Sulfur makeup in an unbleached kraft pulp mill

Sodium sesquisulfate or “sesqui” (Na3H(SO4)2) is a by-product of chlorine dioxide production at kraft pulp mills. It is typically used for sodium and sulfur makeup in the liquor loop. Mondi Hinton Inc. (MHI) in Hinton, AB, Canada, was converting from bleached to unbleached kraft pulp production and was thus losing this source of makeup. The only option that was readily available as a substitute was sodium hydrosulfide (NaHS), which was cost prohibitive. Other options such as sodium sulfate (Na2SO4), emulsified sulfur, sulfuric acid (H2SO4), and sodium bisulfite (NaHSO3) were compared. The mill concluded that pelletized sulfur plus sodium hydroxide or “caustic soda” (NaOH) was the best option. Laboratory-scale experiments showed that pelletized sulfur dissolved in white liquor (WL). A mill-scale trial revealed that pelletized sulfur added to a causticizer had no adverse impacts on the downstream pressure filters or kiln operation. The sulfur reacted to produce polysulfide upstream of the WL storage tank, giving the liquor an orange hue. This polysulfide appeared to partially degrade into thiosulfate before being fed to the digester. The heavy black liquor (HBL) sulfur:sodium (S:Na) ratio did not change significantly, even though the sulfur/soda addition location was upstream of the original one. In addition, other properties such as liquor heating value and elemental analysis did not significantly change. Due to polysulfide/thiosulfate concentration in the white liquor, it was determined that the carbon steel equipment was at risk for corrosion. During the annual turnaround that occurred eight months after the addition of sulfur was started, the wash zone of the digester showed no signs of thinning/damage. The mill has been running exclusively with pelletized sulfur for 22 months (as of August 2024), realizing significant cost savings compared to the use of NaHS or other sulfur/soda addition options.