Pyrolysis behavior, kinetics, and thermodynamics of waste pharmaceutical blisters under CO2 atmosphere.

The disastrous impact of COVID-19 pandemic has caused a significantly increased production and use of pharmaceutical drugs, which is accompanied by the rapid generation of waste pharmaceutical blisters (WPBs). Nonetheless, its treatment has not gained appropriate attentions and a perceptible process development was not achieved. In this study, the WPBs pyrolysis in CO2 atmosphere was conducted as well as the thermodynamics and kinetics were investigated. The thermogravimetric analysis revealed that the WPBs decomposition could be divided into two stages of 25 - 365 °C and 365 - 900 °C with mass loss of 56.5 - 60.5 wt% and 22.5 - 25.9 wt%, respectively. Fourier-transform infrared spectroscopy analysis indicated the dechlorination process initiating at ∼300 °C. The simultaneous asymmetric stretching of HCl and stretching vibration of C-Cl bond was detected in the range of 2600 - 3250 cm-1 and 660 - 750 cm-1, respectively. The dechlorination reactions were almost complete at ∼520 °C and minor peaks (2900 -3100 cm-1) due to C-H vibrations were observed. Gas chromatography-mass spectrometry analysis indicated that the evolved products included alkanes, benzene, olefin, as well as HCl. The cycloalkenes content significantly increased during the second conversion stage, implying the addition reactions between alkanes and olefins. The apparent activation energy was calculated using three model-free methods and the values from Flynn-Wall-Ozawa model increased from 142.0 to 255.8 kJ·mol-1 with an average value of 147.4 kJ·mol-1. The methods of Coats-Redfern as well as Malek were applied to determine the reaction mechanism. The one-dimensional diffusion model was more reliable to describe the WPBs pyrolysis. This study will represent a significant reference case for the thermochemical conversion of multilayer packing waste and facing the increasing demand for the medical waste recycling.

Investigation and modelling of the pyrolysis kinetics of industrial biomass wastes.

Pyrolysis of the waste organic fraction is expected to be a central element to meet the primary energy demand in future: it increases the impact of renewable energy sources on the power generation sector and allows the amount of waste to be reduced, putting an end to landfills. In the present study, kinetic studies on the pyrolysis of biomass wastes are carried out. Two kinds of industrial organic waste are investigated: brewery spent grain (BSG) and medium-density fiberboard (MDF). The main target of this work is to provide a global equation for the one-step pyrolysis reaction of the investigated materials in an argon atmosphere using isoconversional methods. The conducted analysis allowed to estimate the activation energy as 225.4-253.6 kJ/mol for BSG and 197.9-216.7 kJ/mol for MDF. For both materials nth order reaction was proposed with reaction order of 7.69-8.70 for BSG and 6.32-6.55 for MDF. The developed equation allowed to simulate the theoretical curves of thermal conversion. These curves indicated the highest conversion at the temperature of the degradation of dominant component, which was experimentally verified. By this method, a one-step kinetic model is derived, which can be applied for the reaction kinetics in the CFD modelling of, e.g., pyrolysis and gasification processes.

Corrosion Resistance of Inconel 625 CMT-Cladded Layers after Long-Term Exposure to Biomass and Waste Ashes in High-Temperature Conversion Processes.

The present study investigated the effect of corrosion on an Inconel 625-cladded layer using the cold metal transfer (CMT) method. The corrosion was caused by various ashes and high process temperatures. The ashes were obtained from the biomasses of mixed wood and oat straw, as well as from sewage sludge, by ashing. Long-term corrosion tests were carried out at 650 °C over a period of 1000 h. The chemical composition, mineral phases, and corrosion effects were studied by X-ray fluorescence (XRF), scanning electron microscopy equipped with energy-dispersive X-rays (SEM-EDX), and X-ray diffraction (XRD) from the surface and on the cross-section of the samples. The chemical composition of the ashes was quite different, but representative of their particular fuel. Together with the effects of the operating temperature and mass transfer, significant differences in the degree of the corrosion depth were detected for the various ashes. For the investigated samples, the corrosion mechanisms were inferred based on the identified corrosion products.

Surface electronic structure of [XMIm]Cl probed by surface-sensitive spectroscopy.

We apply electron spectroscopy methods with different surface sensitivities to elucidate the DOS of the surface and the near-surface region of [XMIm]Cl (X=octyl, hexyl, butyl, and ethyl alkyl chain) ionic liquids. Using metastable induced electron spectroscopy (MIES) we are able to detect the density of states in front of the outermost surface, whereas ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS) measurements provide lower surface sensitivity. The assignment of certain structures in the valence band spectra to particular atoms/functional groups of the ionic liquid based on DFT calculations and the reconstruction of PES spectra enables us to obtain information on the dominating groups at the surface, or in other words, on the molecular/ionic arrangement and orientation at the surface. From angular resolved XPS it is concluded that the alkyl chains dominate at the outermost surface. In agreement with this a decreasing chlorine signal is observed in the UPS spectra for ionic liquids with increasing alkyl chain length. The analysis of the MIES data shows that in case of [OMIm]Cl--in contrast to UPS and XPS--no Cl-induced features are visible in the MIES spectra at all and that the MIES spectra are dominated by the [OMIm](+) alkyl chain.

Theoretical reconstruction and elementwise analysis of photoelectron spectra for imidazolium-based ionic liquids.

We have recently measured core level and valence band XPS, UPS, and MIES spectra of two room temperature ionic liquids composed of bis(trifluoromethylsulfonyl)imide anions ([Tf(2)N](-)) and either 1-ethyl-3-methyl-imidazolium ([EMIm](+)) or 1-octyl-3-methyl-imidazolium cations ([OMIm](+)). [T. Ikari, A. Keppler, M. Reinmöller, W. J. D. Beenken, S. Krischok, M. Marschewski, W. Maus-Friedrichs, O. Höfft and F. Endres, e-J. Surf. Sci. Nanotechnol., 2010, 8, 241.] In the present work we analyze these spectra by means of partial density of states (pDOS) as calculated from a single ion pair of the respective ionic liquid using density functional theory (DFT). Subsequently we reconstruct the XPS and UPS spectra by considering photoemission cross sections and analyze the MIES spectra by pDOS, which provides us decisive hints to the ionic liquid surface structure.