AndreaBozzo/ceres-open-data-index huggingface dataset:
Oil shale retorting processes:  a technical overview

The challenge facing the oil shale industry is to devise a simple and efficient retorting process that operates at low cost. This will require a thorough understanding of the important physical and chemical processes that occur during retorting, mathematical modeling to analyze the complex interactions, and sophisticated engineering to design a retorting process having the minimum cost. Retorting processes can be classified into two groups, one using hot gas as the heat transfer medium and one using hot solid material. We have constructed mathematical models of two generic processes from each of these groups to represent state-of-the-art processes as well as those under development. The models are based on detailed reaction kinetics, thermodynamics, and process physics. Using these models, we have calculated the process characteristics and the complete mass and energy balances for 50,000-barrel/day shale oil plants. We have made comparisons of these four processes to illustrate their advantages and disadvantages. The comparisons include retort vessel volume, heat exchange capacity, power requirements, water requirements, and waste gas volume. The results indicate no present easy choice of a best process. Oil shale process technology is neither highly developed nor mature, and substantial improvements can be expected from further research and development, and from industrial experience. The hot gas processes can be viewed as first-generation technology, and the hot solid processes, if they can be successfully developed, may be second-generation technology. 23 references, 9 figures, 4 tables.

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Lawrence Livermore National Laboratory oil shale project review: METC second annual oil shale contractors meeting

Lawrence Livermore National Laboratory UCRL--95140 has, over the past decade, conducted research on oil shale retorting via a broad based effort encompassing mathematical modeling, experimental studies of chemical reactions and physical processes, retort systems operations and retort component studies. In recent years, the emphasis has been on surface processes, especially those employing hot-solid as the heat transfer media. Key technical questions in these systems include: (1) the kinetics and stoichiometry of oil generation and degradation (via coking and cracking reactions,10218 ); (2) char and sulfur combustion chemistry; (3) processing alternatives and scale-up considerations; (4) environmental consequences, especially of sulfur and nitrogen bearing species. The LLNL project combines laboratory and pilot-scale experimental measurements with mathematical modeling of fundamental chemistry and physics to provide a technical base for evaluation of oil shale retorting alternatives. Mathematical modeling of the chemical and physical processes involved in oil shale retorting is a key component of our oil shale project. Our models encompass three levels of complexity: individual chemical reaction modeling, multireaction particle models, and overall retort models. One of the most useful general products of our modeling work is the distillation of data and theories into a compact and usable form. 37 refs., 12 figs., 3 tabs.

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Thermal degradation of Green River kerogen at 150/sup 0/ to 350/sup 0/ C

Green River oil shale previously extracted by benzene was heated at 150, 200, 250, 300 and 350C for 0.5 to 360 days to determine the rate at which kerogen degrades to thermal products, the types of thermal products formed, and the effect of prolonged low temperature heating upon subsequent assay yields.

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Composition of a shale-oil naphtha

A naphtha obtained by destructive, recycle hydrogeneation of crude shale oil, produced by gas-combustion retorting of Colorado oil shale, was found by the Bureau of Mines to contain 49.1 percent paraffins, 20.3 percent cycloparaffins, 7.8 percent olefins, and 22.8 percent aromatics. The naphtha contained only minor amounts of sulfur, nitrogen, and oxygen compounds. Compounds containing less than 5 carbon-atoms per molecule were removed by distillation before analysis. The paraffins were predominantly straight-chain compounds; n-Hexane was present in the largest quantity, and the other straight-chain paraffins decreased in amount as the molecular weigh increased. The cycloparaffins, which contained both cyclopentanes and cyclohexanes, were evenly distributed throughout the boiling range. Although the naphtha has been produced by hydrogenation, it contained a small quantity of olefins. Straight-chain olefins with a terminal double bond comprised about two-thirds of these compounds. Among olefins with an internal double bond, those having trans configuration were present in three times the quantity of those in the cis form. In the aromatics all but one of the alkylbenzenes having nine or less carbon-atoms per molecule were identified; toluene was present in the greatest quantity. Only a few o the higher molecular weight homologs were identified.

