The
effects of feedstock type and biomass conversion conditions
on the speciation of sulfur in biochars are not well-known. In this
study, the sulfur content and speciation in biochars generated from
pyrolysis and gasification of oak and corn stover were determined.
We found the primary determinant of the total sulfur content of biomass
to be the feedstock from which the biochar is generated, with oak
and corn stover biochars containing 160 and 600–800 ppm sulfur,
respectively. In contrast, for sulfur speciation, we found the primary
determinant to be the temperature combined with the thermochemical
conversion method. The speciation of sulfur in biochars was determined
using X-ray absorption near-edge structure (XANES), ASTM method D2492,
and scanning electron microscopy–energy-dispersive spectroscopy
(SEM–EDS). Biochars produced under pyrolysis conditions at
500–600 °C contain sulfate, organosulfur, and sulfide.
In some cases, the sulfate contents are up to 77–100%. Biochars
produced in gasification conditions at 850 °C contain 73–100%
organosulfur. The increase of the organosulfur content as the temperature
of biochar production increases suggests a similar sulfur transformation
mechanism as that in coal, where inorganic sulfur reacts with hydrocarbon
and/or H2 to form organosulfur when the coal is heated.
EDS mapping of a biochar produced from corn stover pyrolysis shows
individual sulfur-containing mineral particles in addition to the
sulfur that is distributed throughout the organic matrix.