{gathered} {\text{3CaAl}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftarrows {\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} \hfill \\ {\text{Anorthite garnet}} \hfill \\ {\text{ + 2Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + SiO}}_{\text{2}} \hfill \\ {\text{ sillimanite/kyanite quartz}}{\text{.}} \hfill \\ \end{gathered}$$ This equilibrium, with either sillimanite or kyanite as the aluminosilicate mineral, was used to control \({\text{a}}_{{\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} }^{{\text{gt}}} \) . The compositions of the garnet solutions produced were determined by measurement of their unit cell edges. At 1 bar Fe₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ garnets exhibit negative deviations from ideality at the Fe-rich end of the series and positive deviations at the calcium end. With increasing pressure the activity coefficients for the Ca₃Al₂Si₃O₁₂ component increase because the partial molar volume of this component is greater than the molar volume of pure grossular. Previous studies indicate that the activity coefficients for the Ca₃Al₂Si₃O₁₂ component also increase with increasing (Mg/Mg+Fe) ratio of the garnet. The region of negative deviation from ideality implies a tendency towards formation of a stable Fe-Ca garnet component. Evidence in support of this conclusion has been found in a natural Fe-rich garnet which was found to contain two different garnet phases of distinctly different compositions.     

川西北侏罗系沙溪庙组固体沥青包裹烃的释放及其地球化学意义

固体沥青分子结构中可能存在类似于沥青质的吸附包裹现象,其包裹烃组分属于成熟度较低条件下的产物,包含有早期的地球化学信息.选用 H2O2/CH3COOH 作为氧化体系对其进行轻度化学氧化降解释放其中的包裹烃,并结合有机地球化学研究手段对川西北下寺侏罗系沙溪庙组固体沥青进行研究.结果显示,该固体沥青可溶组分中烷烃类包括生物标志物基本未检测到,仅残留一些简单的芳烃化合物,很难提供有用的地球化学信息.而其包裹组分中检测到一系列偶碳数正构-1-链烯、正构烷烃和部分异构烷烃以及生物标志物等.包裹组分中 Ts/(Ts+Tm)比值为0.26, C29甾烷20S/(20S+20R)比值为0.43,均反映了固体沥青低成熟度的特征;规则甾烷相对含量 C29>C27>C28,显示弱的 C29优势,其中(C27+C28)占52.1%, C29占47.9%;正构烷烃的分布呈微弱偶碳数优势;固体沥青总碳同位素值为–21.5‰,显示强烈富集13C 的特征.分析表明,藻类等低等水生生物对源岩母质有重要贡献,但不能确定是否有陆生高等植物的输入,母源可能沉积于弱的还原环境.沙溪庙组固体沥青与该地区其他层位固体沥青、油砂和油苗可能有不同的来源.     

饱和度对玄武岩微波响应的影响试验研究

岩石的微波处理效果受诸多因素影响,其中水是一种良好的吸波介质,能提高岩石的微波吸收能力。为探索饱和度对微波照射后岩石响应特征的影响效果,以不同饱和度的玄武岩试样为研究对象,以升温特性、波速与孔隙度变化以及动态抗拉强度等为参考指标,开展了3 kW功率微波照射的破岩试验。从细观与宏观角度的分析结果表明：（1）水的存在影响了微波照射过程中岩样的升温特性,照射的前15 s内,饱和度低于75%组明显促进了升温速率,而饱和度达到100%则作用相反,升温速率低于干燥组;15～30 s随着含水率的减少与蒸发吸热,含水试样升温速率降低;30～45 s内水分蒸发完毕,含水试样的升温速率接近干燥试样。（2）饱和度差异导致玄武岩在微波照射后发生不同程度的波速与孔隙率的变化,波速降幅范围为8.18%～17%,孔隙率增长范围为18.71%～43.65%,损伤效果并未随饱和度升高而增强。（3）同样照射条件下,50%饱和度组在蒸汽压力和热应力共同作用下快速达到强度极限,试样直接发生破坏。其余组试样大多未发生明显细观损伤,最终动态抗拉强度差距不明显。     

