Elucidation of the Alum Shale kerogen structure using a multi-disciplinary approach

The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (¹³C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. ¹³C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CH_xO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (f_a), O/C and relative proportions of various carbon types estimated by ¹³C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.     

明矾脱水工艺条件研究

根据硼酸铝晶须合成工艺要求 ,研究了以工业一级品明矾作为反应原料的可行性 ,确定了明矾筛选、脱水、球磨及筛分工艺条件。     

高氟地下水混凝沉淀降氟试验研究

本文开展了山西运城地区高氟地下水的降氟试验，对聚铁、硫酸铝和明矾等不同混凝剂降氟效果进行对比，探讨了地下水硬度对混凝沉淀除氟效果的影响。实验结果表明：明矾混凝沉降效果优于其它混凝剂，0．3g／L的明矾溶液可使含氟浓度4．0mg／L的地下水降低到浓度1．0mg／L以下；地下水的硬度对明矾混凝降氟效果没有明显影响。     

Uranium mineralization in the Alum Shale Formation (Sweden): Evolution of a U-rich marine black shale from sedimentation to metamorphism

The Alum Shale Formation is a metal-rich black shale, deposited on the Baltoscandian platform between Middle Cambrian and Early Ordovician. These black shales may be of particular economic interest for their relatively high uranium content (100–300 ppm) and their wide distribution from Norway to Estonia. Scandinavian Alum Shale may thus constitute a great potential resource of uranium, as a low grade ore. The Alum Shale Formation is particularly interesting to study the mineralogical expression and content of uranium in series submitted to progressive burial and metamorphism. For this purpose, the behavior of U, P, Ti and organic matter was studied on a series of representative samples from most Alum Shale prospection zones. In southern Sweden, where Alum Shale underwent fairly shallow burial, uranium concentrations have no mineralogical expression except a rather high U content of biogenic phosphates. Calcite concretions (beefs) and fractures recorded the migration of hot overpressured hydrocarbons and brines from thermally mature areas to immature Alum Shale. However, thermal maturation and fluid migration did not allow remobilization of uranium and metals. At the opposite, in northern Sweden, where the series were folded, duplicated and submitted to low grade Greenschist metamorphism during Caledonian orogeny, phospho-silicates U-Si-Ca-P (±Ti ±Zr ±Y) and minor amounts of uraninite are identified and indicate that U, P, and Ti were mobile and precipitated as new phases. The effect of metamorphism is therefore important to consider as the leachability of U, especially during (bio)-hydrometallurgical processes, which will be by far different between the two considered areas.     

应用TIMA分析技术研究Alum页岩有机质和黄铁矿粒度分布及沉积环境特征

Alum页岩(中寒武—早奥陶世)是北欧一套重要的海相烃源岩,其成熟度跨度从为成熟-过成熟度阶段。由于我国下古生界海相烃源岩均已过成熟,未成熟-低成熟度的Alum页岩是研究下古海相的烃源岩生烃潜力特征的重要参照样品。因此,对这套成熟度较低的Alum页岩的生物组成特征、矿物组成及其沉积环境的分析,可为后续国内外下古生界海相烃源岩的对比研究奠定基础。本文以欧洲上寒武统富含有机质Alum页岩为主要研究对象,在有机碳含量(TOC)和有机岩石学观察的基础上,应用综合矿物分析技术(TIMA)进行扫描,通过细化样品扫描参数,获得了页岩矿物组成、含量及粒度分布。Alum页岩有机质成熟度较低(固体沥青反射率为0.30),TOC含量在11.16%~12.24%之间。有机质主要为浮游藻类降解形成的层状藻类体、底栖藻类来源的海相镜状体和裂缝中充填的固体沥青。TIMA扫描获得的有机质相对质量百分含量为9.79%~10.64%,略低于碳硫分析仪测定的TOC含量;黄铁矿含量为4.17%~4.49%。TIMA扫描获得的有机质与黄铁矿比值与化学法的C/S比值相近,均分布在2.18~2.55范围。粒径分布特征上,有机质粒径主要分布在0.9~27.0μm之间(80%以上颗粒分布在1.2~5.5μm);草莓状黄铁矿粒径分布在0.9~17.0μm之间(小于0.5μm的颗粒占78%以上),反映了缺氧甚至硫化的环境。综合C/S比、有机岩石学与TIMA黄铁矿粒度分布特征,认为该页岩形成于闭塞封闭甚至硫化的沉积水体体系。该研究为油气地质领域的烃源岩(包括页岩)的研究提供了一种新的技术支持。     

Experimental study of fluid transport processes in the matrix system of the European organic-rich shales: I. Scandinavian Alum Shale

This contribution presents results from a laboratory study investigating the fluid (gas/water) transport properties in the matrix system of the Scandinavian Alum Shale. The maturity of the organic matter of the shale samples ranged between 0.5 and 2.4% vitrinite reflectance (VR_r). Gas (He, Ar, CH₄) and water flow properties were determined at effective stresses ranging between 5 and 30 MPa and a temperature of 45 °C. The effects of different controlling factors/parameters on the fluid conductivity including permeating fluid, moisture content, anisotropy, heterogeneity, effective stress, pore pressure, and load cycling were analyzed and discussed. Pore volume measurements by helium expansion were conducted under controlled “in situ” effective stress conditions on a limited number of plugs drilled parallel and perpendicular to bedding.For Alum Shale the intrinsic permeability coefficients measured parallel and perpendicular to bedding (6·10⁻²²–8·10⁻¹⁸ m²) were within the range previously reported for other shales and mudstones. Permeability coefficients were strongly dependent on permeating fluid, moisture content, anisotropy, effective stress and other sample-to-sample variations. The intrinsic/absolute permeabilities measured with helium were consistently, higher (up to five times) than those measured with argon and methane. Permeability coefficients (He, CH₄) measured on a dry sample were up to six times higher than those measured on an “as-received” sample, depending on effective stress. The effect of moisture on measured permeability coefficients became more significant as effective stress increased. Permeability coefficients (He, CH₄) measured parallel to bedding were up to more than one order of magnitude higher than those measured perpendicular to bedding. Parallel to bedding, all samples showed a nonlinear reduction in permeability with increasing effective stress (5–30 MPa). The stress dependence of permeability could be well described by an exponential relationship.