Spent oil shale use in earthwork construction

Spent oil shale (or blaes) is a potentially valuable engineering material and is present in large quantities in the West Lothian area of Scotland. It can be used successfully as general fill or capping layer. However, due to its high quality it may be more suited to use as selected granular fill or sub-base. In particular, cement stabilisation will reduce frost susceptibility and may be a particularly appropriate outlet for spent oil shale for use as sub-base. However, an increase in control and testing may be required, having an effect on the cost of using such materials. Conditions under which spent oil shale should not be used are also identified.     

Determination of trihalomethanes and the ionic composition of groundwater at Amman City, Jordan

A water-chemistry evaluation was made of the available springs and wells in Amman and vicinity. Trihalomethanes (THM) were found in all analysed samples with concentrations ranging from 0.2–31.88 μg/L. The probable sources of trihalomethanes in the aquifers originate from three sources: (1) chlorinated Deir Alla surface water, (2) reaction of excess chlorine in the leaky, corroded water-distribution network with organic matter in the vadose zone, and (3) sewage seepage from cesspools in the area. Total organic carbon (TOC) ranged from 0.2–1.4 mg/L. Its probable source is either from the vadose zone or the treated surface water at Deir Alla. It was found that TOC was of vital importance in the formation of THM in the presence of chlorine from the water-distribution system. Major ionic composition of the analysed samples reflected the limestone lithology of the aquifer in the investigated area. Heavy-metal content was relatively low due to the high pH of the groundwater samples. Electronic Publication     

抚顺盆地始新统计军屯组油页岩地球化学特征及其沉积环境

沉积物元素地球化学特征是盆地沉积环境变化的响应。本文根据元素Ti、Mn、Li、Cr、Co、Ni、Cu、Zn、Ga、Cd、Ba、Pb、Sr、Rb、V的含量及Sr／Ba、Ni／Co、Ni／V、Cu／Zn、V／（V＋Ni）比值的变化规律，并结合有机地球化学特征，对抚顺盆地始新统计军屯组油页岩的沉积环境进行了分析。以Li、Ti为代表的外源元素，贫矿段的含量高于富矿段；而Sr、Ba等湖盆内化学沉积元素，富矿段的含量高于贫矿。Sr／Ba、V／（V＋Ni）、Ni／Co、Cu／Zn比值从贫矿段到富矿段呈现逐渐增大的趋势。富矿段有机质类型主要为Ⅰ型，而贫矿段主要为Ⅱ1、Ⅱ2。分析表明，本区油页岩富矿段形成于水体盐度较贫矿段高、还原性强的深湖环境，而贫矿段则形成于还原性较弱的半深湖一浅湖环境。     

全球页岩油形成分布潜力及中国陆相页岩油理论技术进展

全球非常规页岩层系油气资源丰富,富有机质页岩主要沉积在劳亚构造域和特提斯构造域的上侏罗统、渐新统—中新统、白垩系和上泥盆统4套页岩层系内。交汇分析北美典型页岩油区块产量与R_o数据关系,提出R_o为0.7%作为低熟页岩油和中高熟页岩油的界限,系统评价了全球116个盆地157套页岩层系中高熟页岩油、低熟页岩油技术可采资源量约2 512亿t,主要分布在北美洲、南美洲、北非和俄罗斯,以前陆盆地中新界、克拉通盆地古生界、裂谷盆地和被动大陆边缘盆地的中生界为主。海相页岩油受显生宙以来的海侵影响,富集在稳定克拉通和前陆等类型盆地中,具大面积稳定分布、成熟度适中等特征;陆相页岩油受暖室期气候影响,主要在坳陷、断陷等类型盆地中发育,以微纳米级无机孔隙和微页理裂缝为主要储渗空间通道,具有沉积相横向变化大、“甜点区段”局部富集等特征。中国石油工业正经历从“陆相页岩生油”向“陆相页岩产油”转变,初步形成源岩油气“进源找油”地质理论、陆相页岩油高效勘探及低成本开发技术体系,推动中国陆相页岩油取得重要突破。着力加强应用基础理论研究与关键技术攻关,构建地质-工程一体化模式,...     

