Dioxin concentrations and congener distribution in biomass ash from small to large scale biomass combustion plants.

Biomass plays a pivotal role in global energy production, with a significant share allocated for industrial heat and power generation. The combustion of biomass generates biomass ash, which is widely utilized as a fertiliser. However, concerns arise regarding the presence of dioxins in biomass ash, which may limit its continued use. Dioxins are toxic compounds listed under the Stockholm Convention due to their persistence and detrimental effects on human health and the environment. This study investigates the dioxin content in biomass ashes produced in various combustion plants with a capacity of 1-50MWth in Estonia, where biomass is widely used for heating and power production. The research encompassed samples from nine biomass combustion plants with varying technical parameters considering both bottom and fly ash. Dioxin concentrations were determined for 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), and 12 dioxin-like PCBs (PCBs). The results indicate that dioxin TEQ content in all samples was well below the European Union's (EU) POP Regulation limit of 5 µg TEQ/kg, with most values being at least tenfold lower. However, some samples failed to meet the EU Fertilising Products Regulation's threshold of 20 ng TEQ/kg. Notably, fly ash exhibited higher dioxin concentrations than bottom ash. While PCBs were in significant concentrations, PCDDs dominated the overall dioxin TEQ content. This study provides essential insights into the dioxin content in biomass ash and its correlation with current EU regulatory limits. It also highlights the complex distribution of dioxin congeners, particularly PCBs, within biomass ash, emphasizing the continued research's importance.

Ecotoxicity assessment of ashes from calcium-rich fuel combustion: contrasting results and regulatory implications.

The European Union's (EU) regulation for the waste classification based on their ecotoxicological hazard (hazardous property HP14) came into force on 5 July 2018. The regulation advocates the utilisation of computational formulae for the hazard classification of waste associated with hazardous property HP14. Concurrently, ecotoxicological testing remains an alternative. To date, the absence of a consensus regarding test organisms and methodologies has vested EU member states with autonomy in determining the approach for conducting ecotoxicity assessments. The discussions on waste classification are also ongoing globally, namely the discussions under the Basel Convention. This paper endeavours to elucidate whether the widely employed test organisms, Daphnia magna and Aliivibrio fischeri, may serve as suitable indicators for the evaluation of the ecotoxicity of waste. The research is grounded in the examination of ashes derived from a combustion process of calcium-rich fuel. Ecotoxicity testing was conducted on 14 ash samples with a liquid-to-solid ratio of 10:1. The results of the Aliivibrio fischeri testing indicated that all 14 ash samples were non-hazardous in terms of their ecotoxicity. However, the results of the Daphnia magna testing showed the opposite, suggesting that the ash samples may have the potential to be ecotoxic. This study offers valuable insights into ecotoxicity assessment and waste classification, emphasising the need for scientific rigour and comprehensive understanding before making regulatory decisions. It also situates its findings within the broader global context of waste management discussions, particularly those related to international agreements like the Basel Convention.

Co-gasification of biomass and oil shale under CO2 atmosphere: Comparative analysis of fixed-bed reactor, gas chromatography and thermogravimetric analysis coupled with mass spectroscopy (TGA-MS).

Co-gasification of biomass with oil shale offers potential for integrating renewable and fossil energy sources, reducing reliance on fossil fuels. Biomass (pine and birch wood and bark) and oil shale blends (10-30 wt%) were gasified under CO2 conditions using thermogravimetric analysis coupled with mass spectrometry (TGA-MS), fixed-bed reactor, and gas chromatography. Results revealed an interaction between oil shale and biomass, enhancing CO and CH4 concentrations in the producer gas. Bark samples demonstrated higher CO concentrations compared to wood samples, particularly in pine, with 16.1 vol% and 5.4 vol%, respectively. While birch wood showed increased H2 evaporation in TGA-MS experiments, oil shale's impact on H2 concentration was inhibitive, as shown by quantitative analysis. Pine bark, with a threefold catalytic index compared to other biomass samples, demonstrated the highest total gas concentrations (19.2 vol%). Interestingly, pine bark char blends exhibited the lowest surface areas (up to 434 m2/g) among the tested samples.

Preparation and characterization of lignin-derived carbon aerogels.

Lignin is considered a valuable renewable resource for building new chemicals and materials, particularly resins and polymers. The aromatic nature of lignin suggests a synthetic route for synthesizing organic aerogels (AGs) similar to the aqueous polycondensation of resorcinol with formaldehyde (FA). The structure and reactivity of lignin largely depend on the severity of the isolation method used, which challenges the development of new organic and carbon materials. Resorcinol aerogels are considered a source of porous carbon material, while lignin-based aerogels also possess great potential for the development of carbon materials, having a high carbon yield with a high specific surface area and microporosity. In the present study, the birch hydrolysis lignin and organosolv lignin extracted from pine were used to prepare AGs with formaldehyde, with the addition of 5-methylresorcinol in the range of 75%-25%, yielding monolithic mesoporous aerogels with a relatively high specific surface area of up to 343.4 m2/g. The obtained lignin-based AGs were further used as raw materials for the preparation of porous carbon aerogels (CAs) under well-controlled pyrolysis conditions with the morphology, especially porosity and the specific surface area, being dependent on the origin of lignin and its content in the starting material.

