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A high-temperature sample holder designed by the National Bureau of Standards was used to determine the dielectric properties of approximately 40 oil shale samples as functions of temperature and frequency. A description of the sample holder characterization is given along with the measurement procedure and the sample preparation.
Heat content studies were conducted on burned shale, spent shale, and three grades of raw oil shale from the Green River Formation. Corrections were made for product enthalpies. The results were compared with previous work, indicating good agreement below retorting temperatures, but some differences at retorting temperatures. A general equatoin was developed relating heat content to oil-shale grade and temperature.
Oil shales are broadly dermed as petroleum source rocks containing sufficiently high contents of organic matter (above ca 10-15 wt. %) to make utilisation a possibility. Like coal, the world's reserves of oil shales are vast being many times larger than those proven for crude oil. Indeed, some of the largest deposits occur in the USA and Europe where Estonia and Turkey have large reserves. The first recorded interest in oil shale retorting was an English patent in 1694 (Eele, Hancock and Porter, No. 330) which refers to distilling noyle from some kind of stone". The oil shale retorting industry dates back to the middle of the last century, notably Scotland, Estonia, France and Sweden in Europe. Indeed, my own Department at the University of Strathclyde has a historical link with James "Paraffin" Young, the founder of the Scottish oil shale industry who endowed a chair in Applied Chemistry. The growth of the oil industry saw the demise of the oil shale industry in most countries with the notable exception of Estonia, where kukersite has continued to be used for power generation and retorting. However, oil shale utilisation has attracted renewed attention since the early 1970s as a source of transport fuels and chemical feedstocks due to the the long term uncertainties over crude oil supplies.
Pyrolysis and Hydropyrolysis of Kentucky oil shale using super-critical toluene as the solvent was studied in a 300 c.c. stirred batch reactor. Organic carbon conversions in excess of 160% Fischer Assay were obtained in less than 30 minutes for those reactions occurring above 400 C with hydrogen atmospheres. It was found that the overall conversion of organic compound to oil and gas products could be adequately modeled using a second order irreversible rate expression. Reactions occurring at 460 C and 300 psig hydrogen partial pressure could be considered instantaneous, yielding organic carbon conversions of 185% Fischer Assay. The effects of hydrogen partial pressure was found to be significant for reactions occurring above 400 degrees C. The selectivity for total carbon conversion to oil was shown to be high, however this value was dependent on the reaction temperature and reaction time. A characterization comparison between a pyrolysis oil produced by Dravo Engineers, Inc. and the oil produced from a run performed at 440 C for 10 minutes demonstrated that the oils were remarkably similar in their chemical make-up.