Inorganic Chemistry during Pyrolysis, Gasification, and Oxyfuel Combustion of Kraft Pulping Black Liquor

Changed utilization of black liquor in the pulp and paper industry has the potential to offer simplified carbon capture and, thus, negative net emissions from these large point sources. This can be achieved either by adapting existing recovery boilers to oxyfuel combustion or by replacing them with black liquor gasification technology. In this work, the chemistry during black liquor conversion was therefore studied in detail under different atmospheres relevant for pyrolysis, gasification, and oxyfuel combustion. Experiments were performed using environmental scanning transmission electron microscopy (ESTEM) and thermogravimetric analysis (TGA), supported with thermodynamic equilibrium calculations (TECs) to understand and interpret the results. Black liquor conversion was found to be generally similar in air and oxyfuel atmospheres containing approximately 20–25 mol % oxygen. The results however indicated that there was a higher probability of forming carbonates in the melt at higher carbon dioxide (CO₂) partial pressures, which in addition was found to be associated with potentially higher sulfur loss during black liquor conversion. Both of these characteristics can negatively affect the chemical recycling at the pulp mill by increasing the need for lime and makeup chemicals.