油页岩的成矿机理研究

油页岩的沉积环境有很多种,而且组成各不相同。油页岩可按照组成（例如方解石等碳酸盐矿物质或石英、粘土等碎屑矿物质）或沉积环境（海相,湖相和陆相）进行分类。油页岩中的大多数有机质起源于藻类,少数起源于陆上维管植物的残骸。有机质的三种主要类型是结构藻类体、层状藻类体和沥青质体。某些油页岩也包括金属钒、锌、铜和铀等。大多数油页...     

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.     

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.     

油页岩原位开采对部分地下水指标影响的分析

目前,油页岩原位开采主要集中于开采技术和工艺研究,针对开采导致的地下水环境风险影响的研究鲜有报道,该方面的研究可为建立油页岩原位开采地下水环境风险水平定量化评价模型奠定基础。本文首先对在不同热解温度、空气气氛和0.1MPa压力条件下产生的粒径≤2mm的油页岩及热解残渣进行了失重率、比表面积、元素及矿物成分分析;其次,在不同热解温度和浸取时间的条件下,通过浸取实验探究了油页岩原位开采后对地下水质量指标pH、色度、硫酸盐、氨氮和化学耗氧量（COD_Mn）的影响。结果表明：油页岩失重率与比表面积的变化规律呈现负相关性;浸取液中各项地下水质量指标主要受有机质含量、岩石组分及各元素占比变化的影响;pH和色度受热解温度及浸取时间共同影响,热解温度对硫酸盐、氨氮和COD_Mn会产生较大影响。油页岩原位开采对地下水质量存在一定的影响,在开采时需采取适当的风险防范措施。     

石长沟油页岩的热解特性及动力学

通过热重、元素和XRD分析,研究了新疆吉木萨尔县石长沟矿区油页岩在不同升温速率下的热解特性及热解机理. 结果表明,油页岩中有机质热解生成页岩油和热解煤气的反应主要集中在300~550℃;升温速率从3℃/min增至15℃/min,热解反应向高温区移动,有机质完全热解温度从530℃升至575℃. 油页岩有机质的热解动力学分析显示,升温速率从3℃/min增至15℃/min,直接Arrhenius法计算的有机质热解活化能从243.52 kJ/mol增至257.32 kJ/mol;反应转化率从0.02增至0.97,Friedman法计算的活化能从96.39 kJ/mol增至292.84 kJ/mol.     

世界油页岩资源的开发利用现状

油页岩是一种非常规能源,世界储量巨大,作为石油的补充能源,开发前景广阔.油页岩在隔绝空气条件下加热至500℃左右,会热解生成页岩油,经加工处理后可以制得汽油、柴油等油品.油页岩也可直接燃烧,产生蒸气、发电,目前利用油页岩燃烧发电的国家有爱沙尼亚、中国、德国等.本文介绍了世界主要油页岩国家的油页岩储量和加工利用情况,目前世界上利用油页岩干馏制取页岩油的国家主要有3个,中国(产量80万吨)、爱沙尼亚(产量50万吨)和巴西(18万吨),其他国家略有生产.中国页岩油产量一直居世界首位,目前有将近10座油页岩干馏厂投入运行,其中抚顺矿业集团年产页岩油35万吨,全国居首,该公司引进的日处理颗粒油页岩量6000t的ATP干馏工艺,目前已经在调试中阶段性运转,并逐渐延长连续运转时间,山东龙口等其他地方的油页岩加工利用也取得很大进展.美国目前没有进行油页岩干馏炼制页岩油的工业化生产,但有多所大学、公司和研究所已经对油页岩进行了长期的地上和地下干馏工艺的研究和开发.文中还介绍了国内外油页岩干馏的3种主要炉型,分别为块状页岩气体热载体干馏炉、颗粒页岩固体热载体干馏炉和粉末页岩流化干馏炉,并对比了不同国家的干馏炉型的优缺点.     

油页岩气体热载体干馏过程模拟

运用Aspen Plus软件,将油页岩定义为常规物流、非常规物流和常规惰性固体物流的混合物流,结合油母质热解机理、总包一级热解动力学模型,建立了油页岩气体热载体干馏炉模型。在干馏炉正常运行温度下,对油页岩中有机质及其热解产物页岩油、热解气体、半焦等物质的质量进行了计算和分析,并对不同温度下有机质及其热解产物的质量进行了计算和分析。模拟结果与干馏炉设计运行参数符合较好,能方便的对不同温度下热解产物的质量进行预测。     

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.     

