Interaction behavior of sand-diluted and mixed Fe-based oxygen carriers with potassium salts

Abstract

Oxygen carriers, in the form of metal oxide particles, are bed materials that transport oxygen in solid form in fluidized bed applications, such as in chemical-looping applications. In biofuel applications, it is well known that alkali from the fuel ash can react with the bed material and cause, among other operation issues, agglomeration. When using oxygen carriers in a fluidized bed, it is likely that the bed material is either a mixture of different metal oxide materials or partly diluted with sand. This is to improve or combine the chemical properties of the materials used or simply for economic reasons.This work investigates how three potassium salts K2CO3, K2SO4 and KH2PO4 interact with the oxygen carriers: Steel converter slag (LD slag), ilmenite, mixtures of the two and each carrier diluted with silica sand. The salts were used as model compounds that can occur in biofuel ash. The set-up used was a fixed bed where a small sample of bed material is mixed with a potassium salt equivalent to 4 wt-% of potassium. The mixture was then exposed to reducing (H2 in steam) conditions at 900 °C during several hours in a tubular furnace. This provides a worst-case scenario for solid–solid interaction in a fluidized bed. If a solid–solid reaction does not take place in this setup, it will most likely never occur in a fluidized bed.When LD slag and ilmenite were combined, the potassium from the salts would prefer to accumulate in the ilmenite rather than the LD slag. Ca from LD slag interacted with KH2PO4 resulting in a less severe agglomeration than when ilmenite was used separately with the same salt. When the oxygen carriers were diluted with silica sand, potassium salt interaction resulted in agglomeration for both the oxygen carriers with all potassium salts. K2CO3 and K2SO4 formed potassium silicates, while KH2PO4 formed a phosphorus-containing melt. When LD slag was present, phosphorus was located in a K-Ca-P phase that was not present if ilmenite was present.