Dependence of the heats of combustion of oil shales on their chemical composition

The dependence of the heats of combustions of 21 shales from 21 different sources on their chemical composition was considered. The simulation of these dependences made it possible to obtain calculation formulas with the very high statistical characteristics. These formulas allowed us to predict the heats of combustions of oil shales with adequate accuracy and reliability for shales that were not investigated experimentally based on only their chemical composition.     

Analysis of rich oil shales by 1H nuclear magnetic resonance

The potential yields of rich oil shales from the Colorado Green River Basin were measured by pulsed ¹H nuclear magnetic resonance. The rates of decay of the signals, as quantified by their second moments, decreased with increasing organic content. This implies that whenever shales of widely varying yields are being compared, their free-induction-decays must be extrapolated to time zero.     

Hydrogen retorting of oil shales from Eastern Canada

The liquid production potential of thirty oil shale samples from Eastern Canada was determined by Fischer assay retort and pyrochem retort. For all shales, the presence of hydrogen during pyrochem retorting resulted in a significant increase in oil yields compared to Fischer assay yields. Ten oil shale samples were selected for detailed evaluation in the pyrochem retort in the presence of nitrogen and hydrogen. Besides increasing yields, the presence of hydrogen lowered the specific gravity of liquid products and the content of sulphur but increased the content of nitrogen. This was attributed to the stabilization of precursors to nitrogen compounds which prevented their polymerization.     

Pressurized fluidized-bed hydro retort ing of raw and beneficiated Eastern oil shales

Bench-scale tests were conducted with raw and beneficiated shales in an advanced multi-purpose research reactor. Raw Alabama shale and raw and beneficiated Indiana shales were retorted at 515 °C using hydrogen pressures of 4 and 7 MPa. Shale feed rates were 15 to 34 kg h⁻¹. High oil yields and carbon conversions were achieved in all tests. Oil yield from Alabama shale hydroretorted at 7 MPa was 200% of Fischer assay. Raw and beneficiated Indiana shales hydroretorted at 7 MPa produced oil yields of 170 and 195% of Fischer assay respectively. Total carbon conversions were >70% for all tests conducted at 7 MPa.     

Correlation between oil yields of oil shales and 13C nuclear magnetic resonance spectra

Using the cross polarization/dipolar decoupling method, ¹³C n.m.r. spectra have been obtained on twenty oil shales and kerogens from around the world. A correlation is found between the integrated signal intensity of the aliphatic region of the spectra and the oil yields of the shales.     

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.     

The Impact of Fatty Acid Composition on Transportation Fuel Yields via the Non-Catalytic Cracking of Triacylglyceride Oils

A wide spectrum of triacylglyceride (TG) oils were decomposed in batch lab and continuous pilot-scale reactors to generate an extensive database, which was then used to construct a model to predict the detailed composition of products generated during non-catalytic cracking. The model was then coupled with additional simulated process steps to determine the yields of transportation products and other chemical co-products meeting specifications of their petroleum analogs as validated with laboratory testing. A statistical study was then performed to use the model to analyze the impact that changes in TG oil composition have upon target product yields. In this study, the model was used to simulate a viable suite of products for every TG oil analyzed. The model predicts minor differences in the ratio of products from various different fatty acid compositions. For example, it was found that stearic (C18:0), oleic (C18:1), and erucic (C22:1) acids show a positive effect on fuel yields. By contrast, palmitic (C16:0), linoleic (C18:2), and linolenic (C18:3) acids have negative impacts on fuel yields. From these results, a hypothetical “ideal” TG oil was constructed. This oil turns out to have a composition that is very close to the composition of high oleic sunflower oil.     

Application of pyrolysis to the characterization and the upgrading of the Toarcian oil shales from the Paris basin

The hydrocarbon potential of oil shales in the lower Toarcian on the eastern edge of the Paris basin has been evaluated by means of borehole studies. The yields and physicochemical properties of oils obtained from the shale by pyrolysis in different atmospheres are reported.     

Fluidized bed steam retorting of Kentucky oil shale

A three-inch (7.6-cm) diameter fluidized bed reactor has been used at the Kentucky Center for Energy Research Laboratory (KCERL), operated by the Institute for Mining and Minerals Research (IMMR), to investigate the fluidized bed retorting characteristics of Kentucky oil shales. Because steam has been indicated to be a reactive pyrolysis gas for both Eastern and Western U.S. oil shales by many, a main objective of the fluidized bed investigation was to determine the effects of steam as a fluidizing medium. This was accomplished by comparing the yields and compositions of the products from steam and N₂ retorting under otherwise equivalent fluidized bed conditions. Oil yields obtained from steam fluidization were approximately 2% greater than oil yields obtained from N₂ retorting. Steam retorting released significantly more pyritic sulfur from the shale, providing evidence that reduced hydrogen scavenging from the kerogen for H₂S production was a possible mechanism for the increased oil production. Steam fluidization resulted in increased oil collection efficiency, and represented the most significant difference between the steam and nitrogen systems. Liquid product quality was similar for both steam and N₂ fluidization and the oils were more aromatic, more viscous, higher in density, higher in nitrogen content, and lower in volatility than Fischer Assay oil derived from the same shale.     

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.     

Trace elements in black and oil shales

Data on the abundance of trace elements in oil and black shales, as well as and the average concentrations of trace elements in these caustobioliths, are considered. In general, oil shales are enriched in Li, Be, B, Rb, Ta, and Se and depleted in Mo, Re, Ag, Au, V, Th, Cu, Hg (and, perhaps, W, As, and U) relative to black shales. Tentative values of minimal concentrations of trace elements oil shales are presented that make the integrated processing of shale organic matter economically viable to obtain by-product concentrates of valuable trace elements useful as feedstock for their recovery.     

