• Energy Research
• 2021-2025close

Despite many advantages of the utilization of biomass as a renewable energy source, certain bottlenecks during biomass plant operation can be identified. Transport and collection of biomass as well as non-uniform material characteristics are issues related to decreasing efficiency of logistics and fuel manipulation which can also cause economic problems with biomass collection, transport, and storage. Since biomass is an especially reactive fuel, this has raised concerns over its safe handling and utilization. Fires, and sometimes explosions, are a risk during all stages of fuel production as well as during handling and utilization of the product. This paper presents a novel method for assessing ignition risk and provides a ranking of relative risk of ignition of biomass fuels. Tests within this method include physical and chemical properties of biomass, thermal analysis measurements, and the calculation procedure steps which were made using characteristic temperatures from thermogravimetry recordings. The results of thermogravimetry analysis were used for determination of tangent slope of the mass loss rate curves in devolatilization zone at considered heating rates for all tested samples. Linear interpolation of the data obtained by tangent slope analysis and used heating rates may provide unique straight line for each sample in the ignition testing. Thermogravimetry index of spontaneous ignition (TGspi) is obtained for all samples based on newly established formula. By varying gradient of linear dependence of self-heating coefficient against reference temperatures, mass and heat transfer limitations for various biomasses were discussed. The proposed method is accurate as well as relatively simple and quick, enabling determination of data necessary for design and application of appropriate measures to reduce fire and explosion hazard related to operation of biomass.

Despite many advantages of the utilization of biomass as a renewable energy source, certain bottlenecks during biomass plant operation can be identified. Transport and collection of biomass as well as non-uniform material characteristics are issues related to decreasing efficiency of logistics and fuel manipulation which can also cause economic problems with biomass collection, transport, and storage. Since biomass is an especially reactive fuel, this has raised concerns over its safe handling and utilization. Fires, and sometimes explosions, are a risk during all stages of fuel production as well as during handling and utilization of the product. This paper presents a novel method for assessing ignition risk and provides a ranking of relative risk of ignition of biomass fuels. Tests within this method include physical and chemical properties of biomass, thermal analysis measurements, and the calculation procedure steps which were made using characteristic temperatures from thermogravimetry recordings. The results of thermogravimetry analysis were used for determination of tangent slope of the mass loss rate curves in devolatilization zone at considered heating rates for all tested samples. Linear interpolation of the data obtained by tangent slope analysis and used heating rates may provide unique straight line for each sample in the ignition testing. Thermogravimetry index of spontaneous ignition (TGspi) is obtained for all samples based on newly established formula. By varying gradient of linear dependence of self-heating coefficient against reference temperatures, mass and heat transfer limitations for various biomasses were discussed. The proposed method is accurate as well as relatively simple and quick, enabling determination of data necessary for design and application of appropriate measures to reduce fire and explosion hazard related to operation of biomass.

The development of carbon materials with desirable textures and new aqueous electrolytes is the key strategy to improve the performance of supercapacitors. Herein, a deep eutectic solvent (DES) was used for in situ templating of a carbon material. A carbon material was characterized (XRD, N2-physisorption, FTIR, SEM and EDS) and used as an electrode material for the first time in multivalent-based supercapacitors. In situ templating of carbon was performed using a novel DES, which serves as a precursor for carbon and for in situ generation of MgO. The generation of MgO and its roles in templating of carbon were discussed. Templating of carbon with MgO lead to an increase in surface area and a microporous texture. The obtained carbon was tested in multivalent-ion (Al3+ and Mg2+) electrolytes and compared with H2SO4. The charge-storage mechanism was investigated and elaborated. The highest specific capacitance was obtained for the Al(NO3)3 electrolyte, while the operating voltage follows the order: Mg(NO3)2 > Al(NO3)3 > H2SO4. Electrical double-layer capacitance (versus pseudocapacitance) was dominant in all investigated electrolytes. The larger operating voltage in multivalent electrolytes is a consequence of the lower fraction of free water, which suppresses hydrogen evolution (when compared with H2SO4). The GCD was experimentally performed on the Al(NO3)3 electrolyte, which showed good cyclic stability, with an energy density of 22.3 Wh kg−1 at 65 W kg−1.

The development of carbon materials with desirable textures and new aqueous electrolytes is the key strategy to improve the performance of supercapacitors. Herein, a deep eutectic solvent (DES) was used for in situ templating of a carbon material. A carbon material was characterized (XRD, N2-physisorption, FTIR, SEM and EDS) and used as an electrode material for the first time in multivalent-based supercapacitors. In situ templating of carbon was performed using a novel DES, which serves as a precursor for carbon and for in situ generation of MgO. The generation of MgO and its roles in templating of carbon were discussed. Templating of carbon with MgO lead to an increase in surface area and a microporous texture. The obtained carbon was tested in multivalent-ion (Al3+ and Mg2+) electrolytes and compared with H2SO4. The charge-storage mechanism was investigated and elaborated. The highest specific capacitance was obtained for the Al(NO3)3 electrolyte, while the operating voltage follows the order: Mg(NO3)2 > Al(NO3)3 > H2SO4. Electrical double-layer capacitance (versus pseudocapacitance) was dominant in all investigated electrolytes. The larger operating voltage in multivalent electrolytes is a consequence of the lower fraction of free water, which suppresses hydrogen evolution (when compared with H2SO4). The GCD was experimentally performed on the Al(NO3)3 electrolyte, which showed good cyclic stability, with an energy density of 22.3 Wh kg−1 at 65 W kg−1.

