AndreaBozzo/ceres-open-data-index huggingface dataset:
Preparation of organic concentrate from Green River oil shale. [Modification of Trent amalgamation process]

Sir: Like other oil shales of the world, those of the Green River formation present difficult analytical problems.  However, determination of the organic elementary  compositions is essential to studies intended to increase the usefulness of oil shales.  To obtain accurate values for the elemental composition of the organic materials in oil shale, complex corrections for the interfering effects of the mineral components are required on direct analysis of shale.  The procedure presented here substantially reduces these interference problems by concentrating the organic matter.  Although the organic and mineral components were not completely separated, the procedure concentrates oil-shale organic matter almost nonselectively in quantities sufficient for extensive study of its properties.

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Chromatographic profiles of oil shale processing by-product waters and selected fractions

Capillary column gas chromatography (GC) and reversed-phase high-performance liquid chromatography (RP-LC) were used to prepare fingerprints (chromatographic profiles) of complex mixtures of organic materials in raw waters from four oil shale processes and from fractions produced in an environmentally mimetic separation scheme. The scheme was liquid-liquid extraction with methylene chloride giving hydrophilic and organophilic fractions. Direct aqueous injection of samples was used for whole waters and hydrophilic fractions when it proved to be an expedient approach to the ''intractable''or extremely hydrophilic materials. Previous work in many laboratories has concentrated on organophilic (hydrophobic) fractions produced in this type of separation scheme. One aim of the present work has been to examine the hydrophilic organic fraction in the same detail as the organophilic fraction to attempt to identify key indicator chemical classes or species which might serve as indicators or tracers in synfuels processing operations in either the laboratory or the environment. Current developments in high-performance liquid chromatography with their implications for aqueous partitioning studies are reviewed and related to the results. Potential key indicator chemical classes were apparent in the neutral fractions of the hydrophilic and organophilic fractions. Amphoteric materials, ordinarily discarded in most extraction protocols, were characterized. 81 refs., 17 figs., 8 tabs.

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Nonspecific detection of arsenic in high performance liquid chromatography: a feasibility study

Both gas-phase and liquid-phase systems were evaluated for their potential application in continuous on-line high performance liquid chromatography (HPLC) detection of arsenic species in oil shale byproduct waters. Previous work on related building blocks was reviewed in detail and possible systems chosen for additional laboratory evaluation. The basic system proposed includes on-line arsine generation followed by continuous gas phase detection with a thermionic ionization detector (TID) operated in the nitrogen/phosphorus mode, or liquid-phase colorimetry with silver diethyldithiocarbamate/pyridine (AgDDTC) reagent. Detection limits were calculated for arsenic based on static tests. The TID was tested in conjunction with gas chromatography of triphenylarsine, yielding 0.1 ng/min As sensitivity. The arsine AgDDTC system calculation was 50 ng/mL. Either system was deemed feasible for application to fractional ppM-level arsenic species detection on-line in HPLC effluents even though on-line sensitivities could be poorer than those calculated from the static tests by an order of magnitude. 62 refs., 4 figs., 4 tabs.

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Adsorption of oxyanions by spent western oil shale. 2. Selenite

The adsorption and desorption behavior of selenite by processed Green River Formation oil shales were examined. The selenite adsorption data could be quantitatively described by both the Freundlich and Langmuir isotherms. However, greater R{sup 2} values were obtained for the Freundlich isotherms. Furthermore, selenite adsorption was not a function of the extraction process. The adsorption of selenite by the processed oil shales was irreversible. Upon dilution of the equilibrium systems, additional selenite removal from solution occurred. A thermochemical analysis of the adsorption and desorption equilibrium solutions indicated that the solutions were undersaturated with respect to a number of metal selenite solids. This indicates that precipitation processes are not influencing selenite behavior. However, not all selenite minerals were examined in the evaluation because of the lack of thermochemical data. An insufficient equilibration period for the adsorption study of the alteration of processed oil shale solids as a result of hydration reactions may also have hastened the additional removal of selenite during the desorption studies.

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Determination of nitrogen in shale oil and petroleum. [Studies by 17 laboratories]

An adequate method for the determination of nitrogen is highly important in the investigation of shale oils because of the large quantities of nitrogen present and the effect of nitrogen compounds on the properties of the oils. The nitrogen contents of three samples, a shale oil and two fractions therefrom, as determined by seventeen different laboratories using their own methods, showed that there was no consistency of results among laboratories. Methods used included both Dumas and Kjeldahl, and micro, semimicro, and macroprocedures. The need for an accurate, reproducible method for the determination of nitrogen in shale oil was demonstrated. No clear superiority for any method or procedure appeared the most promising.

