Exploratory experiments on pyrite removal from oil shale by an electrolytic process

The electrolytic treatment of kerogen concentrate shows that it is potentially an effective method for pyrite removal from oil shale. It has been demonstrated that this process can be carried out by using an alkali salt, which does exist in the oil shale, as electrolyte. Although this method was tested on Appalachian shale, it could probably be applied to other oil shales, coal, tar sands and other carbonaceous rocks. In such extended applications, the development of electrolytic processes to remove pyrite should be encouraged.     

Calculation of qualitative and quantitative composition of Estonian oil shale and its combustion products. Part 1. Calculation on the basis of heating value

A method for calculation of the composition of Estonian oil shale and its combustion products is based on the various correlations governing the composition of this oil shale, and relations between its components. To understand better the properties of oil shale and the influence of mining conditions on oil shale quality, a general characterisation of Estonian oil shale is first presented. This unique fuel is utilized for power production, by direct firing in boilers. This paper presents calculations useful for the boiler design engineer for estimating the average characteristics of received oil shale as well as the possible deviations from these mean values.

The calculations in this part allow finding the composition of oil shale and the composition of combustion products of oil shale based only upon its heating value. Various considerations in performing oil shale combustion calculation are presented. A calculational example is presented in the appendix of this part. Part 2 of this study extends the method, given the availability of additional fuel analysis data.     

Composition of the thermal degradation products of oil shale from the Kotsebinskoe deposit

The pyrolysis of oil shale from the Kotsebinskoe deposit for the manufacture of solid, liquid, and gaseous products was studied. The composition of the resulting oil shale products was determined. The areas of application for the oil shale products are proposed.     

博格达山北麓阜康西区油页岩矿体特征

博格达山北麓油页岩是中国重要的油页岩成矿地带,研究系统采集了阜康西区84件岩石样品,磨制薄片进行了岩石学研究,探讨了研究区油页岩矿体的岩性组合特征、矿体几何特征及对矿体矿段进行了划分。同时,对各类岩石的综合特征进行了细致的分析。结果表明:阜康西区油页岩沿近东西向的向斜展布,矿层巨厚,共生岩石类型区域上较为稳定。总体成矿模式较为简单,且出露地表,有利于油页岩的露面开采。     

页岩灰对油页岩热解特性的影响

以吉林桦甸-公郎头四层油页岩为原料,以掺混SiO2的油页岩为对比样品,利用热重-红外联用仪考察了页岩灰对油页岩热解特性的影响,通过分析热解固相产物组成变化对热解失重及产物析出规律进行了研究. 结果表明,页岩灰对油页岩中的有机质和矿物质失重过程均有促进作用,当页岩灰或SiO2含量为83%时,在300~600, 600~750, 750~900℃三个加热温度区间内,掺混页岩灰样品比掺混SiO2样品的失重率分别提高1.92%, 3.39%和18.99%. 低温段有机质热解过程中CO2先于脂肪烃热解析出,且750℃后CO2析出峰仅出现在掺混页岩灰的样品中,应为油页岩中难分解的碳酸盐在页岩灰作用下加速分解及页岩灰中CaSO4与残炭反应共同作用所致.     

Organic geochemistry of the British Kimmeridge clay: 2. Acyclic isoprenoid alkanes in Kimmeridge shale oils

The C15---C20 isoprenoid alkane composition of Kimmeridge Clay shale oils produced by Fischer assay has been examined, and compared with the isoprenoid composition of corresponding bitumens. C16 and C18 isoprenoid alkanes are generally dominant in shale oils, while pristane (C19) and phytane (C20) dominate in bitumens. A significant proportion of the phytane in many shale oils is derived from simple evaporation of free (bitumen) phytane, while free pristane contributes less to shale oil composition. Some shale oil phytane and a large proportion of pristane is kerogen-derived. Certain shale oils contain lower concentrations of isoprenoid alkanes than corresponding bitumens, suggesting that some free alkane is thermally degraded during pyrolysis. Results thus indicate three sources for shale oil isoprenoid alkanes: thermal evaporation of free alkanes (particularly for phytane), kerogen decomposition, and possibly the cracking of higher homologues for C15---C19 alkanes. Kerogen-derived isoprenoids are suggested to arise by thermal desorption of adsorbed free alkane (particularly for phytane) and from C---O and C---C bonded species (excluding phytane) via postulated clay catalysed hydrogenation of initially formed alkenes. Comparison of shale oil and bitumen pristane/phytane ratios allows groups of oil shales to be defined, dependent on source composition, organic carbon content and maturity. Shale oil pristane/phytane ratios can also help to determine depositional environments and source composition, although maturity, shale mineralogy and competing alkene-forming pyrolytic reactions may also affect the ratios.     

