Biomass material is pyrolyzed in the absence of air, O2, H2, and solvent (e.g., H2O) at 500° C. or above in a reactor containing (i) a catalyst which as charged is a rehydrated calcined calcium-containing layered dihydroxide comprised of particles having an average particle size in the range of about 40 to about 400 microns (preferably in the range of about 50 to about 150 microns), which optionally is in a pre-agglomerized form, and (ii) a particulate fluidizable heat transfer medium, preferably sand; and condensing and isolating pyrolysis oil produced and collecting and isolating non-condensable gases separately from the condensed isolated liquid pyrolysis oil product. Pyrolysis oil obtained directly from the pyrolysis has a total acid number less than 70 mg/KOH/g; and a weight percentage of O2 removal of 72 wt % or more as determined by a described test procedure and as calculated using an expression given in the text.