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.     

Relation between fuel properties and chemical composition. 1. Jet fuels from coal,oil shale and tar sands

Jet fuels derived from coal, oil shale and tar sands were subjected to extensive chemical and physical property analysis. The straight-chain alkane content of each fractionated fuel was determined by gas chromatography and combined GC-mass spectrometry. Average parameters of the aromatic fractions of these fuels were obtained by p.m.r. spectroscopy. These analytical data were used to help explain differences in several important properties of the alternative fuels compared with jet fuel derived from petroleum. While suitable fuels can be produced from these alternative fossil-fuel sources, the processing requirements will be much different. The alternative fossil-fuel crude oils used in this work are similar to the lower-API-gravity petroleum crudes and therefore hydrocracking and delayed coking will be extensively used to produce military fuels.     

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.     

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。     

Microwave applications to oil sands and petroleum: A review

This review provides a general overview of microwave applications in oil sands bitumen or shale oil production in petroleum upgrading. The vast oil reserves in the oil sands of Alberta will become a major source of petroleum products in the near future and a number of alternative technologies have been explored for the production and upgrading of oil sands and heavy oil. This study is based primarily on the unique selective heating capacity associated with exposure of materials to microwaves. Of particular interest are applications of microwaves for bitumen extraction, upgrading heavy oils, removing heteroatoms, and the underground heating of oil sands to reduce bitumen viscosity and allow it to be pumped to the surface. The fundamentally different method of transferring energy from the source to the sample is the main advantage of utilizing microwave energy. By directly delivering energy to microwave-absorbing materials, conventional issues such as long heating periods and energy loses can be minimized. Microwave energy was shown to be effective in some applications; however, it is not used commercially at the present time.     

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.     

非沥青重质煤焦油临氢轻质化研究

加氢是使非沥青重质煤焦油轻质化和清洁化的有效方法之一,采用临氢技术可脱除煤焦油中的S,N,O和金属等杂质,使其成为清洁燃料,芳烃加氢饱和并裂解开环成为优质轻质油组分,胶质被加氢分解成分子较小的烃类.结合国内外煤焦油加氢的技术现状,指出非沥青重质煤焦油难加氢的原因,介绍了200 ℃～540 ℃馏分的高温煤焦油重焦油的性质,此原料采用适宜的加工流程,在针对此原料组成特点开发的专用催化剂作用下,实现了100%转化,石脑油馏分收率13%和柴油馏分收率80%.     

The Catalytic Synthesis of Hydrocarbons from Carbon Monoxide and Hydrogen

The increasing demand for energy, coupled with the uncertainty and expense of crude oil imports, has renewed interest in the production of fuels and chemicals from hydrogen-deficient materials. These energy sources such as coal, residua, oil shale, and tar sands can be gasified with steam and oxygen to produce a gas containing large quantities of carbon monoxide and hydrogen. Once methane is removed from this CO/H₂ mixture it is purified to remove S poisons and then reacted over a catalyst to produce a variety of organic products. The synthesis of hydrocarbon products, with the exception of methane, is commonly referred to as the Fischer-Tropsch synthesis reaction.     

Heavy oil refining and transportation: effect on the feasibility of increasing domestic heavy oil production

As part of a programme to assess the feasibility of increasing domestic heavy oil production from US reservoirs, a study of the crude oil transportation system and petroleum refining industry has been initiated to determine their ability to accommodate additional domestic heavy oil. This paper summarizes refining trends and potential limitations in the production/transportation/refining network that may influence the expansion of domestic heavy oil production outside the current heavy oil producing areas. Although the number of refineries has decreased over the past decade, the remaining large refineries have been able to stabilize charge capacity and increase refinery throughput. A few refineries have been designed to economically process select heavy oils and obtain acceptable yields of products. However, refiners seek more light sweet crude oil and less sour or heavy crude to meet the requirements of clean fuels as mandated by the Clean Air Act Amendments of 1990. Transport of heavy oil poses significant problems in that there are limited heated pipelines, and transport of heavy oil to distant refineries adds to the cost of heavy oil production. Addition of significantly more heavy oil, either domestic or imported, will substantially reduce refinery efficiency and throughput affecting yields and margins. This will not change without significant investment in refinery modification to be able to process heavy oil.     

