METHOD FOR DETERMINING THE KINETICS OF CRACKING AND COKING OF SHALE OIL VAPORS IN FLUIDIZED-BEDS

The secondary cracking and coking of oil vapours produced from oil shale retorting have been previously shown to depend upon the nature and temperature of the substrate over which these reactions occur. To realistically examine the kinetics of these reactions during fluidized bed retorting, an apparatus has been developed which permits shale oil vapours generated in one fluidized bed to pass over selected substrates in a second fluidized bed. Substrates can be fed as a batch or continuously. In the batch mode, the substrate is heated to reaction temperature and is then exposed to shale oil vapours for a chosen period of time. Carbon deposition onto the solid is monitored in real-time by combusting the pyrolysis products and measuring the oxides of combustion with an on-line mass spectrometer. The extent of carbon uptake is also determined by elemental analysis of the substrate following reaction. These two methods of analysis were shown to correspond well under all the conditions investigated. In the continuous mode, substantial amounts of product oil can be collected so the effects of cracking may be evaluated. The rates of carbon deposition onto processed shales and pure minerals have been measured.