鄂尔多斯盆地能源矿产氯仿沥青Sm-Nd同位素研究

对鄂尔多斯盆地石油、煤、含铀砂岩及其围岩的氯仿沥青进行了Sm-Nd同位素研究。结果表明,盆地流体(包括深部流体)活动具有多期性,且后期的流体活动对铀矿床的形成具有重要作用;赋存于同一套地层中的含铀砂岩沥青、煤沥青及石油沥青,虽然均具有富集地幔特征,但并非同期活动的产物;东胜矿区侏罗系直罗组煤沥青和盆地西南部陈家山矿区侏罗系延安组的煤沥青,源区时代上存在较大差异,伴生沥青并非全部由煤的热演化形成,可能还存在外来流体的加入,且东胜直罗组煤的伴生沥青较延安组煤的伴生沥青来源深度更大;盆地内马岭油田的直罗组石油沥青、陈家山延安组煤层石油沥青及其煤沥青在源区特征上具有内在联系。     

Microwave brightness temperature imaging and dielectric properties of lunar soil

Among many scientific objectives of lunar exploration, investigations on lunar soil become attractive due to the existence of He³ and ilmenite in the lunar soil and their possible utilization as nuclear fuel for power generation. Although the composition of the lunar surface soil can be determined by optical and γ/X-ray spectrometers, etc., the evaluation of the total reserves of He³ and ilmenite within the regolith and in the lunar interior are still not available. In this paper, we give a rough analysis of the microwave brightness temperature images of the lunar disc observed using the NRAO 12 meter Telescope and Siberian Solar Radio Telescope. We also present the results of the microwave dielectric properties of terrestrial analogues of lunar soil and, discuss some basic relations between the microwave brightness temperature and lunar soil properties.     

氯羟磷灰石中羟基的FTIR研究

通过固相法合成了一系列氯羟磷灰石(ClHAp)固溶体,经FTIR表征发现,纯羟基磷灰石(HAp)的羟基振动频率为3572cm-1和632cm-1。当Cl-进入HAp晶体结构后,在3494cm-1和673cm-1处各出现新的吸收谱带,说明在其通道结构中形成[Cl…HO]氢键,导致羟基的伸缩振动向低频偏移,弯曲振动向高频偏移。与氟羟磷灰石的FTIR谱比较可知:ClHAp的羟基振动谱带的位置与数量主要受氢键和周围结构环境变化程度影响。     

Geochemical characteristics and families of the Paleozoic oil seepage and solid bitumen in the Southern Guizhou Depression,SW China

Fifteen oil seepage and solid bitumen samples in the Southern Guizhou Depression were analyzed with GC–MS. Characteristics of molecular markers and carbon isotopes are discussed systemically. The results showed that the oil seepage and solid bitumen samples in the Southern Guizhou Depression could be divided into two families: Ordovician and Siluric samples, and Permian samples. The two families are different in alkanes distribution, biomarkers, aromatic hydrocarbon composition,and stable carbon isotopes; differences mainly caused by source rock variation.     

沥青包裹体的拉曼光谱特征

对石油中的沥青质组分进行了拉曼光谱分析,发现有两种不同的拉曼光谱特征的沥青质:一是具碳质拉曼特征峰的沥青质,二是无碳质拉曼特征峰的沥青质,将前者称为碳质沥青质.对储集砂岩中的深色沥青质包裹体拉曼分析并据其拉曼光谱图特征将这类包裹体分为三种类型:含碳质沥青包裹体、碳质沥青包裹体和沥青包裹体.如果烃包裹体形成后经历了地质构造应力而破裂和地热作用而发生轻组分移出,就形成了沥青包裹体;若再经地质高温变质作用而发生了碳化,就形成碳质沥青包裹体;若只经历地质高温变质作用而发生碳化,组分热解但未移出,可能会形成含碳质沥青包裹体.