The organic diagenesis of steroids in sediments as related to the origin and formation of petroleum
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The absolute stereochemistry of pristane in a sample of contemporary marine zooplankton, Messel shale (Germany) and Djatibarang (Java) crude has been determined by gas chromatographic methods. The relative stereochemistry in Irati shale (Brazil), Green River (U.S.) crude, Halibut (Australia) crude has also been determined, and confirmed for a sample of the Green River shale. The stereoisomer distributions indicate a loss of stereospecificity of the phytol-derived 6(R), 10(S) pristane with increasing geological maturation. For example, the least mature geological sample, the Eocene Messel shale, contains solely the 6(R), 10(S) isomer, whereas a mature sample, Djatibarange crude, contains 50% of the 6(R), 10(S) isomer and 25% of each of the 6(R), 10(R) and 6(S), 10(S) isomers.
Rich-lean combustor concepts designed to enhance rich combustion chemistry and increase combustor flexibility for NO(x) reduction with minimally processed fuels are examined. Processes such as rich product recirculation in the rich chamber, rich-lean annihilation, and graduated air addition or staged rich combustion to release bound nitrogen in steps of reduced equivalence ratio are discussed. Variations to the baseline rapid quench section are considered, and the effect of residence time in the rich zone is investigated. The feasibility of using uncooled non-metallic materials for the rich zone combustion construction is also addressed. The preliminary results indicate that rich primary zone staged combustion provides environmentally acceptable operation with residual and/or synthetic coal-derived liquid fuels
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For abstract see A78-26760.
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Three C31 mehylhopanes were synthesized from diplopterol and its 2-alpha-methyl (Me), 2-beta-Me, and 3-beta-Me analogs. These synthetic methylhopanes were then compared with hopanoids from a variety of bitumens by means of gas chromatography and mass spectrometry, demonstrating that all three C31 hydrocarbons may occur in the ancient sediments. The most common type of hopanes, which eluted very close to the corresponding hopane in the mature sediments and oils was the 2-alpha-Me series.
The spectral signature of porphyrin compounds, considered to be biomarkers of depositional environment and thermal maturity, have been identified in reflectance spectra of oil shales. The key bands identified, in order of intensity, are the Soret (0.40 microns), alpha (0.57 microns), and beta (0.53 microns) bands. The observed bands represent the composite spectral signature of all porphyrin compounds present in the sample and, therefore, change position and intensity in accordance with changes in porphyrin chemistry.
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Transportation fuels production (including aerospace propellants) from non-traditional sources (gases, waste materials, and biomass) has been an active area of research and development for decades. Reducing terrestrial waste streams simultaneous with energy conversion, plentiful biomass, new low-cost methane sources, and/or extra-terrestrial resource harvesting and utilization present significant technological and business opportunities being realized by a new generation of visionary entrepreneurs. We examine several new approaches to catalyst fabrication and new processing technologies to enable utilization of these nontraditional raw materials. Two basic processing architectures are considered: a single-stage pyrolysis approach that seeks to basically re-cycle hydrocarbons with minimal net chemistry or a two-step paradigm that involves production of supply or synthesis gas (mainly carbon oxides and H2) followed by production of fuel(s) via Sabatier or methanation reactions and/or Fischer-Tröpsch synthesis. Optimizing the fraction of product stream relevant to targeted aerospace (and other transportation) fuels via modeling, catalyst fabrication and novel reactor design are described. Energy utilization is a concern for production of fuels for either terrestrial or space operations; renewable sources based on solar energy and/or energy efficient processes may be mission enabling. Another important issue is minimizing impurities in the product stream(s), especially those potentially posing risks to personnel or operations through (catalyst) poisoning or (equipment) damage. Technologies being developed to remove (and/or recycle) heteroatom impurities are briefly discussed as well as the development of chemically robust catalysts whose activities are not diminished during operation. The potential impacts on future missions by such new approaches as well as balance of system issues are addressed.
Transportation fuels production (including aerospace propellants) from non-traditional sources (gases, waste materials, and biomass) has been an active area of research and development for decades. Reducing terrestrial waste streams simultaneous with energy conversion, plentiful biomass, new low-cost methane sources, and/or extra-terrestrial resource harvesting and utilization present significant technological and business opportunities being realized by a new generation of visionary entrepreneurs. We examine several new approaches to catalyst fabrication and new processing technologies to enable utilization of these non-traditional raw materials. Two basic processing architectures are considered: a single-stage pyrolysis approach that seeks to basically re-cycle hydrocarbons with minimal net chemistry or a two-step paradigm that involves production of supply or synthesis gas (mainly carbon oxides and hydrogen) followed by production of fuel(s) via Sabatier or methanation reactions and/or Fischer-Tropsch synthesis. Optimizing the fraction of product stream relevant to targeted aerospace (and other transportation) fuels via modeling, catalyst fabrication and novel reactor design are described. Energy utilization is a concern for production of fuels for either terrestrial or space operations; renewable sources based on solar energy and/or energy efficient processes may be mission enabling. Another important issue is minimizing impurities in the product stream(s), especially those potentially posing risks to personnel or operations through (catalyst) poisoning or (equipment) damage. Technologies being developed to remove (and/or recycle) heteroatom impurities are briefly discussed as well as the development of chemically robust catalysts whose activity are not diminished during operation. The potential impacts on future missions by such new approaches as well as balance of system issues are addressed.
