Each year, combustion at municipal solid waste incineration (MSWI) plants produces millions of tons of fly ash globally. This ash is characterized as a hazardous material and is mostly placed in landfills after a stabilization process or stored in hazardous waste sites. Thus, disposal of fly ash leaves a considerable social and environmental footprint and leads to high waste management costs. Thermochemical energy storage (TCES) systems are considered to be outstanding because of their high-energy density and near-zero energy loss over long periods of time. Calcium oxide (CaO), a main MSWI fly ash component, is a promising candidate for TCES. In this study, we investigate the potential of fly ash as a TCES material. To do so, we analyzed representative samples from different MSWIs using simultaneous thermal analysis (STA) under N2, CO2, and CO2/H2O atmospheres. These analyses were supported by additional techniques such as X-ray fluorescence (XRF) spectroscopy, inductively coupled plasma-optical emission spectroscopy (ICP-OES), and scanning electron microscopy (SEM). The STA results illustrate fly ash reactivity under different atmospheres. All samples could store heat through endothermic reactions and one sample was able to release stored heat under selected operating conditions. XRF analysis verified an average fly ash composition of 27% CaO, ICP-OES analysis demonstrated the presence of different heavy metals, and SEM analysis revealed the sintering and agglomeration of fly ash particles at high temperatures (1150 °C). This study shows that the use of fly ash as a TCES material is promising and that further investigation in the field is needed to corroborate this application.
Due to its high potential for thermal energy storage systems (Huber, Setoodeh Jahromy, Jordan, et al, Energies. 2019;12:17) the decomposition of boric acid is of particular interest in the field of applied research. The complexity of the reaction mechanism, with its multiple partial‐overlapping reaction steps, hitherto prevented a clear identification and analysis of each stoichiometric reaction step. So far, various research teams performed different kinetic analyses of boric acid, which led to various reaction mechanisms and stoichiometric reaction steps with yet inconclusive results for process modeling. Thus, a deeper examination of the process was desirable, to validate whether a proposed reaction is reasonable or not. For this purpose, experimental data were used for a deconvolution of the reaction sequence, using the Fraser‐Suzuki function, which clearly revealed the respective single reactions. The results of the deconvolution were compared with the proposed reaction steps in consideration of the stoichiometric ratio and thereby illustrated that the decomposition of polycrystalline boric acid more likely consists of three reaction steps. In contrary to the two‐step mechanism, the three‐step mechanism showed a very good correlation (r > 99%). Based on these outcomes, kinetic analyses were performed for each reaction step, by means of the nonparametric kinetics 2 (NPK2) method with subsequent determination of kinetic parameters. Additionally, for a deeper insight into the reaction, analyzing techniques like X‐ray diffraction (XRD), scanning electron microscopy (SEM) and simultaneous thermal analysis (STA) were applied.
This study aims to investigate the physical and chemical characterization of six fly ash samples obtained from different municipal solid waste incinerators (MSWIs), namely grate furnaces, rotary kiln, and fluidized bed reactor, to determine their potential for CO2 and thermochemical energy storage (TCES). Representative samples were characterized via simultaneous thermal analysis (STA) in different atmospheres, i.e., N2, air, H2O, CO2, and H2O/CO2, to identify fly ash samples that can meet the minimum requirements, i.e., charging, discharging, and cycling stability, for its consideration as TCES and CO2-storage materials and to determine their energy contents. Furthermore, other techniques, such as inductively coupled plasma optical emission spectroscopy, X-ray fluorescence (XRF) spectrometry, X-ray diffraction (XRD), scanning electron microscopy, leachability tests, specific surface area measurement based on the Brunauer–Emmett–Teller method, and particle-size distribution measurement, were performed. XRF analysis showed that calcium oxide is one of the main components in fly ash, which is a potentially suitable component for TCES systems. XRD results revealed information regarding the crystal structure and phases of various elements, including that of Ca. The STA measurements showed that the samples can store thermal heat with energy contents of 50–394 kJ/kg (charging step). For one fly ash sample obtained from a grate furnace, the release of the stored thermal heat under the selected experimental conditions (discharging step) was demonstrated. The cycling stability tests were conducted thrice, and they were successful for the selected sample. One fly ash sample could store CO2 with a storage capacity of 27 kg CO2/ton based on results obtained under the selected experimental conditions in STA. Samples from rotary kiln and fluidized bed were heated up to 1150 °C in an N2 atmosphere, resulting in complete melting of samples in crucibles; however, other samples obtained from grate furnaces formed compacted powders after undergoing the same thermal treatment in STA. Samples from different grate furnaces showed similarities in their chemical and physical characterization. The leachability test according to the standard (EN 12457-4 (2002)) using water in a ratio of 10 L/S and showed that the leachate of heavy metals is below the maximum permissible values for nonhazardous materials (except for Pb), excluding the fly ash sample obtained using fluidized bed technology. The leachate contents of Cd and Mn in the fly ash samples obtained from the rotary kiln were higher than those in other samples. Characterization performed herein helped in determining the suitable fly ash samples that can be considered as potential CO2-storage and TCES materials.
This paper aims to describe the capability of the system boric acid–boron oxide for thermochemical energy storage. As part of the systematic research and in-depth analysis of potential solid/gas reaction systems, performed during the last years, this reaction system appears to be highly promising for the future of worldwide sustainable energy supply. The analysis of the reaction heat, by means of thermogravimetric and macroscopic investigations, not only showed a significantly higher energy density of 2.2 GJ/m3, compared to sensible- and latent energy storages, but the reaction kinetic further demonstrated the reactions’ suitability to store energy from renewable energy and waste heat sources. This paper, therefore, shows a new approach regarding the application of the boric acid–boron oxide reaction system and elaborates on the advantages and challenges for its use as energy storage.
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