OIL SHALE ASH UTILIZATION IN INDUSTRIAL PROCESSES AS AN ALTERNATIVE RAW MATERIAL

Abstract: Oil shale is a fine-grained sedimentary rock with the potential to yield significant amounts of oil and combustible gas when retorted. Oil shale deposits have been found on almost every continent, but only Estonia, who has the 8th largest oil shale deposit in the world has continuously utilized oil shale in large scale operations. Worldwide, Estonia accounts for 80% of the overall activity involving oil shale, consuming approximately 18 million tons while producing 5–7 million tons of oil shale ash (OSA) annually. Since the amounts are quite significant, Estonia has made the choice to store OSA outdoors as ash heaps, which currently average a height of 45m and overall cover an area of approximately 20 km2. Oil shale is primarily composed of organic matter (15%–55%), low–magnesium calcite (>50%), dolomite (<10%–15%), and siliciclastic minerals (<10–15%). When oil shale is combusted in thermal power plants (TPP), temperatures as high as 1500˚C are reached; calcining CaCO3 into CaO in the process. It is the high CaO content (30%–50%; Free CaO 8%–23%) along with trace elements that makes OSA a threat to the environment; it is mainly the CaO and to a lesser degree the trace elements found in OSA that are exploited in this thesis. Currently, only about 5% of the 5–7 million tons of OSA produced annually is being utilized as an alternative raw material, mostly in the construction industry for the production of Portland cement. Multiple studies have been conducted on OSA in the past by various institutions in an attempt to increase its use in industry and reduce the negative environmental effects of storing large quantities of the highly alkaline material. This thesis primarily focuses on the treatment of acid mine drainage (AMD) and the production of precipitated calcium carbonate (PCC) using OSA. In Sweden, CaO is utilized in treating AMD in historical mine sites and in the production of PCC used in the paper industry. Oil shale ash has the potential to become a substitute for lime (CaO) utilized in various industries while Estonia transitions into renewable energy. The mining industry has been abundant in Sweden for hundreds of years, but the poor mining techniques of the past have led to a significant number of mines that require immediate AMD remediation. The Swedish EPA has declared that 600 mines currently need attention, which may cost approximately 2–3 billion SEK (232–350 million USD). 1:200, 1:500, and 1:1000. All ratios yielded a pH greater than 10, most likely inducing the formation and precipitation of secondary minerals such as Schwertmannite and Ferrihydrite. The reduction of metallic cations such as Cu (maximum reduction 99.9%), Pb (99.8%), V (95.5%), Cd (99.9%), As (88.7%), and Ni (99.9%) from AMD waters was observed. The previously mentioned metallic cations most likely adsorbed and co-precipitated to the negatively charged surfaces of Schwertmannite and Ferrihydrite minerals. Metals such as Ba, Cr, and Sb were observed to leach out of OSA, increasing their concentrations in the treated AMD waters, but still within Swedish regulatory limits. Acid mine drainage treatment with OSA significantly reduces heavy metal concentrations; transforming the polluted waters from hazardous to non-hazardous waste (below Swedish leaching limit values). Precipitated calcium carbonate is utilized in many industries, such as in the production of paper, sealants and adhesives, paint, food, and pharmaceuticals. In Sweden, it is common for paper producers to have satellite PCC plants in close proximity so that CO2 (from the paper facility) is used in the carbonation of Ca(OH)2 to form PCC. The CaO in OSA may be mixed with H2O to form the required Ca(OH)2 for PCC production. Potentially replacing raw CaO currently purchased for the production of PCC. The conducted PCC production experiments directly carbonized vacuum filtered OSA leachate with a steady flow of CO2 gas to yield PCC. Precipitate obtained yielded 94%–99% of CaCO3 theoretical values. Throughout the carbonation process; OSA leachate’s pH began >12 and continuously decreased with time, maximum PCC production occurred at pH 9–10, and stabilized at pH 8. Although, the polymorphism and purity of the PCC is not known, the conducted experiments and previous studies on the topic indicate the feasibility of producing high quality PCC from OSA to be used in industry. Additionally, oil shale thermal power plants have the potential to produce PCC and other minerals by injecting flue gases into the highly alkaline (Ca(OH)2) water used to hydraulically transport OSA from the furnaces to ash heaps; reducing or seizing the production of alkaline leachates and emission of gases that currently contaminate the environment. Other applications for OSA were also investigated and reviewed, such as the lucrative extraction and refinement of rare earth elements. Estonian oil shale ash was tested for Ce, Nd, Y and Sc using ICP-MS and compared to Chinese OSA and selected European REE ores. Estonian OSA had the lowest concentrations of REEs in the comparison, nevertheless, previous studies have shown up to 80%-90% REE recovery via an acid leaching process. Rare earth recovery from OSA may be successful in the future if a practical and cost-effective method is developed. Reducing Europe’s dependence on China for REE.