油页岩生产技术研究

总结了世界上从油页岩中制取页岩油的两大类生产技术方法:即地面干馏方法和地下转化方法,并总结了各方法的优缺点。根据我国油页岩资源的特点,认为应在发展和改进目前地面干馏技术的同时着力发展地下转化技术,为开采油页岩油进行技术改进。     

Studies of distribution, release and environmental influences of Fushun oil shale and its self-combustion

Three dumping sites have been formed at the northern region of Fushun City, Liaoning Province, for a large number of gangues including much oil shale that had been piled onto ground as gangue during long-term coal exploitation at West Fushun Open-pit Mine. Under appropriate conditions, self-combustion occurs after long-term exposure of oil shale and consequently such phenomena could be found almost everywhere at the three dumping sites. Much polycyclic aromatic hydrocarbons （PAHs） must be generated through oil shale self-combustion, a kind of incomplete combustion. In this paper, in order to make clear the PAHs distribution in oil shale and its self-combustion and their potential effects on surrounding environment, coal, low-grade oil shale, high-grade oil shale, burning oil shale, burnt oil shale and shaly soil collected from West Fushun Open-Pit Mine and West Dumping Site were analyzed quantitatively in 16 US EPA priority PAHs for the first time. Results showed that 16 PAHs in all samples were less than those in some bitumites and carbonaceous coals and were as much as those in lignites and anthracites from some Chinese mining areas. Coal and low-grade oil shale were abundant in lower molecular-weighted PAHs in contrast to high-grade oil shale with rich higher molecular-weighted PAHs. They had more benzo[a] pyrene than the highest background value in soils in Liaoning Province. So PAHs in these crude oil shales could cause potential effects on environment. There were at least 5121.40 p.g/kg PAils generated and at least 3976.70 μg/kg PAHs released into environment in the period from combustion beginning to sampling on the basis of calculation. Furthermore, the concentrations of 3-4 ring PAHs among them were very high. Therefore it could be said that oil shale self-combustion aggravated the environmental impacts of PAHs in oil shale. The low concentrations of PAHs in shaly soil showed that much PAHs had been released through recultivation and biodegradation.     

鄂尔多斯盆地南缘延长组长7油页岩地球化学特征及其地质意义

微量、稀土元素和有机地球化学参数对于揭示油页岩沉积环境、古气候等沉积成矿作用、预测油气、油页岩资源潜力具有重要意义。对鄂尔多斯盆地南部延长组长7油页岩获得的地球化学参数进行研究,油页岩微量元素与地壳平均值及其他地区油页岩相比,W、Mo、As、Sb、U等元素明显富集,Sc、Cr、Ni、Cl等元素明显亏损。油页岩稀土元素总量较低,轻稀土元素富集,重稀土元素亏损,稀土元素较球粒陨石发生了明显分异,较北美页岩分异不明显。油页岩有机质类型为Ⅰ型和Ⅱ_1型,以Ⅱ_1型为主,有机质丰度达到最好级,成熟度为低成熟-成熟。通过对这些地球化学参数及特征的进一步分析,获得以下认识:1长7油页岩是在温暖潮湿的气候条件下,形成于陆相淡水深湖-半深湖还原环境中,这种沉积环境有利于油页岩有机质的富集和保存;2本区不具备形成油气田的潜力,具备形成中-高品级的特大型油页岩矿床的潜力。     

油页岩的综合开发与利用

油页岩是一种重要的能源矿产，其资源量巨大，是石油和天然气的重要替代资源。本文简介了国内外油页岩开发利用的历史和现状，综述了油页岩综合开发利用的方式和途径。油页岩除用来炼油、燃烧发电外，其灰渣可用于材料制造、废气和污水处理。油页岩还在农业、制取氢气和有机酸以及提取金属元素等方面有广泛的用途。研究表明，油页岩综合开发利用能取得良好的资源、环境、经济及社会效益，对实现资源可持续发展具有重要作用。     

