Effect of ion-exchangeable calcium on carbonaceous particulate matter formation during coal pyrolysis.

• The addition of ion-exchangeable calcium reduces the soot mass yield during coal pyrolysis. • Ion-exchangeable calcium decreases the sizes of soot primary particles and soot aggregates. • Calcium loading shrinks the disordered cores of soot, promotes the soot graphitization, and leads to more compact aggregates. • The size distributions of inorganic species show that calcium and sodium play different roles in soot formation. This work investigated the effect of ion-exchangeable calcium on the mass yield, size distribution and structural properties of carbonaceous particulate matter from coal pyrolysis. The raw, acid washed and calcium-exchanged coal samples were pyrolyzed in a flat-flame burner at 1600 K. The particulate matter was collected with a three-stage dilution sampler. Then, the particle size distributions were measured by a low pressure impactor (DLPI+) and a scan mobility particle sizer (SMPS). The results show that, with the addition of ion-exchangeable calcium, the soot yield reduces, and the size growth of soot particles is inhibited. Transmission electron microscopy (TEM) analysis shows that ion-exchangeable calcium diminishes the sizes of disordered cores in soot primary particles, accelerates the graphitization of soot and makes the soot aggregates more compact. The chemical structures derived from Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR) indicate that the graphitization degree of the soot is first enhanced and then inhibited with increasing calcium loading amount. Additionally, the inorganic species in the size-segregated soot particles were characterized. The fractions of calcium and sodium in soot show opposite trend with particle size. Unlike Na, which nucleates before soot inception, Ca tends to participate in both the soot nucleation and surface growth processes, and is enriched at larger particle size. [ABSTRACT FROM AUTHOR]