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Physics of oil shales:  a program of theoretical and experimental studies. Quarterly progress report, January 1-April 1, 1983

In the in-situ electromagnetic heating process some of the oil evolved during pyrolysis of Kerogen is lost to coking, cracking and combustion. An understanding of these decomposition processes is important in order to design appropriate technology to minimize them. Additionally, a mathematical description of these processes will enable realistic modeling of the oil shale. Combustion refers to exothermic chemical reactions of the gases. This process is controlled by the oxygen concentration present in the shale and is primarily a high temperature phenomena (T > 700/sup 0/C). Since such temperatures are not obtained in the electromagnetic process, combustion can be neglected. The Braun model (Braun, R. L., Mathematical Modeling of Modified In-Situ and Aboveground Oil Shale Retorting, Report No. UCRL-53119, Lawrence Livermore Laboratory, 1981) has been verified for heating rates of .0005 K/sup 0//S to .05 K/sup 0//S. This model should be valid for electromagnetic heating processes where the heating rate is about .0005 K/sup 0//S. Currently we are using this model in our numerical calculations, and the results will be presented in later reports. 4 references.

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Physics of oil shales:  a program of theoretical and experimental studies. Quarterly progress report, December 21, 1983-March 21, 1984

The roles of water on the dielectric properties of oil shales is being studied. Extensive modeling has been performed including parameters reflecting shale richness, water content, and interfacial polarization from 10Hz to 1MHz in an effort to interpret the data on dielectric properties of oil shales. Reasonable agreement between the model calculations and data are obtained. Work from previous quarters modeling the oil shales as random networks simulating the heterogeneous character is continuing. The numerical work using the mathematical model developed for in-situ oil shale retorting by electromagnetic methods is continuing. A very comprehensive report giving all the details of this model is under preparation and will be available next quarter.

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Physics of oil shales:  a program of theoretical and experimental studies. Quarterly progress report, September 21, 1981-January 1, 1982

Major results obtained this quarter are as follows: (1) Data presented in a report by Jesch (Jesch, R. L., Dielectric Properties of Oil Shale as a Function of Frequency (DOE) LETC report, No. SR-723-71-80) have been analyzed. Non-Debye behavior characteristic of several other non-crystalline materials has been found in the case of oil shale samples studied by Jesch. (2) Microwave propagation in cylindrical geometry filled with a lossy dielectric has been studied. Preliminary calculations indicate that the attenuation length for several cavity modes are large enough to provide efficient mechanisms for efficient energy deposition in the medium. 36 references, 15 figures, 2 tables.

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Physics of oil shales:  a program of theoretical and experimental studies. Quarterly progress report, January 1-March 31, 1982

The analysis of the data presented in the report by Jesch (Jesch, R. L., Dielectric Properties of Oil Shale as a Function Frequency, (DOE) Report No. SR-723-71-80 (October, 1980)) has been continued. The literature survey on the low frequency dielectric response of non-crystalline materials has been continued. Attention has been focussed on the analysis of dielectric response of glassy materials (vitreous ionic conductors) available in the literature. Based on this a scheme is proposed to interpret the dielectric data on oil shales. Analysis based on this scheme will be conducted in the third quarter. The study of microwave propagation in cylindrical geometry filled with lossy dielectric is continued. Explicit expressions for Q (quality factor) of the dielectric cavity is obtained. Some numerical results using data of Jesch are given. Literature survey on the thermal properties of non-crystalline materials is continued. Preliminary calculations on the heat transfer problem have been begun. 18 references, 1 table.

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Physics of oil shales:  a program of theoretical and experimental studies. Quarterly progress report, April 1-June 31, 1982

The analysis of the data presented in the report by Jesch (Jesch, R. L., Dielectric Properties of Oil Shale as a Function of Frequency (DOE) Report No. SR-723-71-80 (October 1980)) has been continued using the model discussed in detail in the previous quarterly progress report. For the limited amount of dielectric data available at this time, this analysis is now complete. The study of microwave propagation in cylindrical geometry filled with lossy dielectric is continued. The transfer matrix appropriate for wave guide appropriate for the oil shale problem has been obtained. A beginning has been made to set up a laboratory experiment for microwave propagation in oil shale materials. Data acquisition from this experiment will begin during the next quarter. Explicit calculations for heat flow in oil shales using the mixture theory of Murukami have begun and will be completed next quarter.

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Physics of oil shales:  a program of theoretical and experimental studies. Quarterly progress report, June 31-September 21, 1982

The study of oil shales pertaining to volumetric heating oil shales is comprised of the following four major tasks for the period June 31, 1982 to September 21, 1982: (1) dielectric properties of oil shales; (2) heat transfer in oil shales; (3) electromagnetic wave propagation in dielectric wave guides; and (4) microwave measurements on oil shale dielectrics. Progress reports are presented for each task. 8 references, 12 figures.