黑龙江省柳树河盆地始新统八虎力组油页岩元素地球化学特征及沉积环境

黑龙江省柳树河盆地始新统八虎力组发育多层油页岩。通过对油页岩样品元素地球化学分析测试,研究了其常量元素、微量元素和稀土元素特征,分析了油页岩沉积环境。研究结果表明,常量元素以富Al₂O₃、Fe和CaO,贫SiO₂、MgO、Na₂O和K₂O为特征,微量元素总体上表现出不同程度的亏损特征,稀土元素总量平均为140.7×10^-6,表现出轻稀土元素轻度富集特征。稀土元素具有较为一致的变化趋势,表明油页岩沉积时物源和沉积环境较为稳定。Mn/Ti值表明油页岩组成物质的搬运距离随着时间变化经历了远→近→远的变化,反映水体深度经历了深→浅→深的变化。Sr/Cu值和Rb/Sr值表明油页岩沉积时为相对炎热干旱的环境。Sr/Ba值反映当时为炎热干旱气候条件下的过渡相咸水湖泊沉积环境。V/(V+Ni)值、δEu和有机碳含量表明油页岩沉积时处于缺氧的还原沉积环境中。总体上,柳树河盆地油页岩发育于炎热干旱气候、咸水、缺氧条件下的湖泊沉积环境中。     

Mineralogical and geochemical constraints on environmental impacts from waste rock at Taojiang Mn-ore deposit,central Hunan,China

The mineralogy and geochemistry of the waste rocks distributed at Taojiang Mn-ore deposit, central Hunan province, China, were studied using X-ray powder diffraction (XRD), electron microprobe analysis (EMPA) fitted with energy dispersive spectrometer (EDS) and inductively coupled plasma mass spectrum (atomic emission spectra) ICP-MS (AES), with the aim of predicting the environmental impacts of weathering of the waste rocks. The mineralogical results from microscope observation and XRD and EMPA studies show that the waste rock is composed of black shale and minor Mn carbonates. The oxidation of sulfide minerals such as galena, pyrite and chalcopyrite is accompanied by decomposition of Mn carbonates and K-feldspar during exposure to atmospheric O₂. The geochemical characteristics of major, rare earth elements (REE) and trace elements of the waste rocks also show that the waste rock can be divided into black shale and Mn carbonate, and both of them are currently under chemical weathering. The major alkalies and alkaline elements (Ca, Mg, Na, K, Rb, Sr and Cs) and major elements (Fe, S and P) and heavy metals (Sc, V, Cr, Th, U, Sn, Co, Ni, Cu, Zn, Pb, Mo, Cd, Sb, an Tl) are being released during weathering. The mobility of alkalis and alkaline elements Ca, Mg, Na, K, Rb, Sr and Cs is controlled by decomposition of Mn carbonates. The dispersion of Cr, Sc and Th (U) might be related to weathering of K-feldspar, and the release of the heavy metals Co, Ni, Cu, Zn, Pb, Mo, Cd Sb and Tl is dominated by the breaking of sulfide minerals. The REE of the waste rocks and surrounding soils and the spidery distribution patterns of heavy metals in the waste rocks, the surrounding soils and the surface waters show that weathering of the waste rocks and bedrock might be the sources of heavy metal contamination for the surrounding soils and surface water system for the mining area. This is predicted by the mass-balance calculation by using Zr as an immobile element. Therefore, it is urgently necessary take measures to treat the waste rocks distributed throughout the area for the local environmental protection.     

国外油页岩的地下开采及环境恢复

介绍了国外油页岩地下开采方法、疏干井、加热井／生产井和监测井的分布，以及开采结束后环境的恢复治理方法。值得国内借鉴。     

油页岩提硅渣铝溶出实验研究

针对提取氧化硅后的油页岩灰渣,对改良碱石灰烧结法提取氧化铝过程中的铝溶出进行了实验研究,主要探讨了烧结温度、烧结时间、碱铝比及钙硅比对烧结熟料中的物相特点及铝溶出率的影响。运用X射线粉末衍射(XRD)对烧结熟料进行的物相分析结果显示,主要物相为铝酸钠(NaAlO₂)和硅酸钙钠(Na₂CaSiO₄)。烧结实验结果表明,当烧结温度为1 150℃,保温时间为1.5 h,碱铝比为1.0,钙硅比为1.0时,烧结熟料中氧化铝的标准溶出率可达94%。     

Chemical characterization of the kerogen from Moroccan Timahdit oil shale by analysis of oxidation products

A 33 step alkaline permanganate degradation of the kerogen from Moroccan Timahdit oil shale (M-Zone) was carried out. A very high total yield of oxidation products was obtained (95.4% based on original kerogen). Detailed GC-MS analyses of ether-soluble acids, acids isolated from aqueous solutions and soluble products of further controlled permanganate dedradation of precipitated, ether-insoluble acids, served as a basis for the quantitative estimation of the participation of various types of products and for comparison with other kerogens. The most interesting finding was the observed uniquely high yield of aromatic oxidation products from an intermediate type I–II kerogen. Taking into account the almost equally dominant aliphatic (50.2%) and aromatic (43.2%) nature of the acidic oxidation products, the existence of an aliphatic cross-linked nucleus mixed with cross-linked aromatic units in the Timahdit shale kerogen is postulated. Uniform distribution of oxidation products throughout the degradation suggested a similar reactivity of the various kerogen constituents towards alkaline permanganate.     