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Hydrocarbon-induced cancer risks in oil shale processing

An estimate of occupational cancer risks due to hydrocarbon exposure during retorting, upgrading, and transportation was derived using epidemiological studies in a surrogate industry. The oil refining industry was selected as a surrogate with the goal of adjusting that workforce's risk based upon toxicologic and exposure data. Risk estimates were derived for those cancers which may be excessive in refinery workers, namely lung, stomach, kidney, brain, and skin cancer. The magnitude of health risks for these diseases was very small, with the estimated 15,000 exposed workers suffering 3.7 excess internal cancers per year and 21 excess skin cancers per year. This morbidity would be expected to produce about 3 deaths per year. In spite of considerable uncertainty regarding these figures, the conclusion that hydrocarbon-induced cancers are overshadowed by dust-related respiratory disease as an occupational health risk in the oil shale industry is warranted. The implications of these results for further health research and industrial hygiene practices are discussed. 34 references, 3 tables.

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Optimization of carbon deposition experiments in thermal oil recovery by statistical analysis

"The Bureau of Mines used regression analysis and applied  statistical methods in an effort to rationalize the results of an experiment examining the effects of certain variables on carbon deposition in a reservoir for thermal  recovery of petroleum. Although none of the 15 trials of the original experiment resulted in the response of weight-percent of carbon regarded by the experimenter as adequate, values calculated using canonical analysis in two  trials yielded responses 33 and 54 percent higher than the minimum acceptable figure. The actual responses differed by less than 3 and 6 percent, respectively, from the predicted responses. Methods are described for defining a path of increasing response based on the minimum point and the response surfaces and for defining a set of values  for the parameters in question, which result in increased response.  A detailed explanation of the mathematical process used in this analysis is presented in the appendix for ease in computer programming the technique."

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Cutting action of rotary bits in oil shale

This paper presents some research studies of the rotary drilling of oil shale at the Bureau of Mines Oil-Shale Mine, Rifle, Colorado.  The experimental procedures and the rotary bit cutting action, and bit design are presented and discussed.  The actions of various bit designs are analyzed and compared with the observed results of actual drilling tests.  A cost estimate is made for drilling Colorado oil shale.

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Synthetic liquid fuels. Annual report of the Secretary of the Interior for 1954. Part II. Oil from oil shale

In its research and development program on synthetic liquid fuels, the Bureau of Mines is obtaining engineering and cost data for the day when industry will require such figures and has increased its more basic research work during the last year to learn more about the nature of the raw materials and their suitability for new processes to convert both coal and shale to oil.

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Purification, purity estimation, and spectra of some organic derivatives of fluorine, silicon, boron, and aluminum

"Nine organic derivatives of fluorine, silicon, boron, and aluminum were purified for thermodynamic studies using distillation, zone melting, and gas liquid chromatography. The unusual properties of these compounds required the  development of special techniques for handling and purification. To determine purities of purified samples, new techniques for analyzing spectral data were developed."

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Waterflooding of oilfields in Wyoming to 1968

"This Bureau of Mines report provides information on 138 waterflood projects in Wyoming. Injection was in 25 producing zones and 65 fields. Specific data presented include field location, discovery and development, water supply and injection, oil and water production, estimates  of oil in place, and oil recoveries by primary and  secondary methods. The 138 projects studied will, if successful, recover about 800 million barrels of secondary oil. Almost all of the injection water is from deep water wells."

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Combustion rates for oil shale carbonaceous residue

The combustion rate of the residual carbon remaining in retorted oil shale was investigated using oil shale core samples. Laboratory data indicates the combustion front penetration rate is proportional to the square root of time and increases linearly with the square root of the sweep gas oxygen concentration, implying an ash layer diffusion control mechanism. Equations are presented relating the residual carbon combustion rate to shale richness and the oxygen concentration in the sweep gas.