A Predictive Approach towards Using PC-SAFT for Modeling the Properties of Shale Oil.

Equations of state are powerful tools for modeling thermophysical properties; however, so far, these have not been developed for shale oil due to a lack of experimental data. Recently, new experimental data were published on the properties of Kukersite shale oil, and here we present a method for modeling the properties of the gasoline fraction of shale oil using the PC-SAFT equation of state. First, using measured property data, correlations were developed to estimate the composition of narrow-boiling-range Kukersite shale gasoline samples based on the boiling point and density. These correlations, along with several PC-SAFT equations of the states of various classes of compounds, were used to predict the PC-SAFT parameters of aromatic compounds present in unconventional oil-containing oxygen compounds with average boiling points up to 180 °C. Developed PC-SAFT equations of state were applied to calculate the temperature-dependent properties (vapor pressure and density) of shale gasoline. The root mean square percentage error of the residuals was 13.2%. The average absolute relative deviation percentages for all vapor pressure and density data were 16.9 and 1.6%, respectively. The utility of this model was shown by predicting the vapor pressure of various portions of the shale gasoline. The validity of this model could be assessed for oil fractions from different deposits. However, the procedure used here to model shale oil gasoline could also be used as an example to derive and develop similar models for oil samples with different origins.

Comparison of the most likely low-emission electricity production systems in Estonia.

To meet targets for reducing greenhouse gas emissions, many countries, including Estonia, must transition to low-emission electricity sources. Based on current circumstances, the most likely options in Estonia are renewables with energy storage, oil shale power plants with carbon capture and storage (CCS), or the combination of renewables and either oil shale or nuclear power plants. Here we compare these different scenarios to help determine which would be the most promising based on current information. For the comparison we performed simulations to assess how various systems meet the electricity demand in Estonia and at what cost. Based on our simulation results and literature data, combining wind turbines with thermal power plants would provide grid stability at a more affordable cost. Using nuclear power to compliment wind turbines would lead to an overall levelized cost of electricity (LCOE) in the range of 68 to 150 EUR/MWh (median of 103 EUR/MWh). Using oil shale power plants with CCS would give a cost between 91 and 163 EUR/MWh (median of 118 EUR/MWh). By comparison, using only renewables and energy storage would have an LCOE of 106 to 241 EUR/MWh (median of 153 EUR/MWh).

Design of High Volume CFBC Fly Ash Based Calcium Sulphoaluminate Type Binder in Mixtures with Ordinary Portland Cement.

Growing concerns on global industrial greenhouse gas emissions have boosted research for developing alternative, less CO2 intensive binders for partial to complete replacement of ordinary Portland cement (OPC) clinker. Unlike slag and pozzolanic siliceous low-Ca class F fly ashes, the Ca- and S-rich class C ashes, particularly these formed in circulating fluidised bed combustion (CFBC) boilers, are typically not considered as viable cementitious materials for blending with or substituting the OPC. We studied the physical, chemical-mineralogical characteristics of the mechanically activated Ca-rich CFBC fly ash pastes and mortars with high volume OPC substitution rates to find potential alternatives for OPC in building materials and composites. Our findings indicate that compressive strength of pastes and mortars made with partial to complete replacement of the mechanically activated CFBC ash to OPC is comparable to OPC concrete, showing compared to OPC pastes reduction in compressive strength only by <10% at 50% and <20% at 75% replacement rates. Our results show that mechanically activated Ca-rich CFBC fly ash can be successfully used as an alternative CSA-cement type binder.

Mineral and Heavy Metal Composition of Oil Shale Ash from Oxyfuel Combustion.

Oxyfuel combustion can reduce CO2 emissions from fossil fuels. Hence, it is currently being investigated for potential use in oil shale-fired power plants, which currently produce most of Estonia's electricity. Here, experiments were performed with kukersite oil shale for both oxyfuel and conventional combustion in a 60 kWth circulating fluidized bed combustor. In this paper, we provide data on the ash composition including mineral compositions and heavy metal concentrations. Oxyfuel conditions did not noticeably influence the concentrations of heavy metals in the ash but did have significantly lower amounts of free lime because of inhibition of the carbonate decomposition reactions. The results suggest that oxyfuel combustion would produce no significant problems in terms of the behavior of the ash or the fate of heavy metals contained in the ash.

Distribution of Hydroxyl Groups in Kukersite Shale Oil: Quantitative Determination Using Fourier Transform Infrared (FT-IR) Spectroscopy.

This article describes the use of Fourier transform infrared (FT-IR) spectroscopy to quantitatively measure the hydroxyl concentrations among narrow boiling shale oil cuts. Shale oil samples were from an industrial solid heat carrier retort. Reference values were measured by titration and were used to create a partial least squares regression model from FT-IR data. The model had a root mean squared error (RMSE) of 0.44 wt% OH. This method was then used to study the distribution of hydroxyl groups among more than 100 shale oil cuts, which showed that hydroxyl content increased with the average boiling point of the cut up to about 350 °C and then leveled off and decreased.