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Thirteen Liassic sedimentary rocks of increasing depth and three petroleums from the Paris Basin were studied for 13C/12C isotopic compositions and biological markers, including steranes, sterenes, methylphenanthrenes, methylanthracenes, and triaromatic steroids. The isotopic compositions of n-alkanes from mature sedimentary rocks and petroleums fall in a narrow range (2%), except for the deepest Hettangian rock and the Trias petroleum, for which the short-chain n-alkanes are enriched and depleted in 13C, respectively. Most of the molecular parameters increase over the 2000-2500 m depth range, reflecting the transformation of the organic matter at the onset of petroleum generation. In this zone, carbonate content and carbon isotopic composition of carbonates, as well as molecular parameters, are distinct for the Toarcian and Hettangian source rocks and suggest a migration of organic matter from these two formations. Two novel molecular parameters were defined for this task: one using methyltriaromatic steroids from organic extracts; the other using 1-methylphenanthrene and 2-methylanthracene from kerogen pyrolysates. The anomalous high maturity of the Dogger petroleum relative to the maturity-depth trend of the source rocks is used to estimate the minimal vertical distance of migration of the organic matter from the source rock to the reservoir.
The 'low nitrogen oxides heavy fuel combustor' program is described. Main program objectives are to generate and demonstrate the technology required to develop durable gas turbine combustors for utility and industrial applications, which are capable of sustained, environmentally acceptable operation with minimally processed petroleum residual fuels. The program will focus on 'dry' reductions of oxides of nitrogen, improved combustor durability, and satisfactory combustion of minimally processed petroleum residual fuels. Other technology advancements sought include: fuel flexibility for operation with petroleum distillates, blends of petroleum distillates and residual fuels, and synfuels (fuel oils derived from coal or shale); acceptable exhaust emissions of carbon monoxide, unburned hydrocarbons, sulfur oxides and smoke; and retrofit capability to existing engines.
The paper deals with the 'Low NO/x/ Heavy Fuel Combustor Program'. Main program objectives are to generate and demonstrate the technology required to develop durable gas turbine combustors for utility and industrial applications, which are capable of sustained, environmentally acceptable operation with minimally processed petroleum residual fuels. The program will focus on 'dry' reductions of oxides of nitrogen (NO/x/), improved combustor durability and satisfactory combustion of minimally processed petroleum residual fuels. Other technology advancements sought include: fuel flexibility for operation with petroleum distillates, blends of petroleum distillates and residual fuels, and synfuels (fuel oils derived from coal or shale); acceptable exhaust emissions of carbon monoxide, unburned hydrocarbons, sulfur oxides and smoke; and retrofit capability to existing engines.
A fuel quality processing study to provide a data base for an intelligent tradeoff between advanced turbine technology and liquid fuel quality, and also, to guide the development of specifications of future synthetic fuels anticipated for use in the time period 1985 to 2000 is given. Four technical performance tests are discussed: on-site pretreating, existing refineries to upgrade fuels, new refineries to upgrade fuels, and data evaluation. The base case refinery is a modern Midwest refinery processing 200,000 BPD of a 60/40 domestic/import petroleum crude mix. The synthetic crudes used for upgrading to marketable products and turbine fuel are shale oil and coal liquids. Of these syncrudes, 50,000 BPD are processed in the existing petroleum refinery, requiring additional process units and reducing petroleum feed, and in a new refinery designed for processing each syncrude to produce gasoline, distillate fuels, resid fuels, and turbine fuel, JPGs and coke. An extensive collection of synfuel properties and upgrading data was prepared for the application of a linear program model to investigate the most economical production slate meeting petroleum product specifications and turbine fuels of various quality grades. Technical and economic projections were developed for 36 scenarios, based on 4 different crude feeds to either modified existing or new refineries operated in 2 different modes to produce 7 differing grades of turbine fuels. A required product selling price of turbine fuel for each processing route was calculated. Procedures and projected economics were developed for on-site treatment of turbine fuel to meet limitations of impurities and emission of pollutants.