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Development and application of a Permit Information System for Shale Oil (PERMISSO). Final report, June 1978--May 1979

The development of a Permit Information System for Shale Oil (PERMISSO) is an attempt at examining public laws, regulations and resulting requirements regarding permits required in projects involving the development and extraction of oil from oil shale.  This study includes only the western oil shale deposits located in Colorado, Wyoming and Utah.

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Retorting ungraded oil shale as related to in situ processing

A study of the retorting characteristics of large pieces of oil shale has been started to obtain information applicable to processing broken oil shale such as that which might be expected in a nuclear chimney. Oil shale charges ranging in grade from 26.0 to 48.0 gal per ton and in size from small grains up to pieces 20 by 20 in. have been processed using air rates lower than 2.0 scf per min. per sq ft. of bed. Yields of oil as high as 80.8% of Fischer assay were obtained.

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Preliminary analysis of surface mining options for Naval Oil Shale Reserve 1

The study was undertaken to determine the economic viability of surface mining to exploit the reserves. It is based on resource information already developed for NOSR 1 and conceptual designs of mining systems compatible with this resource. Environmental considerations as they relate to surface mining have been addressed qualitatively. The conclusions on economic viability were based primarily on mining costs projected from other industries using surface mining. An analysis of surface mining for the NOSR 1 resource was performed based on its particular overburden thickness, oil shale thickness, oil shale grade, and topography. This evaluation considered reclamation of the surface as part of its design and cost estimate. The capital costs for mining 25 GPT and 30 GPT shale and the operating costs for mining 25 GPT, 30 GPT, and 35 GPT shale are presented. The relationship between operating cost and stripping ratio, and the break-even stripping ratio (BESR) for surface mining to be competitive with room-and-pillar mining, are shown. Identification of potential environmental impacts shows that environmental control procedures for surface mining are more difficult to implement than those for underground mining. The following three areas are of prime concern: maintenance of air quality standards by disruption, movement, and placement of large quantities of overburden; disruption or cutting of aquifers during the mining process which affect area water supplies; and potential mineral leaching from spent shales into the aquifers. Although it is an operational benefit to place spent shale in the open pit, leaching of the spent shales and contamination of the water is detrimental. It is therefore concluded that surface mining on NOSR 1 currently is neither economically desirable nor environmentally safe. Stringent mitigation measures would have to be implemented to overcome some of the potential environmental hazards.

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Organic constituents in process water from the in-situ retorting of oil from oil-shale kerogen

Capillary-column gas-chromatography/mass-spectrometry (GC/MS) was performed on the acid, base, and neutral fractions of liquid- and particulate-phase methylene chloride extracts of a composite sample of raw process water collected from separator Tank 6 by the Laramie Energy Technology Center. Of the 160 extractable and chromatographable organic compounds tentatively identified, the following compound classes were found (listed in decreasing order of abundance): quinolines and lower fatty acids, aminoindoles, neutral oxygenated heterocyclics, pyridines, pyrroles, pyrazoles, phenols, and alkanes. Noticeably absent or in low concentration were alkyl benzenes and alkenes. Assuming 100% extraction efficiency, these organics constitute approximately 0.035% of the retort water; approximately 50% of this amount is represented by the quinolines, fatty acids, aminoindoles, and oxygenated heterocyclics. The following differences were noted in the composition of the particulate and liquid extracts of the neutral and base fractions, respectively: (1) alkanes are a major portion of the particulates, whereas oxygenated hereocyclics are most prominent in the liquid; and (2) aminoindoles are only a minor portion of the particulates, but are prominent in the liquid phase. The concentration of a compound occurring in both the liquid and particulate extracts is approximately 40 to 100 times higher in the liquid than in the particulate extract.