This study aims to investigate the slow pyrolysis behavior of uncontaminated (MSC-I - reference) and heavy metals contaminated (MSC-R) samples with heavy metals from the tailings of a Pb-Zn-Cu flotation mine, consisting of whole stems of Miscanthus. Physicochemical properties of raw materials were investigated through instrumental characterization techniques (Atomic Absorption Spectrometry (AAS), Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, and X-ray diffraction (XRD)), while the pyrolysis process was monitored by simultaneous thermal analysis techniques (thermogravimetry (TG) – derivative thermogravimetry (DTG)), coupled with Mass spectrometry (MS), for evolved gas analysis. After determination of the lignocellulose content (cellulose, hemicellulose, and lignin) and extractive of the MSC-I and MSC-R samples, it was found that Pb, Zn, Fe, and Mn in MSC-R lead to very fast decomposition of extractive fraction, which facilitates their distribution in formed bio-char, together with lignin char-participation, acting catalytically. It was established that a much greater fraction of extractives decomposition products and non-volatile heavy metals are incorporated in MSC-R bio-char increasing its yield (23 %), compared to MSC-I bio-char yield (21.5 %). It was identified that MSC-R has increased production of H2, CO, and CO2, while decreased production of CH4, influenced by Fe (Fe has a significant positive effect on CO2 evaluation during MSC-R pyrolysis, enhancing decarboxylation process). It was established that CH4 reforming reactions catalyzed by iron additionally affect methane reduction, and increase production of H2, compared to the reference sample. Isoconversional kinetic analysis showed that pyrolysis reactions profile was strongly conditioned by the presence of heavy metals, such as Cd, Pb, and Zn, because they affect the modification of biomass lignocellulosic structure. Also, it was found that small amounts of Cd present in MSC-R can increase pyrolysis activation energy of three pseudo-components, and inhibit their deoxygenation, thus increasing yield of bio-char.

This study aims to investigate the slow pyrolysis behavior of uncontaminated (MSC-I - reference) and heavy metals contaminated (MSC-R) samples with heavy metals from the tailings of a Pb-Zn-Cu flotation mine, consisting of whole stems of Miscanthus. Physicochemical properties of raw materials were investigated through instrumental characterization techniques (Atomic Absorption Spectrometry (AAS), Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, and X-ray diffraction (XRD)), while the pyrolysis process was monitored by simultaneous thermal analysis techniques (thermogravimetry (TG) – derivative thermogravimetry (DTG)), coupled with Mass spectrometry (MS), for evolved gas analysis. After determination of the lignocellulose content (cellulose, hemicellulose, and lignin) and extractive of the MSC-I and MSC-R samples, it was found that Pb, Zn, Fe, and Mn in MSC-R lead to very fast decomposition of extractive fraction, which facilitates their distribution in formed bio-char, together with lignin char-participation, acting catalytically. It was established that a much greater fraction of extractives decomposition products and non-volatile heavy metals are incorporated in MSC-R bio-char increasing its yield (23 %), compared to MSC-I bio-char yield (21.5 %). It was identified that MSC-R has increased production of H2, CO, and CO2, while decreased production of CH4, influenced by Fe (Fe has a significant positive effect on CO2 evaluation during MSC-R pyrolysis, enhancing decarboxylation process). It was established that CH4 reforming reactions catalyzed by iron additionally affect methane reduction, and increase production of H2, compared to the reference sample. Isoconversional kinetic analysis showed that pyrolysis reactions profile was strongly conditioned by the presence of heavy metals, such as Cd, Pb, and Zn, because they affect the modification of biomass lignocellulosic structure. Also, it was found that small amounts of Cd present in MSC-R can increase pyrolysis activation energy of three pseudo-components, and inhibit their deoxygenation, thus increasing yield of bio-char.

The preliminary thermogravimetric studies of co-pyrolyzed low rank coals (lignites Kostolac and Kolubara) with waste materials (spent coffee ground and waste rubber granulate) in a form of blends have been performed. Thermal analysis measurements of blend samples were carried out in a nitrogen, atmosphere at three different heating rates of 10, 15, and 20 K per minute. The coal-waste blends were prepared in the percentage ratios of 90:10, 80:20, and 70:30. This work analyzed the synergy analysis for considered blends shown via descriptive parameters during co-pyrolysis process. According to the performed analysis, the presence of synergistic effect was identified, where strong interactions were also observed. For lignite-spent coffee ground blends, it was found that two factors which affect the synergy effect with coal are concentration of added biomass material and the heating rate. For lignite-tire rubber granulate blends, the blending ratio take on a decisive role for positive consequences of a synergistic effect (ratios below 30% of tire rubber granulate in coals are desirable). Also, in this work the influence of micro-scale condition parameters such as heating rate (as the experimental regulatory factor) was analyzed on the magnitude response of synergism during co-pyrolysis.