Effect of the concentration of organic matter on the yield of thermal bitumen from the baltic oil shale kukersite

The low-temperature (360°C) autoclave pyrolysis of the oil shale kukersite, which has carbonatetype mineral matter, with various organic matter (OM) concentrations of 31.8–90.1% and the separation of the pyrolyzate from the mineral matter at the stage of thermal bitumen formation by extraction with various solvents such as benzene, ethanol, and their mixtures were considered. The OM distribution between a gas, an extract, and a residue insoluble in a given solvent was characterized. It was found that, in the pyrolysis of oil shale in an autoclave, the extract yield on an OM basis somewhat increased as the OM content of oil shale increased because the concentration of OM adsorbed on the mineral matter of oil shale remained constant.     

油页岩中矿物质对挥发分不凝气释放过程的影响

对桦甸油页岩（OS-R）采用HCl/HF/HNO3处理,分别得到去碳酸盐样品（OS-C）、去碳酸盐及硅酸盐样品（OS-F）以及有机质样品（OS-N）,用XRD鉴别其矿物组成,然后通过TG-FTIR-MS研究有机质脱挥发分机理及不同矿物质对挥发分不凝气释放过程的影响。结果表明：黄铁矿的存在使挥发分不凝气体释放的初始温度明显降低,反应更易进行,且使生成的不凝气产量更高,尤其是对不凝气中H2O生成促进作用更显著;硅铝酸盐的存在使不凝气体产量明显减少,提高了不凝气释放的初始温度,减少了不凝气释放的过程时间。然而碳酸盐的存在能增加不凝气产量,使CO2脱出的初始温度更低。     

油页岩微波热解气态产物析出特性

利用微波化学试验装置研究了油页岩微波热解过程中挥发分析出特性, 考察了微波功率、热解温度、不同热解温度阶段和催化剂对气体组成的影响。结果表明:微波加热能够提高油页岩热解气中H₂、CO和C₂H₄的析出, 降低CO₂的析出;50%(1600W)微波功率时烃类的析出量最大;在150~350℃的低温阶段热解气的析出量大, 主要由吸附气体的释放, 不稳定支链和基团的分解产生;温度升高, 气态产物的析出主要由脱氢、芳构化、缩聚和自由基反应产生。催化剂促进了气体的析出, 但不同类型催化剂对油页岩热解气组成的影响不同, 分子筛的吸附作用促进二次分解和缩聚反应;黏土类催化剂在质子酸作用下促进有机质催化裂解加氢反应, 加快断链和基团的稳定;金属类催化剂是强吸波性介质, 能够提高升温速率, 促进热解反应, 其次促进氢自由基的产生和转移。     

重质有机质热解过程中挥发物的产出与逸出气体分析研究进展

煤、重质油、生物质等重质有机质富含碳氢共价结构,其轻质化和定向化学品转化是加工利用的主要目标。热解是重质有机质加工过程中最直接、最基础的反应过程,挥发物作为重要的热解产物,其组成分布及在热解过程的演变规律解析是研究的关键和热点问题。本文综述了重质有机质热解过程中挥发物的生成过程,总结了反应类型及产物组成随温度升高的阶段性变化,并以煤、油砂、油页岩、生物质、含油污泥、市政污泥以及废橡胶为例,对比了不同种类的重质有机质热解挥发物产出的异同。针对重质有机质挥发物逸出特性分析方法,本文重点介绍了质谱、傅里叶变换红外光谱逸出气体分析技术,举例说明了各方法在重质有机质有机结构解析、热解工艺条件优化、污染物控制、催化剂设计等研究上的应用,并且就现阶段热解过程逸出气体的定量分析方法和应用进行了概述。最后,本文还就重质有机质热解逸出气体分析技术提出了建议和展望,以期为重质有机质的热解研究提供参考和借鉴。     

Chemical depolymerization of oil shale

The chemical structure of the organic matter from Krassava oil shale has been investigated by means of chemical degradation with metallic sodium in liquid ammonia and with phenol in the presence p-toluenesulphonic acid. The former reaction yielded 20 wt% of pyridine-soluble material and the latter ≈ 65 wt%. Extensive depolymerization of the oil shale was achieved by a combination of both methods in which case the solubility of the organic matter was increased to 85–95 wt%. The characterization of soluble and insoluble products by pyrolysis g.c. and elemental analysis indicated that aliphatic chains were prevalent in the organic matter of the Krassava oil shale.     