Some chemistry of organosulphur compound types occurring in heavy oil sands: 2. Influence of pH on the high temperature hydrolysis of tetrahydrothiophene and thiophene

The hydrolysis of thiophene at high temperatures and pressures has been examined in relation to the steam-stimulated recovery of high-sulphur tar sands and heavy oils. The influence of pH has been examined in the hydrolysis of both thiophene and tetrahydrothiophene considered to be reasonable models for organosulphur molecular types in heavy oils. Mechanisms are proposed to account for the products observed under acidic, neutral and basic conditions.     

Nitrogen compound distribution in middle distillate fuels derived from petroleum,oil shale,and tar sand sources

Nitrogen compounds present in crude sources constitute serious problems both for producers and consumers. For producers, these compounds are responsible for poisoning catalysts during the refining processes. For consumers, these compounds are responsible for the degradation observed in fuels during storage and handling. The quality of petroleum, as measured by °API gravity, continues to decrease in quality. This, coupled with the inevitable use of other crude sources, if used in quantity will further decrease the stability of middle distillate fuels. In this article we present our method for the separation and quantitation of the slate of nitrogen compounds present in middle distillate fuels derived from petroleum, oil shale and tar sand sources. Results from our laboratory indicate that of all of the nitrogen compounds present in middle distillate fuels, the indole type structure is the most deleterious.     

Processing oil shales with heavy oil recycle

Recycle of heavy oil (>340 °C) to the retort, in order to crack/coke the oil to lighter fractions, was investigated as a means of producing shale oil of more desirable product slates. Conversion of heavy oil to light oil (<340 °C) by thermal cracking and coking in the absence of and during oil shale retorting was studied using the CSIRO BIRCOS retort. As expected, the conversion by thermal cracking increased as temperature increased, with most of the net oil loss in the form of gas. By contrast, the conversion by coking alone decreased as temperature increased, with coke representing all the net oil loss. Thermal cracking was found not to be a first-order reaction, by showing a reduced conversion of heavy oil with reduced concentration of oil vapour. Retorting Stuart oil shale with heavy oil feeding and simultaneous cracking and coking showed a conversion of 19.1 g per 100 g feed heavy oil to 10.9 g light oil, 2.2 g gas and 6.0 g coke, with a net oil loss of 3.8 g per 100 g shale oil produced. These data were used to generate a set of parameters for a mathematical model which simulated a heavy oil recycle loop.     

Catalyst-Feedstock-Engineering Interactions in Fluid Catalytic Cracking

Fossil fuels, amassed over eons of geologic prehistory, are being irreversibly depleted about 10⁶ times more rapidly than they were formed. With this sort of kinetics, there is little question that there exists, in the ultimate sense, an energy crisis [1-3]. That is, there will be fuel deficits for whatever time interval declining volumes of hydrocarbon reserves are not compensated for by increased supply from new energy sources such as nuclear, solar, and geothermal. In the interim period, the petroleum refiner is forced to utilize higher molecular weight, more hydrogen-deficient crudes, and crude fractions which have higher concentrations of impurities. Eventually, substantial quantities of “synthetic crudes” derived from coal, oil shale, tar sands, and bitumens may also become available.     

油页岩与煤路线制油的技术经济分析和比较

液体燃料广泛应用于交通、物流和生活等行业,然而液体燃料的生产严重依赖石油。我国石油资源相对贫乏,石油对外依存度高达60%。为减少对石油的依赖,我国正积极开发石油替代资源,特别是油页岩和煤炭。但迄今少有文献报道对油页岩与煤路线生产液体燃料过程进行全面的技术经济分析和比较。本文通过对油页岩制油和煤制油分别进行建模和模拟,根据模拟从能效、投资和成本等方面对这两种路线进行分析和比较。结果表明油页岩制油的能效比煤制油低5个百分点,因为油页岩制油的原料利用率低,产品收率低。经济方面,油页岩制油的固定投资为63.34元/GJ,相比煤制油节省70%,因为油页岩制油流程短,设备结构简单。但油页岩制油的原料消耗大,生产1t液体燃料消耗24.5t油页岩,所以其成本相比煤制油仅节省6%。     

Influence of coal,shale, and petrochemical binders and fillers on the properties of cold-rammed hearth mass

Heat-treated tar from the high-speed pyrolysis of Kansko-Achinsk lignite (Russia) and Baganursk lignite (Mongolia), asphalt from Yaregsk petroleum, A-10 softener, and heavy shale oils from gas-generator stations and UTT-3000 systems are promising binders for the manufacture of cold-rammed hearth mass.     