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Contamination of groundwater by organic pollutants leached from in-situ spent shale

The potential for contamination of groundwater by organic pollutants leached from in-situ spent shale was studied in a series of laboratory leaching experiments. Both batch-mode and continuous-flow column experiments were conducted to study the leaching phenomenon. Experimental variables included retorting characteristics of spent shale, leaching time, initial quality of leach water, temperature of leach water, and particle size of spent shale. The results presented here suggest that groundwater resources in regions of potential in-situ development may be significantly degraded in quality as a consequence of leached organic contaminants. Overall, the leaching phenomenon represents a potentially chronic problem which may preclude beneficial uses of groundwater for decades.

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Occidental vertical modified in situ process for the recovery of oil from oil shale, phase I. Final report, November 1, 1976 through April 30, 1979

The Department of Energy (DOE)/Occidental Oil Shale, Inc. (OOSI) Cooperative Agreement is a two-phase agreement consisting of engineering development of the Occidental modified in situ process as the first phase and a technical feasibility demonstration as the second phase. The primary objective of the first phase is to evaluate two specific retort designs (vertical free face retort system vs horizontal free face retort system) for the purpose of selecting a particular retort design for the technical feasibility demonstration. Based upon the results of Retorts 5 and 6, the design using horizontal rooms and a new technology of blasting to a horizontal free face, developed from the Occidental sponsored Rock Fragmentation Program, was selected over the vertical slot because: field results have confirmed that the horizontal free face retort (HFFR) system is much more amenable to the achievement of a rubble pile with uniform flow characteristics than is the vertical free face retort (VFFR) system; and the more uniform void volume distribution with the HFFR design will result in improved retort operability and oil yield. In spite of the operational problems experienced during start-up, resulting in a poor distribution of air to the top of Retort 6, OOSI was able to produce 64% of the theoretical oil yield. Corrective actions taken included secondary combustion and initiation of retorting via a relocated air injection system. The vertical slot design of Retort 5 had the inherent disadvantage of producing the greatest potential for non-uniform permeability in the flow. The rapid flame front movement down the center of Retort 5, and its associated problems, resulted in the oil recovery being much lower than anticipated.

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Minimum bed parameters for in situ processing of oil shale. Third quarterly report, April 1-June 30, 1980

Oil shale retort runs 028 (16% void) and 029 (7% void), composed of competent shale blocks plus shale rubble, were completed. Retort 028, processed with air at a flux of 0.017 kg/sub air//m/sup 2/ /sub shale/.second, had peak temperatures of 700/sup 0/C, a retorting rate of 1.1 m/day, and a yield of 82% FA. Retort 029, processed with air at a flux of 0.027 kg/sub air//m/sup 2//sub shale/.second, had peak temperatures of 750/sup 0/C, a retorting rate of 1.6 m/day, and a yield of 75% FA. Comparisons of retort model calculations with experimental data from previous retort run 027 (16% void, air flux of .029 kg/sub air//m/sup 2//sub shale/.second were good; observed experimental yield was 95% FA, calculated yield, 92.8%; experimental retorting rates varied from 9.5 to 8.9 cm/h, calculated rates from 10.3 to 10.0 cm/h; observed local heating rates ranged from 29 to 14/sup 0/C/h, calculated heating rates from 20 to 16/sup 0/C/h; and observed peak temperatures ranged from 815 to 825/sup 0/C, calculated from 820 to 825/sup 0/C.

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Geotechnical properties of oil shale retorted by the PARAHO and TOSCO processes. Final report, Oct 76-Apr 79

Waste disposal schemes using spent shale in embankments require a thorough knowledge of its geotechnical engineering properties for environmentally safe disposal. In this context, the objective of this laboratory investigation was to determine the physical properties, geotechnical properties, and composition of spent oil shale retorted by the PARAHO and TOSCO processes. Physical properties consisted of mechanical analyses, Atterberg limits, and specific gravity determinations. Geotechnical engineering properties were determined by compaction, maximum-minimum density, unconfined compression, triaxial compression, and permeability, direct shear, Ko, cyclic triaxial, resonant column, and Los Angeles Abrasion test. Petrographic, chemical, and scanning electron microscopy analyses were used to determine compositional features.

