Impact of solid fuel combustion technology on valence speciation of chromium in fly ash

• Biomass and high combustion temperature favor enrichment of fly ash with Cr(VI).
• Biomass combustion favor enrichment of fly ash with water soluble Cr(VI).
• Alkali compounds and Fe oxides play a key role in shaping Cr(VI/III) speciation.
• Cr(VI) level in coal fly ash drops in order: PCC boiler ≫ FBC boiler ≈ SF boiler.
• An influence of combustion technologies on Cr speciation in fly ash was explained.

Fly ash (FA) generated in real furnaces was used to evaluate the impact of the kind of the solid fuel burnt and combustion technology on chromium speciation, particularly the presence of Cr(III) and Cr(VI) forms as well as readily and hardly leachable chromium(VI) species in FAs. The FAs originated from a pulverized coal combustion boiler (PCC boiler), a fluidized bed combustion boiler (FBC boiler), a stoker-fired boiler (SF boiler), a municipal solid waste incinerator (MSWI), a cement rotary kiln (CRK) and a modern domestic boiler (DB). The speciation analysis of chromium was carried out by means of extraction followed by catalytic cathodic stripping voltammetry with adsorption of Cr(III)-DTPA complexes (CCSV-DTPA) for determination of Cr(VI) and AAS was used for determination of Cr content.It has been revealed that the antagonistic action of alkali metal compounds and iron oxides plays a crucial role in shaping valence speciation of chromium. According to the proposed transformation path of oxidation of Cr(III) to Cr(VI), hard coal combustion in an SF boiler, an FBC boiler or a domestic boiler will generate FAs with a low Cr(VI) level. Replacing fuel with biomass should create favorable conditions for generating FA enriched with Cr(VI). Relatively high concentrations of Cr(VI) can also be expected in FA generated in the process of high-temperature combustion of coal in PCC boilers.