Riho Mõtlep

Phosphorus removal using Ca-rich hydrated oil shale ash as filter material--the effect of different phosphorus loadings and wastewater compositions.

We studied the phosphorus (P) binding capacity of Ca-rich alkaline filter material - hydrated oil shale ash (i.e. hydrated ash) in two onsite pilot-scale experiments (with subsurface flow filters) in Estonia: one using pre-treated municipal wastewater with total phosphorus (TP) concentration of 0.13-17.0 mg L(-1) over a period of 6 months, another using pre-treated landfill leachate (median TP 3.4 mg L(-1)) for a total of 12 months. The results show efficient P removal (median removal of phosphates 99%) in horizontal flow (HF) filters at both sites regardless of variable concentrations of several inhibitors. The P removal efficiency of the hydrated ash increases with increasing P loading, suggesting direct precipitation of Ca-phosphate phases rather than an adsorption mechanism. Changes in the composition of the hydrated ash suggest a significant increase in P concentration in all filters (e.g. from 489.5 mg kg(-1) in initial ash to 664.9 mg kg(-1) in the HF filter after one year in operation), whereas almost all TP was removed from the inflow leachate (R(2) = 0.99). Efficiency was high throughout the experiments (median outflow from HF hydrated ash filters 0.05-0.50 mg L(-1)), and P accumulation did not show any signs of saturation.

Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments

Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years.

Reuse potential of phosphorus-rich filter materials from subsurface flow wastewater treatment filters for forest soil amendment

The aim of this study was to test P-enriched filter materials from a wastewater treatment experiment regarding their fertilizing efficiency in pot experiments with silver birch (Betula pendula Roth.) seedlings. Tested materials included hydrated calcium-rich oil shale ash and well-mineralised peat. A mixture of peat and hydrated ash demonstrated the best results: seedlings grown on that mixture had the highest P concentration and an optimal N:P:K ratio in leaves. Hydrated ash has a low concentration of heavy metals and almost the same composition as common lime fertilizers. The hydrated ash sediment and its combination with well-mineralised peat enriched with phosphorus in wastewater treatment filters are promising materials for forest soil fertilization.

Self-cementing properties of oil shale solid heat carrier retorting residue

Oil shale-type organic-rich sedimentary rocks can be pyrolysed to produce shale oil. The pyrolysis of oil shale using solid heat carrier (SHC) technology is accompanied by large amount of environmentally hazardous solid residue—black ash—which needs to be properly landfilled. Usage of oil shale is growing worldwide, and the employment of large SHC retorts increases the amount of black ash type of waste, but little is known about its physical and chemical properties. The objectives of this research were to study the composition and self-cementing properties of black ash by simulating different disposal strategies in order to find the most appropriate landfilling method. Three disposal methods were simulated in laboratory experiment: hydraulic disposal with and without grain size separation, and dry dumping of moist residue. Black ash exhibited good self-cementing properties with maximum compressive strength values of >6 MPa after 90 days. About 80% of strength was gained in 30 days. However, the coarse fraction (>125 µm) did not exhibit any cementation, thus the hydraulic disposal with grain size separation should be avoided. The study showed that self-cementing properties of black ash are governed by the hydration of secondary calcium silicates (e.g. belite), calcite and hydrocalumite.

SELF-CEMENTING PROPERTIES AND ALKALI ACTIVATION OF ENEFIT280 SOLID HEAT CARRIER RETORTING ASH

The composition and cementitious properties upon hydration and alkali activation of the solid heat carrier (SHC) ash produced in a new Enefit280 retort was studied. The Enefit280 waste heat boiler (WHB) ash is different from other SHC solid residues. It does not contain residual organics, but is characterized by a low content of reactive Ca-phases and the soluble amorphous (aluminium)-silicate phase/glass material. Cementation of Enefit280 ash upon hydration with plain water is limited and its uniaxial compressive strength stays < 4 MPa after 28 days of curing. Ash mixtures activated with sodium silicate based mixtures show higher compressive strength values, reaching > 10 MPa after 28 days of curing. The Enefit280 ash, compared to other ash types forming in the Estonian oil shale processing industry, has significantly poorer self-cementing properties. This needs to be taken into account when designing waste depositories, if other types of ash with better self-cementing properties are not co-deposited with this ash.