Oil shale as a promising source of raw materials for advanced solid fossil fuel technologies

Information on the chemical nature and structure of the organic matter of oil shale from different deposits, the composition and distribution of mineral impurities in the volume of oil shale, and the elemental composition of the organic matter is considered in this article. It was found that the composition and properties of oil shale from different deposits are essentially different, and significant differences can also be observed within the limits of a deposit. Oil shale from some deposits contain trace impurity elements such as uranium, molybdenum, vanadium, and rhenium. In a number of cases, the concentrations of such impurities are increased, and their extraction can be of industrial interest.     

桦甸油页岩的二级萃取溶解行为

以吉林桦甸油页岩为研究对象,通过二氯甲烷、石油醚两级萃取,对油页岩原矿、两级萃余物进行SEM扫描,对二氯甲烷萃取液、石油醚萃取液进行GC/MS检测,研究桦甸油页岩在两级溶液的溶解行为以及各级萃余物表面物理形貌。结果表明,随着萃取的加深,油页岩颗粒相对光滑的片层结构逐渐消失,颗粒粒径趋于细小,表面沟壑逐渐增多,后级萃取时液固接触面积增加。二氯甲烷和石油醚对油页岩中烷烃溶出能力较强。两级萃取物组分主要由C15～C28饱和烷烃构成。溶剂萃取法可以有效地提取油页岩中一类或相似的化合物群,对研究油页岩构成及提取高经济价值成分有重要意义。     

Variation of kerogen content and mineralogy in some Australian tertiary oil shales

Oil shale is a potential alternative source of petroleum products. The processes of retorting oil shale and refining shale oil are both affected by the composition of the parent rock. Mineralogical and geochemical data obtained from two bore holes in Queensland oil shale deposits are presented and discussed here. The data includes the variation with depth of mineralogy, ash content, moisture content and kerogen content. A strong correlation of hydrogen and organic carbon, and higher H/C ratios suggest that organic matter is present mainly as aliphatic compounds. Pyrite was identified as the major source of sulphur. This may provide some possibilities for easier removal of sulphur before the oil shale is processed.     

固有碳酸盐和硅酸盐对太姥油页岩热解产物的影响

通过逐级酸洗脱除新疆太姥油页岩中的碳酸盐和硅酸盐矿物,采用铝甑炉对油页岩原样和脱矿样进行热解,分析油气产物的组成性质,基于产物产率和性质考察了固有矿物质对油页岩热解的影响。结果表明,碳酸盐能促进热解生油,且使页岩油中含氮、氧化合物含量增大,硅酸盐则抑制热解生油,并抑制含氧化合物的生成,二者均使页岩油的H/C降低。硅酸盐可促进烷基自由基与氢自由基的结合,使页岩油中烷烃含量升高、烯烃含量降低,且使H₂产率减小,并能催化长链脂肪烃的裂解,使页岩油中长链烃含量降低、短链烃含量升高,且使烃类气体产率增大,而碳酸盐则抑制自由基的结合和长链脂肪烃的裂解。     

Treated Oil Shale Ashes as a Substitute for Natural Aggregates,Sand, and Cement in Concrete

Oil shales are rocks that contain organic matter and are used as a low-grade fuel for energy production. The oil shale combustion process produces large quantities of ash as combustion wastes. These residues contain a high concentration of calcium anhydrite (CaSO₄) and calcium carbonate (CaCO₃), which can be utilized to neutralize acidic wastes (e. g., wastes from the phosphate industry) .Using untreated oil shale bottom ash as partial substitutes for aggregates, natural sand, and cement in concrete mixtures has resulted in a significantly decreased performance of the concrete mixtures. However, by blending the oil shale with acidic materials, the concrete properties improved, as manifested by the development of compressive strength and the workability of the concrete mixtures. In the current study, it was shown that treatment of the oil shale ash with the acidic waste of the Israeli phosphate industry or with phosphoric acid significantly improves the properties of the concrete mixtures, by partial replacement of the natural aggregates and sand by the treated oil shale ash.     

