New Albany shale flash pyrolysis under hot-recycled-solid conditions: Chemistry and kinetics, II

摘要

The authors are continuing a study of recycle retorting of eastern and western oil shales using burnt shale as the solid heat carrier. Stripping of adsorbed oil from solid surfaces rather than the primary pyrolysis of kerogen apparently controls the release rate of the last 10--20% of hydrocarbons. Thus, the desorption rate defines the time necessary for oil recovery from a retort and sets the minimum hold-time in the pyrolyzer. A fluidized-bed oil shale retort resembles a fluidized-bed cat cracker in this respect. Recycled burnt shale cokes oil and reduces yield. The kerogen H/C ratio sets an upper limit on yield improvements unless external hydrogen donors are introduced. Steam can react with iron compounds to add to the H-donor pool. Increased oil yield when New Albany Shale pyrolyzes under hot-recycled-solid, steam-fluidization conditions has been confirmed and compared with steam retorting of acid-leached Colorado oil shale. In addition, with retorted, but unburnt, Devonian shale present at a recycle ratio of 3, the authors obtain 50% more oil-plus-gas than with burnt shale present. Procedures to make burnt shale more like unburnt shale can realize some increase in oil yield at high recycle ratios. Reduction with H(sub 2) and carbon deposition are possibilities that the authors have tested in the laboratory and can test in the pilot retort. Also, eastern spent shale burned at a high temperature (775 C, for example) cokes less oil than does spent shale burned at a low temperature (475 C). Changes in surface area with burn temperature contribute to this effect. 15 refs., 8 figs., 4 tabs.