Carbon-13 NMR analysis of shale oil and shale oil derived jet fuels
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Ursenbach, W. O.↗
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In-situ laser retorting of oil shale
Oil shale formations are retorted in situ and gaseous hydrocarbon products are recovered by drilling two or more wells into an oil shale formation underneath the surface of the ground. A high energy laser beam is directed into the well and fractures the region of the shale formation. A compressed gas is forced into the well that supports combustion in the flame front ignited by the laser beam, thereby retorting the oil shale. Gaseous hydrocarbon products which permeate through the fractured region are recovered from one of the wells that were not exposed to the laser system.
Bloomfield, H. S.↗
Coupling dynamic in situ X-ray micro-imaging and indentation: A novel approach to evaluate micromechanics applied to oil shale
Oil and gas shales are a system where understanding the mechanical properties at the microscale is of paramount importance, e.g. to better understand the behavior of proppant-shale contacts and their role in the evolution of propped fractures in unconventional reservoirs. Here we show for the first time an experiment coupling indentation testing with in situ X-ray imaging in a Green River shale sample. A full compliance curve has been measured with the sample in water, allowing to visualize the indentation of the sample in function of axial load, in a purpose-built system for combined in situ indentation and X-ray imaging. A series of 3D datasets were used for a digital volume correlation study to obtain local strain fields. This analysis has been complemented with the analysis of cracks. Finally, geomechanical modeling has been carried out to replicate and generalize the observed behavior in the shale. This study validated this experimental approach, providing a breakthrough in understanding micro-mechanics in shales, and demonstrates how this class of experiments can be important for studies involving the prediction of the evolution of propped fractures in shale reservoirs, with possible applications in a much larger number of application fields (geothermal, materials science, etc.)
04 OIL SHALES AND TAR SANDS↗
Solar heated oil shale pyrolysis process
An improved system for recovery of a liquid hydrocarbon fuel from oil shale is presented. The oil shale pyrolysis system is composed of a retort reactor for receiving a bed of oil shale particules which are heated to pyrolyis temperature by means of a recycled solar heated gas stream. The gas stream is separated from the recovered shale oil and a portion of the gas stream is rapidly heated to pyrolysis temperature by passing it through an efficient solar heater. Steam, oxygen, air or other oxidizing gases can be injected into the recycle gas before or after the recycle gas is heated to pyrolysis temperature and thus raise the temperature before it enters the retort reactor. The use of solar thermal heat to preheat the recycle gas and optionally the steam before introducing it into the bed of shale, increases the yield of shale oil.
Qader, S. A.↗
Thermal stability of some aircraft turbine fuels derived from oil shale and coal
Thermal stability breakpoint temperatures are shown for 32 jet fuels prepared from oil shale and coal syncrudes by various degrees of hydrogenation. Low severity hydrotreated shale oils, with nitrogen contents of 0.1 to 0.24 weight percent, had breakpoint temperatures in the 477 to 505 K (400 to 450 F) range. Higher severity treatment, lowering nitrogen levels to 0.008 to 0.017 weight percent, resulted in breakpoint temperatures in the 505 to 533 K (450 to 500 F) range. Coal derived fuels showed generally increasing breakpoint temperatures with increasing weight percent hydrogen, fuels below 13 weight percent hydrogen having breakpoints below 533 K (500 F). Comparisons are shown with similar literature data.
Reynolds, T. W.↗
Synthesis and analysis of jet fuel from shale oil and coal syncrudes
Thirty-two jet fuel samples of varying properties were produced from shale oil and coal syncrudes, and analyzed to assess their suitability for use. TOSCO II shale oil and H-COAL and COED syncrudes were used as starting materials. The processes used were among those commonly in use in petroleum processing-distillation, hydrogenation and catalytic hydrocracking. The processing conditions required to meet two levels of specifications regarding aromatic, hydrogen, sulfur and nitrogen contents at two yield levels were determined and found to be more demanding than normally required in petroleum processing. Analysis of the samples produced indicated that if the more stringent specifications of 13.5% hydrogen (min.) and 0.02% nitrogen (max.) were met, products similar in properties to conventional jet fuels were obtained. In general, shale oil was easier to process (catalyst deactivation was seen when processing coal syncrudes), consumed less hydrogen and yielded superior products. Based on these considerations, shale oil appears to be preferred to coal as a petroleum substitute for jet fuel production.