Effect of demineralization of El-lajjun Jordanian oil shale on oil yield

The effect of demineralization on oil yield and mineral composition of Jordanian oil shale was investigated. A standard digestion procedure using a range of inorganic and organic acids including HCl, HNO₃, HF, and CH₃COOH was used to enhance the oil recovery of oil shale samples collected from the El-lajjun area. The total yield of the digested samples, as determined by Fischer Assay, has shown a maximum value (two folds the untreated sample) obtained when using CH₃COOH. The kaolin in the treated oil shale with a high concentration of CH₃COOH is believed to have transformed to illite as found in the XRD analysis. The treatment of oil shale using HCl has shown an increased ratio of oil to gas as a result of the digestion of calcite in the oil shale. At higher concentrations of HNO₃, the acid is believed to react with the kerogen in the oil shale resulting in high levels of low molecular weight compounds. Therefore, the amount of non-condensable gases produced by Fischer assay after treatment with a high concentration of HNO₃ is relatively high. HF is believed to drive off water from the oil shale by dissolving the clay minerals leading to increased oil to gas ratio.     

煤系共伴生油页岩热解残渣利用技术

油页岩残渣是油页岩热解过程中排放的固体废物,约占油页岩的80%~90%。中国油页岩残渣利用率较低,残渣堆积量日益增多,后续问题十分突出。煤系油页岩残渣的资源化利用成为油页岩热解提油产业发展的瓶颈。介绍了油页岩热解加工利用现状及其残渣在废水处理和废气吸附方面的应用,分析了当前页岩热解残渣利用过程中存在利用方式单一的问题,并结合油页岩热解残渣结构和组成的特殊性,提出了油页岩残渣用作环保材料如吸附剂的发展方向。     

Chemical and pyrolysis characteristics of two types of oil shale from the Condor deposit in Queensland,Australia

The Condor oil shale deposit contains two major seams: a brown seam of almost pure lamosite origin and a black, or carbonaceous, seam of mixed lignite—lamosite origin. These differences in origin of the organic matter in the shale are reflected in their pyrolysis characteristics and particularly in the chemical composition of the oil retorted from them. The brown shale was found to have oil and gas evolution profiles similar to those reported for shales from the Green River (Colorado) deposit and to give a highly aliphatic oil containing < 2 vol.% of phenols. In contrast, the carbonaceous shale showed gas and oil evolution profiles resembling those of coal, and gave an oil high (≈ 10–15 vol. %) in phenols typical of coal pyrolysis products.     

Comparison of hydrogenated shale oils with standard jet fuels

The characteristics of jet fuels obtained from typical U.S. shale oils (Geokinetics, Occidental, Paraho and Tosco II) were compared with standard petroleum jet fuels in order to study the possibility of using these shale oils as a substitute. The shale oil fractions distilling below 343°C were catalytically hydroprocessed at low, medium and high severities and fractionated to the jet fuel range (121–300°C). The hydroprocessed products and jet fuels were compared for composition and physical properties. High severity hydroprocessing of shale oils decreased the nitrogen, sulfur, olefin and aromatic content while increasing the hydrogen content. The nitrogen content in shale oil jet fuels was considerably higher even after the high severity treatment. The aromatic content, except in Paraho shale oil, was relatively higher and the hydrogen content was slightly lower. Sulfur and olefin contents were lower at all severities. The physical properties and heat of combustion, except the high freezing point of shale oil jet fuels, were comparable to those of standard petroleum jet fuels.     