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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. Equation are presented relating the residual carbon combustion rate to shale richness and the oxygen concentration in the sweep gas.

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Olefins in naphthas. [Determination in shale oil and petroleum naphthas by Br-No. , N/sub 2/O/sub 4/, and silica-gel methods]

Olefins comprise one of the major groups of hydrocarbons in shale-oil and cracked-petroleum naphtha's. A quantitative determination of this group of compounds may be made with reasonable accuracy by either the nitrogen tetroxide absorption or silica-gel absorption method. Calculation of olefins from bromine number, this method used extensively in the petroleum industry, gives high results. The absolute variation of shale-oil naphtha's may be as much as 35 percent. Consequently, bromine number seldom provides a satisfactory estimate of olefins when the content of these compounds is high. Sulfur and nitrogen compounds cause large errors in olefin content as determined by bromine number. Also substitution reactions and unequal distribution of the olefins throughout the boiling range probably play an important part.  An accurate determination of olefins is extremely important in processing studies of materials such as shale oil naphtha that contain a high concentration of these compounds.  In the past, the index of reliability of methods for determining olefins usually has been based on the titration of pure olefins or on the analysis of relatively simple synthetic mixtures.  Little information is available upon the reliability of results that may be obtained when methods so tested are applied to complex samples.  This article presents a direct comparison of results obtained by applying three olefin determination methods-bromine number, nitrogen tetroxide absorption and silica-gel adsorption-to a number of shale oil and petroleum naphthas.

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Flash pyrolysis of oil shale with various gases

The flash pyrolysis of Colorado Oil Shale with methane at a temperature of 800/sup 0/C and pressure of 500 psi appears to give the highest yield of hydrocarbon gas and liquid followed by hydrogen and lowest with helium. In the methane pyrolysis over 54.5% of the carbon in the kerogen is converted to ethylene and benzene. The flash pyrolysis with hydrogen (flash hydropyrolysis) of the oil shale at increasing temperatures showed a rapidly increasing amount of methane formed and a decrease in ethane formation, while the BTX (benzene mainly) yield remained at approximately 10%. At 950/sup 0/C and 500 psi almost all (97.0%) of the carbon in the kerogen is converted to liquid and gaseous hydrocarbons. Experiments with a mixture of a New Mexico sub-bituminous coal and oil shale under flash hydropyrolysis and methane pyrolysis conditions indicated higher yields of methane and ethylene and slightly lower yields of benzene than predicted by partial additive calculations. These exploratory experiments appear to be of sufficient interest to warrant a fuller investigation of the interaction of the natural resources, oil shale, coal and natural gas under flash pyrolysis conditions.

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The IITRI RF process laboratory and field results on oil shale and tar sands

The IITRI RF process for oil shale can be carried out at 350/sup 0/ to 375/sup 0/C instead of 500/sup 0/C, as normally used for other processes. This lower temperature makes the economics of the process even more favorable. Some investigations have measured low yields at 350/sup 0/C, which would not be cost effective. However, the authors have found that high yields are obtained if the shale is very slowly heated from 300/sup 0/ to 350/sup 0/ or 375/sup 0/C. This allows time for autogenously developed vapor to produce the liquid shale oil. In this way, the oil is not exposed for long periods to temperatures at which it can crack to light ends and char. Evidence for these effects was found in thermogravimetric analysis (TGA) experiments, which were two orders of magnitude faster than core pyrolysis experiments. This indicates that physical processes can limit the production rate for core experiments. The permeability as measured parallel to the bedding planes during pyrolysis of cores was 4400 millidarcies. The yield in core pyrolysis experiments ranged from 30 to over 100 percent of Fisher assay (depending on grade, temperature, and physical conditions) when the heating rate was 5/sup 0/C/min. When the core was heated from 300/sup 0/ to 350/sup 0/C at 10/sup 0/C/day the yield was 90 to 100 percent of Fisher assay. A field experiment on Utah tar sands heated a 60-ton volume of tar sand in situ to 200/sup 0/C. Eight barrels, or 24 percent of the bitumen in this volume was produced in 20 days. This extrapolates to 50 to 70 percent overall recovery in 6 months, which would allow production of upgraded oil below the world price.