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。     

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.     

Development of FT-i.r. procedures for the characterization of oil shale

A characterization of oil shale from the Mahogany Zone of the Green River Formation has been obtained by FT-i.r. A quantitative analysis of the mineral component by FT-i.r. spectroscopy is shown to be comparable to that obtained by X-ray diffraction when considering broad mineral types, i.e., carbonates. Methods for FT-i.r. analysis of the organic component, both from the whole shale and from kerogen specimens, have been refined. There is a good correlation between the intensity of alkyl bands and Fischer assay yields. An assessment is made of the applicability of extinction coefficients obtained from paraffins to their use in quantitative analysis of oil shales.     

The effects of alkali cooking on the yields of crude and neutral oil from cottonseed meats

Summary Equal quantities of flaked cottonseed meats of identical composition were similarly cooked at high moisture conditions with and without alkali present. The cooked flakes were exhaustively extracted with commercial hexane, and the yields of crude oil, neutral oil, and meal were determined. The yields from an equal quantity of uncooked flakes were similarly determined, chiefly to serve as a neutral oil control. Analyses of the crude oils and meals were compared to determine the effects of the presence of alkali while cooking on the composition of the products. These experiments show that there was a reduction in the yields of both crude and neutral oil resulting from the admixture of alkali with cottonseed flakes while cooking. Assuming yields from flakes cooked with water as 100%, and average of 0.6% less crude oil was obtained from alkali-cooked than from watercooked flakes. A similar comparison of the yields of neutral oil shows that those from the alkali-cooked flakes averaged about 0.75% less than from the flakes cooked with water. The crude oils from alkali-cooked flakes contained only about one-fifth as much gossypol as those from the water-cooked flakes and were appreciably lower in free fatty acids. The crude oils from alkali-cooked flakes were significantly higher in phosphorus. The sodium content of the oils from alkali-cooked flakes indicated that their content of soaps ranged from 0.07% to 0.19%. Presented at the spring meeting, American Oil Chemists’ Society, New Orleans, La., April 28–May 1, 1957. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Determination of shale oil yields by petrographic analysis

Rundle-type oil shales from five Australian deposits (Rundle, Stuart, Condor, Byfield and Duaringa) contain abundant lamellar alginite that is easily recognized using fluorescence microscopy. Shale oil yield, as determined by modified Fischer assay, is directly related to the volume per cent of alginite in the parent shales for each of the above deposits. Data provided show that interdeposit estimates of shale oil yield, based on alginite content, are more reliable than estimates based on specific gravity of the parent shales. Application of petrographic techniques should provide rapid assessment of the shale oil yield for other deposits with Rundle-type oil shale. The method requires initial calibration of alginite content, in a limited number of samples, with Fischer assays.     

Isopropanol fractionation of butter oil and characteristics of fractions

Fractionation of butter oil from isopropanol and characterization of the chemical composition and the melting properties of the fractions obtained have been investigated. Butter oil was fractionated from isopropanol (1∶4 wt/vol) at 15 to 30°C. The yields of stearins and oleins were dependent on the temperature employed during fractionation. Thus, 24.8 to 48.9% of stearins and 51.5 to 75.2% of oleins could be obtained as the crystallization temperature varied from 15 to 30°C. The stearin fractions displayed a distinct variation in the fatty acid compositions. The palmitic acid content of the stearin fractions varied from 39.1 to 44.0%, and that of stearic from 15.1 to 16.8%, respectively. The olein fractions contained 43.2% stearic acid, and 2.4 to 2.8% palmitoleic acid (C16∶1). The solid fat content values of the stearin fractions obtained were 62–67, 39–50, and 21–25 at 10, 20, and 30°C, respectively. From the results, it is evident that anhydrous milk fat can be fractionated at relatively high temperatures from isopropanol to produce stearin and olein fractions of specific composition and properties.     

Supercritical carbon dioxide extraction of spearmint oil from mint-plant leaves

Spearmint oil (essential oil of Mentha spicata) was extracted from Turkish mint-plant leaves using supercritical CO₂ in a basket-type extractor. Effects of temperature, pressure, extraction time, amount of CO₂, and entrainer (ethanol) concentration on composition of essential-oil extracts and oil yield, relative to hydro-distillation, were investigated. Relative yields were as high as 80%. Monoterpenes fraction in extracts was inversely correlated with relative oil yields. Monoterpenes were preferentially extracted by CO₂ due to their high vapor pressure, low molar mass and low polarity. Supercritical extraction presented advantages over the conventional hydro-distillation by yielding extracts lower in monoterpenes fraction and by enabling high yields at temperatures safe for the heat-sensitive essential oil.     

Characterization of shale oil solids removed by the high-gradient magnetic separation technique

The high-gradient magnetic separation (HGMS) technique has been previously shown to remove solid particles successfully from several types of shale oil. The nature of the separated solids was investigated in this study, principally by thermomagnetic measurements over the temperature range 4.2–1173 K and in applied fields up to 1600 kA m^?1. Several phase transformations were identified in the magnetization profiles as a function of temperature. These transitions varied depending on the particular sample, although the low-temperature behaviour was qualitatively similar for all the solids. The magnetization increased over the range of external field studied. The magnetometric data reflect the differences in composition of the different solid samples and indicate the general occurrence of a paramagnetic phase mixed with a trace amount of ferromagnetic component. The bulk mineralogy and elemental composition of the solids were similar to those of the oil shales prior to retorting. Relatively large concentrations of iron sulphides were identified.