油页岩开发利用技术进展

在介绍油页岩性质的基础上,系统总结了国内外油页岩热解开发利用的最新研究进展,主要包括油页岩热解化学、热解工艺、页岩灰利用以及油页岩开发利用的技术分析等。油页岩资源的开发利用对缓解石油资源供应紧张和保障能源安全供应具有重要意义。油页岩资源的开发利用必须结合油页岩资源赋存、地质结构和油页岩的性质选择合适的工艺和技术,实现油页岩资源的高效清洁利用。     

油页岩灰渣制备空心陶瓷微球及机理探讨

以油页岩灰渣为实验原料,利用火焰喷枪熔射法制备了空心陶瓷微球.采用TG-DSC对油页岩灰渣进行热分析,采用SEM和XRD分别对油页岩灰渣和空心陶瓷微球的微观形貌和物相组成进行分析.研究结果表明,利用火焰喷枪熔射法制备的微球绝大多数为球状,极少部分为不规则形状,微球破碎后可发现其为空心结构;空心微球的形成机理为:油页岩灰渣粉末受热熔化、发气物质形成气泡、气泡合并、降温凝固、最终形成空心微球;油页岩灰渣自身疏松的结构、所含充足的发气物质和适宜的熔射温度是形成微球空心结构的重要因素.     

Composition of the heteroorganic compounds of oil shale in Cambrian rocks from the east of the Siberian Platform

The molecular composition of the S-, O-, and N-containing heterocyclic aromatic compounds of bitumen separated from the rocks of the Cambrian oil shale formation was studied. Among the sulfur compounds, dibenzothiophene, its alkyl and naphthene derivatives, naphthobenzothiophenes, and their alkyl homologs were identified. Among the oxygen compounds, unbranched dibenzo- and naphthobenzofuran and their C₁–C₄ and C₁–C₂ alkyl homologs, respectively, were detected. Acridinones, benzoacridinones, and their alkyl homologs were present among the nitrogen compounds.     

N.m.r. study of US Eastern and Western shale oils produced by pyrolysis and hydropyrolysis

Shale oils produced from US Eastern and Western oil shales by pyrolysis and hydropyrolysis processes have been investigated by both ¹H and ¹³C high-resolution n.m.r. techniques. Eastern shale oils produced by hydropyrolysis, and subsequently hydrotreated, were also included. From the n.m.r. data of the shale oils, the average molecular structure parameters were calculated. These parameters quantitatively represent the differences observed in the n.m.r. spectra of the various shale oils because of changes in the chemical composition. Mol percentages of aromatics, olefins, and alkanes were also determined for the shale oils, and show that the composition of the shale oil is dependent upon the geographic origin of the oil shale, the pyrolysis method, and the hydrogenation process. In addition to the study of shale oils, solid-state ¹³C n.m.r. spectra of Eastern and Western oil shales before and after pyrolysis and hydropyrolysis were obtained. The spectral data show that the carbon aromaticities for the Eastern oil shales and shale oils are higher than for the Western oil shale and shale oils. The data also show that hydropyrolysis relative to pyrolysis reduces the amount of residual organic carbon remaining on the spent shales. Carbon aromaticity data for both oil shale and shale oil suggest that the organic moieties present in kerogen may be retained in the shale oils to a greater extent after hydropyrolysis than after pyrolysis.     

Effect of acid dissolution on the mineral matrix and organic matter of Zefa EFE oil shale

Kerogen of the Israeli Zefa oil shale was isolated and the changes which occur in the initial organic matter during the removal of the inorganic matrix were investigated. Benzene-methanol extraction dissolved the bitumens, hydrochloric acid and hydrofluoric acid dissolution removed the carbonate and silicate minerals and lithium aluminium hydride treatment destroyed pyrite mineral which was unaffected by the attack of acids. X-ray diffractograms and FTIR spectra of the original oil shale and its demineralized products were measured. Benzene-methanol extraction of the oil shale increased the resolution of peaks in the X-ray diffractograms X-ray diffractograms and FTIR spectra indicated the presence of calcite, α-quartz, kaolinite, illite and pyrite in the mineral matrix of the shale. Hydrochloric and hydrofluoric acid dissolution did not cause hydrolysis and oxidation of the organic matter. Lithium aluminium hydride treatment reduced the carbonyl functionalities to newly formed hydroxyl groups, therefore the kerogen isolated seemed to have a chemical composition different from that of the original oil shale.