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Environmental research on a modified in situ oil shale task process. Progress report

This report summarizes the progress of the US Department of Energy's Oil Shale Task Force in its research program at the Occidental Oil Shale, Inc. facility at Logan Wash, Colorado. More specifically, the Task Force obtained samples from Retort 3E and Retort 6 and submitted these samples to a variety of analyses. The samples collected included: crude oil (Retort 6,8641 ); light oil (Retort 6,8641 ); product water (Retort 6,8641 ); boiler blowdown (Retort 6,8641 ); makeup water (Retort 6,8641 ); mine sump water; groundwater; water from Retorts 1 through 5; retort gas (Retort 6,8641 ); mine air; mine dust; and spent shale core (Retort 3E). The locations of the sampling points and methods used for collection and storage are discussed in Chapter 2 (Characterization). These samples were then distributed to the various laboratories and universities participating in the Task Force. For convenience in organizing the data, it is useful to group the work into three categories: Characterization, Leaching, and Health Effects. While many samples still have not been analyzed and much of the data remains to be interpreted, there are some preliminary conclusions the Task Force feels will be helpful in defining future needs and establishing priorities. It is important to note that drilling agents other than water were used in the recovery of the core from Retort 3E. These agents have been analyzed (see Table 12 in Chapter 2) for several constituents of interest. As a result some of the analyses of this core sample and leachates must be considered tentative.

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The preferable technologies for eastern oil shale as defined by bench-scale retorting studies

The oil shale of Kentucky has a reputation as a low quality synthetic fuel resource. If only one-third of the available organic carbon can be converted to shale oil, then it certainly deserves this reputation. However, techniques for enhancing process yields are available. The techniques fall into two broad categories that involve optimizing conditions and chemistry for the conversion of kerogen predominantly to liquid product, and preventing oil destruction due to coking, cracking, and oxidation. Methods of yield improvement worthy of special attention are flash pyrolysis, steam retorting, and reduced air oxidation. Bench-scale studies that provide information in these areas are reviewed and discussed.

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Fluidized-bed pyrolysis of oil shale

Several quartz isothermal fluidized-bed reactors have been constructed in order to measure kinetics and oil properties relevant to surface retorting by fluidized-bed processes. The rate of volatile total hydrocarbon evolution is measured with a flame ionization detector, although various techniques are currently being evaluated for doing species-selective (as opposed to total hydrocarbon) kinetics. Oil yield experiments are performed separately from the kinetic experiments due to the experimental conditions necessary to minimize mist formation and maximize oil collection. Oil composition is determined via subsequent analysis (gas chromatography). Gas evolution kinetics, oil yield and oil composition are determined both as a function of oil shale parameters (e.g., particle size, grade, Eastern vs. Western deposits) and fluidized-bed parameters (temperature, sweep gas composition, gas velocity, bed particle size, and bed geometry). An ultimate goal is the development of diagnostic methods relating oil composition to processing parameters.

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/sup 13/C spin diffusion of adamantane

Two-dimensional exchange spectroscopy of natural abundance /sup 13/C--/sup 13/C spin diffusion in solid adamantane illustrates the influence that /sup 13/C--/sup 1/H dipole--dipole coupling exerts on /sup 13/C spin diffusion by determining spectral overlap in the /sup 13/C system. 2D /sup 13/C spectra were obtained for several values of mixing time tau/sub m/ and compared with spectra calculated in the limit of nearest-neighbor coupling. Good agreement is obtained for short tau/sub m/, during which the equilibration of neighboring spins dominates. For longer tau/sub m/, slower spin diffusion that is not acounted for by the simple model is seen; after nearest-neighbor spins equilibrate, communication over larger distances produces further mixing. It is possible to modify spin diffusion rates by altering experimental conditions, e.g., magic-angle spinning, low-power /sup 1/H decoupling, or spin locking /sup 13/C in the rotating frame during tau/sub m/.

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Modified in situ retorting:  results from LLNL pilot retorting experiments

Experiments designed to simulate various modified in situ (MIS) retorting conditions are being carried out in large (6-t) and small (150-kg) pilot retorts at Lawrence Livermore National Laboratory (LLNL). Both retorts are operated under near adiabatic conditions by a system of computer-controlled sidewall heaters. Access ports positioned every 15 cm down the length of the retorts provide locations for inserting thermocouples and gas probes into the rubble bed. All data acquisition and real-time analysis are presently carried out via a dedicated Hewlett-Packard 1000 computer system. To date, 25 experiments have been conducted using these retorts. The results from these experiments are summarized in a set of process correlations showing the effects of: inlet gas composition; particle size; grade; grade changes; and retorting rate. From these data, it is possible to estimate the results from a particular field MIS retorting experiment operating under a given set of conditions. In several instances, results from the LLNL mathematical retort model are used to extend and explain the results of the experiments. Recently, we have also used the retorting model as a process control tool for establishing the proper operating conditions prior to the burn. The results of the preburn calculations are found to be in good agreement with the actual pilot retorting data.

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