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Synthetic gasolines and diesel fuels from processing of shale oils and coal liquids

Seven test fuels were provided to research projects in the Department of Energy Alternative Fuels Utilization Program. Current refining technology was applied for conversion of shale- and coal-derived feedstocks to gasolines, diesel fuel, and turbine fuel. Hydrogenation was used in all four processing sequences, supplemented by catalytic reforming, distillation, and blending as needed to meet the product objectives. Major operating conditions are described for each process step. Laboratory analyses are provided for feedstocks, intermediates, and final products.

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Literature survey of in situ processes for application to the US tar sand resource

Tar sands in the United States and worldwide are a large potential source of hydrocarbon liquids that has yet to be sufficiently developed. The development of the US tar sand resource lags the worldwide development and poses a challenge that has not been eagerly accepted by the petroleum industry. This paper reviews the developmental status of in situ enhanced oil recovery techniques that have been proposed for the production of heavy oils or bitumen and determines which process or processes are in the forefront for application to the US resource. Also noted is what developmental work, if any, remains to be accomplished before field testing of the process(es). The review used only information available in the public domain. 196 refs., 1 fig., 2 tabs.

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Field and laboratory leaching studies of retorted Kentucky oil shale

The purpose of this report is to present the results of a field study on the environmental and reclamation characteristics of retorted eastern oil shale and associated materials. Retorted, raw and raw and retorted mixtures of eastern oil shale from a pilot test using the Dravo Traveling Grate Retort were placed in field lysimeters and sampled weekly or biweekly over a period of 1300 days. Retorting the oil shale induced significant changes in the clay minerals, with the decrystallization of kaolinite and illite being the major effects. The leachates generated in the field lysimeters were highly acidic, with pH's varying from approximately 2.5 to 3.5. The leachates had high concentrations of dissolved elements with sulfate, Mg and Fe present at tens of thousands or thousands of ppM. Acid generation and elemental concentrations in the leachates were highest in the first year. Even after 1300 days, the leachates remained very acidic with pH's in the 2.9 to 3.4 range and sulfate concentrations of 3,000 to 5,000 ppM. Iron, Mg and sulfate were present in the highest concentrations in the leachates from the unretorted oil shale. The clay minerals of the retorted shale were found relatively reactive in comparison to the raw shale as indicated by much higher Al and K concentrations in their leachates compared to that of the raw shale. In general, the chemistry of the leachates was determined by the kinetics of solution reactions and materials transport. Calcium concentration however appeared to be controlled by mineral equilibria with respect to gypsum. Laboratory-based leaching experiments produced leachates with elemental concentrations much lower than the field study. Leachates from column experiments, that closely simulated field conditions, were found to have chemical compositions comparable to that from the field and also produced similar elemental release patterns. 38 refs., 22 figs., 12 tabs.

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Control strategies for abandoned in-situ oil shale retorts

Prevention of groundwater pollution resulting from in-situ oil shale development will require a novel control technology. Based upon information available regarding the problems and related technologies, certain candidate control technologies appear technically and economically feasible. These technologies and their projected costs are listed. Pending verification of certain assumptions, it appears possible to prevent pollution of groundwater for about $0.59 to $0.67 per barrel by recovering leachate and treating it on the surface; for about $0.74 to $2.85 per barrel by placing a grout curtain around an entire block of retorts; or for about $0.35 to $1.30 per barrel by backfilling abandoned retorts with a grout of surface-retorted spent shale. These cost projections are preliminary and subject to change as experimental data are generated and as design criteria are developed. The technical feasibility of these technologies has not been demonstrated, and many uncertainties remain concerning technologies as well as site-specific issues. Therefore, these cost projections are initial approximations which may not reflect actual costs at any specific site. Nevertheless, the projections are useful for RD and D decision-making. Detailed cost projections for each control technology are provided in this study.

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