页岩油分类与评价

页岩油是以游离(含凝析态)、吸附及溶解(可溶解于天然气、干酪根和残余水等)态等多种方式赋存于有效生烃泥页岩地层层系中且具有勘探开发意义的非气态烃类。根据泥页岩地层中所含烃类相态、成因机理及勘探开发等特点,将页岩类油气划分为页岩气和页岩油等两类八种。结合页岩油特点,指出了我国页岩油形成条件和分布规律,即规模分布的有效生烃泥页岩、形成于深水-半深水相的富有机质泥页岩、较高的有机质丰度和适当的热演化程度以及较好的基质物性条件等是页岩油形成的主要条件。建立了中国陆相断陷湖盆页岩油发育模式,指出概率体积法可以作为页岩油资源评价的主要方法,提出了页岩油远景区、有利区及目标区优选的参数体系和标准。作为非常规油气能源的主要类型之一,页岩油将会对我国能源结构产生重要影响。     

民和盆地窑街煤田油页岩沉积环境分析及开发前景预测

通过岩芯钻井资料的综合分析,对民和盆地窑街煤田油页岩沉积特征、层序地层、古地理演化和成矿规律进行了研究。结果表明,油页岩段主要为水进体系域和高水位体系域发育时期,油页岩主要形成于沼泽和浅湖-半深湖相的沉积环境中。其中油四层油页岩品质较好,平均含油率>8%,属于湖泊沼泽相,具有良好的工业品位。研究区油页岩具有中含油率高灰分的特征,资源总储量为2.3×108t,具有良好的开发前景。     

Kinetics and Equilibrium Sorption Studies of 4-Nitrophenol on pyrolyzed and activated oil shale residue

Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO₂ at 830 °C, while chemical activation was achieved by using KOH and ZnCl₂ as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl₂, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl₂-oil shale sorbents.     

Laboratory simulation of natural leaching processes of eastern USA oil shale

Raw and retorted spent oil shales from Kentucky, as well as soil and overburden materials, were subjected to laboratory and field leaching tests. Standard batch leaching tests grossly undervalue the amount of dissolved ions as measured in the field, being too brief to enable slow reactions of the mineral matrix, such as hydrolysis and oxidation of sulfides or reactions of acidic leachates with soluble components of the clays. Laboratory column tests, devised to closely simulate natural leaching processes, achieved concentration levels and elemental release patterns similar to those found in field tests. The column tests provide a reliable means to assess the leachability of metals in these materials.     

陕西铜川—延安地区油页岩及油气资源特征

鄂尔多斯盆地东南部的铜川—延安地区是我国油页岩资源最丰富的地区之一,其中,三叠系延长组是盆地内最具潜力的油页岩产出层位.为了掌握和评价该区三叠系延长组长7油页岩矿床特征、资源品级和勘探远景,为该区油页岩勘探开发提供依据,在对油页岩地质调查、钻探及测井等资料解释和样品分析的基础上,进行了综合研究和远景资源量估算.结果表明:该区油页岩厚度较大、油页岩段集中,分布稳定,含油率较高,为厚层中品级富—高硫油页岩;沉积环境控制了油页岩的厚度及含油率,半深湖—深湖与浅湖过渡带及湖湾环境是油页岩形成的最有利相带;该区仅500 m以浅的长7油页岩资源量达1346.46×108 t,干馏油页岩油资源量为63.70×108 t,资源潜力巨大,具有大型—特大型油页岩矿床远景.     

黄县盆地褐煤与油页岩的泥炭沼泽类型分析

对黄县第三纪褐煤与油页岩共生盆地中煤₁和油₁的煤岩学特征及煤相参数特征的分析表明,黄县盆地煤₁形成于较深覆水的森林沼泽,油₁形成于湖泊沼泽,而海水侵入控制着盆地的覆水变化,进而影响了植物群落的演化与更叠。