Extraction of El-Lajjun Oil Shale

Abstract

Extraction of the bitumen fraction of El-Lajjun oil shale was carried out using 17 different solvents, pure and combined. Out of all the solvents used, toluene and chloroform were found to be the most efficient for extraction of the bitumen to perform the major part of the experiments. This selectivity was based on the quality and quantity of the yield and on the quantity of solvent recovered. Extraction was carried out using a Soxhlet extractor. For complete recovery of solvent the extract phase was subjected to two stages of distillation, simple distillation followed by fractional distillation, where different cuts of oil were obtained. It was found that an optimum shale size of 1.0 mm offered better solvent recovery. One hour was the optimum time needed for complete extraction. The yield of oil was determined from the material balance gained from fractional distillation after testing for the existence of any traces of solvent trapped in the different cuts by using a gas chromotography technique. When chloroform was used, it was found that the average amount of bitumen extracted was 0.037 g/g of shale, which corresponds to 98% of the actual bitumen trapped in the oil shale (by assuming the bitumen represents 15% of the organic matter) and 84.1% of solvent recovered. When toluene was used, it was found that the average amount of oil extracted was 0.0293 g/g of shale, which corresponds to 78% of the actual bitumen trapped in the oil shale (by assuming bitumen represents 15% of the organic matter) and 89.9% of solvent for extraction with toluene.     

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.     

Influence of Temperature on the Hydrogenation of Oil Shale from the Kashpir Deposit

The effect of the hydrogenation temperature of oil shale from the Kashpir deposit on the yield and the properties of the resulting liquid hydrocarbons and gasoline and diesel fractions separated from them was studied. It was found that synthetic oil can be obtained from high-sulfur oil shale with the use of hydrogenation processing. In this case, it is possible to extract more than 90% of the organic matter of oil shale. Depending on the temperature of this processing, the sulfur content of the synthetic oil varied from 2.8 to 4.2 wt %, and the nitrogen and light fraction contents varied from 1.3 to 1.6 and from 34 to 67 wt %, respectively.     

宁东地区延安组泥页岩油气资源勘探潜力评价

宁东地区延安组沉积有泥页岩岩层,该套泥页岩至今仍是页岩油气资源勘探的盲区。本文通过对宁东地区的泥页岩野外露头和岩芯样品进行泥页岩基本性质的测定,发现研究区延安组泥页岩粘土矿物含量较高,有机碳含量高,干酪根类型以Ⅱ2型为主。但是,此套泥页岩的有机质成熟度较低,未达到烃源岩生烃门限,因此不具备页岩气的勘探潜力。同时,通过对泥页岩进行含油率的测定和岩石热解分析,发现其含油率及生油潜量达不到油页岩的标准,因此研究区延安组也不具备油页岩的勘探潜力。     

Composition of the liquid products of the supercritical fluid extraction of oil shale from the Chim-Loptyugskoe deposit

Data on the liquid product composition of the thermal degradation of the organic matter of an oil shale sample from the Chim-Loptyugskoe deposit in benzene under supercritical conditions in temperature ranges to 200, 200–300, and 300–400°C were acquired with the use of a set of analytical methods. It was found that the concentration of tar–asphaltene substances in the pyrolyzates decreased with temperature; in the structure of these substances, the fraction of aromatic fragments increased and the fraction of aliphatic fragments decreased. The fraction of polar compounds in the composition of oil components decreased.     

Thermal solution of Kashpir shale in pressurized benzene under supercritical conditions

The results of the thermal solution of oil shale in benzene in a flow unit under supercritical conditions are reported. It was found that the conversion of shale organic matter into liquid products increased by a factor of 2.5 with an increase in the solvent pressure from 5 to 15 MPa.     

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.