Long-term mineral transformation of Ca-rich oil shale ash waste

Power generation and other industries using solid fossil fuels like coal, lignite, oil shale and peat are responsible for producing large quantities of solid residues that are often chemically reactive and/or unstable and are disposed in holding ponds and deposition sites. Stability and long-term behaviour of such deposits are typically studied in short-term laboratory experiments that cannot describe nor predict long-term changes taking place in these materials. Here, we study long-term (>40 years) transformations, in highly alkaline conditions, of the Ca-rich ash deposit in Estonia composed of oil shale processing residues from the Eesti power plant. Detailed mineralogical, chemical and micromorphological analyses using X-ray diffraction, X-ray fluorescence, 29Si nuclear magnetic resonance, scanning electron microscopy and other methods were applied in order to identify the composition of the waste with a focus on formation and transformation of semicrystalline phases in the deposit. The results show progressive formation of calcium-silicate-hydrate (C-S-H) type phase at the expense of silicate minerals and amorphous glass phases with increasing depth and age of the sediments, from about 25% in the upper part of the depository to over 60% in the oldest-deepest part. This demonstrates that over time the high alkalinity of the ash is responsible for initiating natural alkali-activation. The formation of C-S-H-type phases increases the mechanical strength of the sediment and ensures long-term stability of waste deposits. These findings may encourage the use of these ashes in binder or other construction material production or as construction aggregates

Ash and Flue Gas from Oil Shale Oxy-Fuel Circulating Fluidized Bed Combustion

Carbon dioxide emissions are considered a major environmental threat. To enable power production from carbon-containing fuels, carbon capture is required. Oxy-fuel combustion technology facilitates carbon capture by increasing the carbon dioxide concentration in flue gas. This study reports the results of calcium rich oil shale combustion in a 60 kWth circulating fluidized bed (CFB) combustor. The focus was on the composition of the formed flue gas and ash during air and oxy-fuel combustion. The fuel was typical Estonian oil shale characterized by high volatile and ash contents. No additional bed material was used in the CFB; the formed ash was enough for the purpose. Two modes of oxy-fuel combustion were investigated and compared with combustion in air. When N2 in the oxidizer was replaced with CO2, the CFB temperatures decreased by up to 100 °C. When oil shale was fired in the CFB with increased O2 content in CO2, the temperatures in the furnace were similar to combustion in air. In air mode, the emissions of SO2 and NOx were low (<14 and 141 mg/Nm3 @ 6% O2, respectively). Pollutant concentrations in the flue gas during oxy-fuel operations remained low (for OXY30 SO2 < 14 and NOx 130 mg/Nm3 @ 6% O2 and for OXY21 SO2 23 and NOx 156 mg/Nm3 @ 6% O2). Analyses of the collected ash samples showed a decreased extent of carbonate minerals decomposition during both oxy-fuel experiments. This results in decreased carbon dioxide emissions. The outcomes show that oxy-fuel CFB combustion of the oil shale ensures sulfur binding and decreases CO2 production