Gallagher, J. P.↗
Method of rubblization for in-situ oil shale processing
A method that produces a uniformly rubblized oil shale bed of desirable porosity for underground, in-situ heat extraction of oil. Rubblization is the generation of rubble of various sized fragments. The method uses explosive loadings lying at different levels in adjacent holes and detonation of the explosives at different levels in sequence to achieve the fracturing and the subsequent expansion of the fractured oil shale into excavated rooms both above and below the hole pattern.
Yang, Lien C.↗
Oil shale extraction using super-critical extraction
Significant improvement in oil shale extraction under supercritical conditions is provided by extracting the shale at a temperature below 400 C, such as from about 250 C to about 350 C, with a solvent having a Hildebrand solubility parameter within 1 to 2 Hb of the solubility parameter for oil shale bitumen.
Compton, L. E.↗
Estimating diffusion coefficients of shale oil, gas, and condensate with nano-confinement effect
Molecular diffusion plays an important role in oil and gas migration in tight shale formations. However, there are insufficient reference data in the literature to specify the diffusion coefficients within porous media. This study aims at calculating diffusion coefficients of shale gas, shale condensate, and shale oil at reservoir conditions with CO 2 injection for EOR/EGR. The large nano-confinement effects including large gas-oil capillary pressure and critical property shifts could alter the phase behaviors. This paper estimates the diffusivities of shale fluids in nanometer-scale shale rock from two perspectives: 1) examining the shift of diffusivity caused by nanopore confinement effects from phase change (phase composition and fluid property) perspective, and 2) calculating the effective diffusion coefficient in porous media by incorporating rock intrinsic properties (porosity and tortuosity factor). The tortuosity is obtained by using tortuosity-porosity relations as well as the measured tortuosity of shale from 3D imaging techniques. The results indicated that nano-confinement effects could affect the diffusion coefficient through altering the phase properties, such as phase compositions and densities. Compared to bulk phase diffusivity, the effective diffusion coefficient in porous shale rock is reduced by 10 2 to 10 4 times as porosity decreases from 0.1 to 0.03.
04 OIL SHALES AND TAR SANDS↗
Quantifying Fluid-Wettable Effective Pore Space in the Utica and Bakken Oil Shale Formations
Combined (ultra-) small angle neutron scattering measurements [(U)SANS] and a contrast matching technique were employed to quantify the porosity and pore size distribution from 1 nm to 10 μm and to differentiate accessible (open) pores and inaccessible (closed) pores with respect to organophilic and hydrophilic fluids for two Utica and two Bakken shale samples. Overall, the results indicate that around 40–70% of the pores in the Utica oil shales (mixed carbonate mudstone) are accessible to oil, and 34–37% of the pore surfaces are water-wet. In contrast, the Bakken oil shales (mixed siliceous mudstone and carbonate/siliceous mudstone), which have high total organic carbon contents, have a higher proportion of isolated pore space that is not preferentially wet by oil or water, with less than 36% of the pores accessible to both fluids. In addition, for both formations, pores less than 3 nm in diameter are not oil accessible (organic matter related) but water accessible (clay tactoids related).
58 GEOSCIENCES↗
Synthesis and analysis of jet fuels from shale oil and coal syncrudes
The technical problems involved in converting a significant portion of a barrel of either a shale oil or coal syncrude into a suitable aviation turbine fuel were studied. TOSCO shale oil, H-Coal and COED coal syncrudes were the starting materials. They were processed by distillation and hydrocracking to produce two levels of yield (20 and 40 weight percent) of material having a distillation range of approximately 422 to 561 K (300 F to 550 F). The full distillation range 311 to 616 K (100 F to 650 F) materials were hydrotreated to meet two sets of specifications (20 and 40 volume percent aromatics, 13.5 and 12.75 weight percent H, 0.2 and 0.5 weight percent S, and 0.1 and 0.2 weight percent N). The hydrotreated materials were distilled to meet given end point and volatility requirements. The syntheses were carried out in laboratory and pilot plant equipment scaled to produce thirty-two 0.0757 cu m (2-gal)samples of jet fuel of varying defined specifications. Detailed analyses for physical and chemical properties were made on the crude starting materials and on the products.
