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.     

油页岩固体热载体流化干馏炼油工艺中试研究

介绍了以依兰粉末页岩作原料的页岩流化干流中试装置概况及试验流程,并对试验结果进行了分析。中试结果表明,中试装置页岩油产率为铝甑干馏法的90.15%,经冷凝回收系统及油泥处理后获得的页岩油收率为铝甑的82%;固体热载体流化干馏工艺所产页岩油较轻,337℃以前馏分大于80%。     

油页岩地面干馏技术研究

近年来,随着国际石油供求矛盾的不断突出和石油价格的居高不下,油页岩资源逐渐引起了众多科研人员的青睐.油页岩是一种重要的非常规油气资源.世界油页岩分布范围广,储量十分丰富,其探明可采储量如果折算成页岩油,数倍于世界原油的探明储量.页岩油作为石油的一种理想替代品,进行油页岩制油技术的研究不仅蕴含巨大的商业利益和经济价值,对国家安全和能源战略也具有十分重要的意义.油页岩制取页岩油的技术可分为地面干馏技术和原位开采技术.地面干馏技术的工艺和设备发展比较成熟,也是目前制取页岩油最主要的途径.根据颗粒粒度的大小又可分为块状干馏技术和小颗粒干馏技术.着重介绍的块状油页岩干馏技术有抚顺炉技术、Kiviter技术和Petrosix技术,小颗粒干馏技术有Tosco-Ⅱ技术、ATP 工艺和Enefit-280工艺等.最后指出了油页岩地面干馏技术的发展趋势.     

国内油页岩加工工艺及展望

结合国内油页岩资源现状,分析了国内油页岩干馏加工的方法,以及未来油页岩加工的发展趋势。各种油页岩性质不同,需要选择合适的加工工艺。开发油页岩干馏制油成套技术与装备是我国油页岩加工行业的发展方向。     

页岩灰对油页岩低温干馏产物的影响

分别介绍了油页岩低温干馏试验、油页岩与页岩灰掺混的干馏试验,结果表明,其他条件相同时,页岩灰与油页岩以4:1比例掺混时,油页岩干馏所产页岩油(凝点10℃,密度0.898 2g/cm3)与油页岩不掺混页岩灰干馏所得页岩油(凝点26℃,密度0.909 6g/cm3)相比,页岩油品质有所提升,有助于后续加工。     

我国页岩油的加工

页岩油性质和天然石油相似,因此,天然石油加工制取轻质油品工艺,一般也适用于页岩油。但和天然石油不同的是,页岩油含氮、硫、氧等非烃化合物量高,不饱和烃多,轻馏分少,所以必须采用深度加工与精制的工艺流程,才能得到合格的轻质液体燃料。由于石油资源日趋紧张,页岩油的开发利用得到了关注。介绍了我国对页岩油加氢精制、加氢裂化与非加氢精制研究的进展。     

Attrition and abrasion models for oil shale process modelling

As oil shale is processed, fine particles, much smaller than the original shale, are created. This process is called attrition or, more accurately, abrasion. In this paper, models of abrasion are presented for oil shale processed in several unit operations. Two of these unit operations, a fluidized bed and a lift pipe, are used in the Lawrence Livermore National Laboratory hot recycle solid (HRS) process being developed for the above-ground processing of oil shale. Abrasion occurs so commonly in the handling and processing of paniculate materials that numerous studies have been conducted to characterize the phenomenon and to attempt to minimize it. In the review of the literature, materials which have been studied for attrition potential are examined, as are the specific unit operations for which either experimental or modelling studies have been conducted. Several papers are discussed in which attrition in fluidized beds or lift pipes is addressed. In this paper, empirical models are derived for the processes occurring in the HRS process from the experimental studies conducted on oil shale. The derived models are presented, as are comparisons with experimental results.     

Gewinnung von Öl durch Schwelen von Ölschiefer und Teersand als Beitrag zur Energieversorgung

The contribution to energy supply of oil recovered by distillation of oil shale and tar sands . Following a world-wide survey of the most important deposits of oil shale and tar sands, the current activities in the USSR, China and Canada in the field of the industrial recovery of shale oil and bitumen from tar sand are described in broad terms. Thereafter, the current large-scale projects for the production of synthesis oil from these feedstocks are dealt with. The operating method and development status of modern processes for distilling oil shale are covered, as is the working principle of the hot water extraction of tar sand which is already commercially in application. The LR-Process method of operation and its especial feature of circulating the distilled residue as solid heat carrier are discussed in more detail. This is followed by information on the throughput potential of this process. The characteristic reactions influencing the quality of the LR products (oil, gas, residue, flue gas) are handled. Typical quality data for oil and gas obtained from oil shale and tar sands are given. A route is indicated for further processing of the condensate streams from the Lurgi-Ruhrgas Process. This consists of precipitation of solids, distillative separations and one hydrogenation step for the naphtha and oil fraction. These process steps produce a ?syncrude”? which can be further processed together with crude oil in conventional refineries. Examples are given for the independent further processing of syncrude to end-products customary on the market.     