Comparison of the chemical structure of coal hydrogenation products,athabasca tar sand bitumen and Green River shale oil

Coal hydrogenation products, Athabasca tar sand bitumen, and Green River shale oil produced by retorting were analyzed by the Brown—Ladner method and the Takeya et al. method on the basis of elemental analysis and ¹H-NMR data, by ¹³C-NMR spectroscopy and by FT-IR spectroscopy. Structural characteristics were compared.The results show that the chemical structure of oils from Green River shale oil and Athabasca tar sand bitumen, and the oils produced in the initial stage of hydrogenation of Taiheiyo coal and Clear Creek, Utah, coal is characterized as monomers consisting of units of one aromatic ring substituted highly with C_3–6 aliphatic chains and heteroatom-containing functional groups. The chemical structure of asphaltenes from Green River shale oil and Athabasca tar sand bitumen is characterized by oligomers consisting of units of 1–2 aromatic rings substituted highly with C_3–5 aliphatic chains and heteroatom-containing functional groups. The chemical structure of asphaltenes from coal hydrogenation is characterized by dimers and/or trimers of unit structures of 2 to 5 condensed aromatic rings, substituted moderately with C_2–5 aliphatic chains and heteroatom-containing functional groups.The close agreement between fa(¹H-NMR) and fa(¹³C-NMR) for Green River shale oil derivatives and Athabasca tar sand derivatives indicates that the assumption of 2 for the atomic H/C ratio of aliphatic structures is reasonable. For coal hydrogenation products, a value of 1.6–1.7 for the H/C ratio of aliphatic structures would be more reasonable.     

The Use of Clays for the Hydrotreatment of Heavy Crude Oils

The increasing supply of heavy crude oils is a matter of serious concern for the petroleum industry. In order to satisfy the changing pattern of product demand, significant investments in refining conversion processes will be necessary to profitably utilize these heavy crude oils. Although the most efficient and economical solution to this problem will depend to a large extent on individual country and company situations, the most promising technologies will likely involve the conversion of vacuum bottom residual oils, asphalt from deasphalting processes, and superheavy crude oils into useful light and middle distillate products.     

利用页岩油制取20#重质燃料油的研究

实验研究采用的是抚顺页岩油厂生产的页岩油,其组成类似天然石油,富含烷烃和芳烃,但烯烃要比天然石油高的多.此外,页岩油中氧、氮、硫等非烃化合物含量也较多,类似煤焦油的组成.本文对抚顺页岩油的一般性质做了初步评价,研究了由抚顺页岩油通过减压蒸馏的方法制取20#重质燃料油.考查了在减压蒸馏过程中温度和真空度对原料油的影响,从...     

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.     

Extraction of tar acids from tar oils by aqueous acetamide

Aqueous acetamide has been found to be a good solvent for the extraction of tar acids from low temperature carbonisation tar oils. Saturated acetamide solution at 15–30° in the molar ratio acetamide/tar acids of 3 : 1 effects a recovery of about 90% of tar acids originally present in the oil in two extraction stages. The tar acids are obtained in 77% purity, the impurities consisting of neutral oils and tar bases. Re-extraction with light petroleum can raise the purity of tar acids to 94%. Tar acids can be separated from the purified acetamide extract by suitable dilution with water. The system tar acids—(bases + neutral oils)—saturated aqueous acetamide has been studied. It has been shown that three theoretical counter-current extraction stages are required to effect a recovery of 95% of tar acids from a feed oil containing 45% tar acids. 98% recovery of the tar acids could be achieved in four stages.