Kinetic study of bitumen release from heated shale

Physics

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Scientific paper

With rising temperature shales evolve hydrocarbons discontinuously. At low temperatures, bitumens are thermally distilled (Peak 1) while at higher temperatures kerogen is pyrolyzed to lower molecular weight products (Peak 2). Hydrocarbon release occurring between these two peaks is less well understood. We have studied the kinetics of thermal bitumen release (Peak 1) from samples of the Excello and Woodford Shales and find that they are second order with activation energies of 19,000 cals/mole and 17,048 cals/ mole, respectively. The thermal release of nC 26 adsorbed on a siliceous support also followed second order kinetics. Activation energies, along with the determined Arrhenius A factor, permits the calculation of Peak 1 shape so that its contribution can be subtracted from the total hydrocarbon release. The residual curve shows two smaller peaks between the bitumen and kerogen peaks. These are tentatively assigned to adsorption on the mineral matrix and adsorption on kerogen. An important consequence of second order kinetics is that the temperature for the Peak 1 maximum varies with the amount of bitumen in the rock.

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