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.     

Oxidative pyrolysis of oil shale in tubular flow reactors with external heating

This article discusses the possibilities of the multipurpose use of oil shale based on the methods of their thermal processing. The main current concepts of oxidative pyrolysis processes are considered. A facility for the oxidative pyrolysis of powdered oil shale in tubular reactors of the gas-suspension type with external heat supply to the reaction zone is described.     

Current trends in the pyrolysis of oil shale: A review

The review surveys recent publications on the pyrolysis of oil shale. The effect of process parameters on the composition and properties of the resulting products and problems related to the further thermal processing of shale oils are considered.     

Complex Processing of Oil Shale from the Volga Basin

The currently available thermal methods of the processing of oil shale were analyzed. The composition and properties of Volga shale and prospects for their complex processing were considered for the purpose of obtaining a wide range of valuable products.     

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.     

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.     

抚顺页岩油加工方案初步研究

介绍了世界上页岩油的各种加工方法,从工程设计的角度出发,研究了抚顺页岩油加工精制的工艺路线和工艺方法,提出了以煤制氢作为氢源的加氢精制工艺流程。     

Separation of kerogen from green river oil shale

The complex analysis of the chemical composition and technological properties of oil shale from the Green River formation was carried out. The technical characteristics and granulometric composition of test samples and the element compositions of the mineral and organic matters of shale rocks were determined. The structure of organomineral aggregates formed upon the crushing of shale rocks was studied by electron microscopy. Based on the experimental data, a procedure was developed for the separation of kerogen from the oil shale by physicochemical processing.     

The prediction of clay contents in oil shale using DRIFTS and TGA data facilitated by multivariate calibration

The prediction of clay content in oil shale is important for the optimisation of oil shale processing conditions and process feasibility. The multivariate calibration technique of partial least squares regression (PLSR) was implemented in order to predict clay content in oil shale samples taken from the Stuart oil shale deposit, Queensland, Australia. The calibration data used were the diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) spectra of 34 oil shale samples. DRIFTS data from another set of 20 oil shale samples were used for model validation. The data pre-processing includes the use of derivatives facilitated by the Savitsky-Golay nine-points’ method. A four components model was constructed and it showed a root mean square error of calibration (RMSEC) of 4.79% and a root mean square error of prediction (RMSEP) of 4.35%. TGA data sets were also used to construct a calibration model, which produced less accurate results than DRIFTS. DRIFTS, when combined with multivariate calibration, provided an accurate in situ method of evaluating clay content in oil shale. Clay content measured using XRD was used as a reference.     

窑街油页岩粉末成型的工业干馏试验分析

采用河南理工大学研制的HPU-B黏结剂,将窑街油页岩粉末在甘肃窑街油页岩综合利用公司现场加工成型200 t页岩球,并于神木三江SJ型干馏方炉中完全取代块岩进行工业试验。结果显示：干馏炉运行完全正常,半焦能从熄焦池中顺利刮出,除页岩球半焦中残油率偏高外,油页岩粉末成型制备的页岩球完全可满足干馏工艺要求,通过对成型工艺和干馏炉参数进一步优化和调整后,页岩球完全可以替代块岩进行干馏。     

中国油页岩加工业新的发展机遇

从科学发展观的角度,论述了油页岩加工业在我国能源结构中的独特位置与发展优势,在我国已有的生产实践的基础上,总结了国内外油页岩加工业在加工工艺、环境保护以及副产品回收等方面积累的经验和未来的发展要求,以使我国拥有的丰富的油页岩资源能够得以充分的综合利用.     

Mineral and trace element composition of the Lokpanta oil shales in the Lower Benue Trough, Nigeria

The concentrations of minerals and trace elements in the Lokpanta oil shale from the Lower Benue Trough, Nigeria have been determined by X-ray diffraction (XRD) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), respectively. X-ray diffraction data were evaluated using the SIROQUANT™ interactive data processing system based on Rietveld interpretation methods. A new method of trace element determination in oil shale, involving LA-ICP-MS analysis of glass beads prepared by fusing oil shale ash on an iridium strip heater was used, and the accuracy of the method was assessed by including a standard shale reference material (SGR-1b) in the analysis program.The minerals in the raw oil shales are mainly quartz, calcite and clay minerals, with the latter being represented by kaolinite and interstratified illite/smectite. Ashes of the oil shale samples prepared at 815 °C have quartz and (in some cases) illite as the dominant mineral phases, along with a significant proportion of amorphous materials. The Lokpanta oil shales are highly enriched in some potentially hazardous trace elements, including V, Cr and Ni, when compared with oil shales from other deposits around the world. The results obtained for the trace elements in the reference material show that the LA-ICP-MS method described in this study is very accurate and precise for the determination of a wide range of trace elements in oil shales.