Antoine, A. C.↗
USAF shale oil program status
The test and evaluation program on shale derived fuel being conducted by the Air Force is intended to accomplish the minimum amount of testing necessary to assure both the safe use of shale oil derived turbine fuels in operational USAF aircraft and its compatibility with USAF handling systems. This program, which was designed to take advantage of existing R&D testing programs, began in 1981. However, due to a problem in acquiring the necessary fuel, the testing program was suspended until July 1983 when an additional sample of shale derived fuel was received. Tentatively, the Air Force is planning to make three relatively minor revisions to the procurement specifications requirements for the production shale derived fuel. These are: (1) Aromatic Contest (min) - 9% (by volume); (2) Nitrogen (max - 20 ppm by weight); and (3) Antioxidants - 9.1 g/100 gal (U.S.)
Delaney, C. L.↗
High-resolution mass spectrometry of nitrogenous compounds of the Colorado Green River formation oil shale.
Basic nitrogenous compounds isolated from extracts of Green River Formation oil shale were analyzed. The major homologous constituents found were the compositional types - namely, quinolines, tetrahydrequinolines with minor amounts of pyridines and indoles series and traces of more aromatized nitrogen compounds. These results are correlated with nitrogen compounds isolated from Green River Formation retort oil and are a survey of the unaltered nitrogen compounds indigeneous to the shale.
Simoneit, B. R.↗
In-situ 4D visualization and analysis of temperature-driven creep in an oil shale propped fracture
Here, the proppant embedment due to creep in shales is a known issue affecting the useable lifetime of wells in unconventional oil and gas recovery. One of the factors influencing creep is the presence of organics, whose properties can be very sensitive to temperature. In this work we investigated for the first time the role of temperature-induced creep increase in proppant embedment in an organics-rich Green River oil shale sample via in-situ synchrotron X-ray micro-computed tomography. We observed that temperatures as low as 75 °C already induce fast creep, with a fracture aperture closing rate of 13 μm/h and a loss of fracture conductivity rate of 8.7%/h, due only to proppant embedment, in the measured interval at the first heating stage. Local displacement data analysis provided evidence for markedly plastic deformation around the proppant-shale contacts, in contrast with the brittle proppant embedment observed on more cemented and less organics-rich shales at room temperature. The results highlight how the problem of temperature-dependent mechanical behavior might be more important than previously thought, in shales with a high content in organics, and that in-situ micro-imaging techniques can play a key role in understanding the underlying mechanisms, contributing to solve creep-related problems associated with hydraulic fracturing in complex scenarios.
02 PETROLEUM↗
Nitrogenous compounds of the Colorado Green River Formation oil shale - A preliminary analysis by mass spectrometry
Nitrogenous compounds from Colorado Green River Formation oil shale using high resolution mass spectrometry
Burlingame, A. L.↗
Military jet fuel from shale oil
Investigations leading to a specification for aviation turbine fuel produced from whole crude shale oil are described. Refining methods involving hydrocracking, hydrotreating, and extraction processes are briefly examined and their production capabilities are assessed.
Coppola, E. N.↗
Tri- and tetraterpenoid hydrocarbons in the Messel oil shale
The high-molecular-weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high-resolution gas chromatography and combined gas chromatography/mass spectrometry. The following compounds are present: perhydrolycopene, together with one or more unsaturated analogs with the same skeleton; a series of 4-methylsteranes in higher abundance than their 4-desmethyl analogs; two series of pentacyclic triterpanes, one series based on the hopane structure, and the other based on the 17 alpha-H hopane structure; and an intact triterpene hop-17(21)-ene. Only two additional triterpanes were detected in minor concentrations - namely, 30-normoretane and a C31 triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment.
Kimble, B. J.↗
Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale
The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.
NASA Discipline Exobiology↗